WO2025094716A1 - Resin composition - Google Patents

Abstract

This resin composition contains a resin having at least one selected from the group consisting of repeating units represented by formula (1A) and repeating units represented by formula (2A). X₁, X₂, Y₁, and Y₂ each independently represent an organic group. W₁, W₂, W₃, and W₄ each independently represent a linking group. P₀₁, P₀₂, P₀₃, and P₀₄ each independently represent at least one organic group selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. a, b, c, and d each independently represent an integer of 0 or more. At least one of a and b represents an integer of one or more, and at least one of c and d represents an integer of one or more. m, n, p, and q each independently represent an integer of one or more. W₁, W₂, W₃, W₄, P₀₁, P₀₂, P₀₃, and P₀₄, when existing in a quantity of more than one, may each be the same or may each be different.

Description

Resin composition

The present invention relates to a resin composition.

Polyimides and polyamides are used in a variety of fields, including semiconductor devices and the aerospace industry.

Patent Document 1 describes a varnish composition containing a polyimide resin having a radically polymerizable group or a cationic polymerizable group bonded to the main chain of the polyimide resin and containing a skeleton derived from a bisphenol of a specific structure in the constituent units constituting the main chain of the polyimide resin, and an organic solvent.
Furthermore, Patent Document 2 describes a photosensitive resin composition containing a polyimide precursor having a specific structure, a photosensitizer, and a solvent.

Japanese Patent Application Publication No. 2022-73127 Japanese Patent Application Publication No. 2022-54416

One application of polyimide and polyamide is a film used in a semiconductor device (for example, an insulating film such as an interlayer insulating film for a redistribution layer).
Recently, with the increasing miniaturization and integration density of semiconductor devices, high resolution is required for resin compositions that are materials for forming films.
In addition, due to miniaturization and high integration of semiconductor devices, films are more susceptible to heat. For this reason, in order to prevent deformation (warping, distortion, generation of voids, etc.) when exposed to heat, films are required to have a small expansion coefficient when exposed to heat. In other words, there is a demand for a resin composition capable of forming a film with a small coefficient of thermal expansion (CTE).

The objective of the present invention is to provide a resin composition that can form a film with excellent resolution and a small CTE.

The following are examples of typical embodiments of the present invention.

[1]
A resin composition comprising a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (2A):

In formula (1A) and formula (2A),
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent an organic group.
W ₁ , W ₂ , W ₃ and W ₄ each independently represent a linking group.
P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
m, n, p and q each independently represent an integer of 1 or more.
When a plurality of W ₁ , W ₂ , W ₃ , W ₄ , P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ are present, they may be the same or different.
[2]
A resin composition comprising a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):

In formula (1) and formula (2),
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent an organic group.
W ₁ , W ₂ , W ₃ and W ₄ each independently represent a linking group.
_P1 , _P2 , _P3 and _P4 each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
Q ₁ , Q ₂ , Q ₃ and Q ₄ each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
m, n, p and q each independently represent an integer of 1 or more.
When a plurality of _W1 , _W2 , _W3 , _W4 , _P1 , _P2 , _P3 , _P4 , _Q1 , _Q2 , _Q3 and _Q4 are present, they may be the same or different.
[3]
At least one of P ₀₁ and P ₀₂ in the above formula (1A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group,
The resin composition according to [1], wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group.
[4]
At least one of P ₀₁ and P ₀₂ in the above formula (1A) has a branched structure,
The resin composition according to [1] or [3], wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) has a branched structure.
[5]
At least one of P ₀₁ and P ₀₂ in the above formula (1A) has at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1-PA) and repeating units represented by the following formula (2-PA),
The resin composition according to [1], [3] or [4], wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) has at least one selected from the group consisting of a repeating unit represented by the following formula (1-PA) and a repeating unit represented by the following formula (2-PA).

In formula (1-PA) and formula (2-PA),
X _1p , X _2p , Y _1p and Y _2p each independently represent an organic group.
W _1p , W _2p , W _3p and W _4p each independently represent a linking group.
P _01p , P _02p , P _03p and P _04p each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
ap, bp, cp, and dp each independently represent an integer of 0 or more, provided that at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more.
mp, np, pp and qp each independently represent an integer of 1 or more.
When a plurality of _W1p , _W2p , _W3p , _W4p , _P01p , _P02p , _P03p and _P04p are present, they may be the same or different.
[6]
The resin composition according to any one of [1] to [5], wherein the resin has at least one crosslinkable group at at least one terminal.
[7]
At least one of P ₀₁ and P ₀₂ in the above formula (1A) has a crosslinkable group,
The resin composition according to any one of [1] and [3] to [5], wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) has a crosslinkable group.
[8]
The resin composition according to [6] or [7], wherein the crosslinkable group includes at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.
[9]
At least one of P ₀₁ and P ₀₂ in the formula (1A) has a phenol group, and at least one of P ₀₃ and P ₀₄ in the formula (2A) has a phenol group. The resin composition according to any one of [1], [3] to [5], and [7].
[10]
The resin composition according to any one of [1] to [9], further comprising a polymerization initiator.
[11]
The resin composition according to any one of [1] to [10], further comprising a polymerizable compound.
[12]
The resin composition according to any one of [1] to [11], further comprising a light absorbing agent.
[13]
The resin composition according to [12], wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.
[14]
[14] The resin composition according to any one of [1] to [13], wherein when a dissolution rate of the film formed from the resin composition is measured in gamma-butyrolactone before and after exposure to 100 mJ/ ^cm2 , the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm/sec or more.
[15]
[15] Any one of the resin compositions according to [1] to [14], wherein when a dissolution rate of the film formed from the resin composition in an aqueous tetramethylammonium hydroxide solution is measured before and after exposure at 100 mJ/ ^cm2 , the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm/sec or more.
[16]
The resin composition according to any one of [1], [3] to [5], [7], and [9], wherein the resin has a repeating unit represented by the formula (1A) and a repeating unit represented by the formula (2A).
[17]
The resin composition according to any one of [1] to [16], which is used for forming an insulating film.
[18]
The resin composition according to any one of [1] to [17], which is used for forming an interlayer insulating film for a redistribution layer.

The present invention provides a resin composition that can form a film with excellent resolution and a small CTE.

The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described.
In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values before and after "to" as the lower limit and upper limit, respectively.
In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, an "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams, ion beams, etc. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise stated. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns. Unless otherwise stated, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. Unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise specified, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, combinations of preferred aspects are more preferred aspects.
As used herein, an "organic group" refers to a group containing at least one carbon atom.

[Resin composition]
The resin composition of the present invention will be described.
The resin composition of the present invention is a resin composition containing a resin (also referred to as "resin (A)" or "specific resin") having at least one type selected from the group consisting of a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (2A):

In formula (1A) and formula (2A),
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent an organic group.
W ₁ , W ₂ , W ₃ and W ₄ each independently represent a linking group.
P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
m, n, p and q each independently represent an integer of 1 or more.
When a plurality of W ₁ , W ₂ , W ₃ , W ₄ , P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ are present, they may be the same or different.

According to the resin composition of the present invention, a film having excellent resolution and small CTE can be formed. The mechanism by which the above-mentioned effect is obtained by the present invention is not clear, but the present inventors presume as follows. However, the present invention is not limited by the following presumed mechanism.
It is considered that the resin contained in the resin composition of the present invention has at least one selected from the group consisting of a repeating unit represented by formula (1A) and a repeating unit represented by formula (2A), and thereby the density of the three-dimensional mesh structure of an exposed film obtained by exposing a film formed from the resin composition of the present invention is improved, and the resolution is improved.
In addition, it is considered that the inclusion of specific groups represented by P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ in formula (1A) and formula (2A) reduces entanglement of resins and improves orientation, thereby improving CTE.

The components contained in the resin composition of the present invention will be described in detail below.

<Resin (A)>
The resin composition of the present invention contains at least one resin (A).
The resin (A) is a resin having at least one repeating unit selected from the group consisting of the repeating unit represented by the above formula (1A) and the repeating unit represented by the above formula (2A).
The resin (A) may be a polyimide or a polyamide.
The resin (A) may have a repeating unit represented by the above formula (1A) and a repeating unit represented by the above formula (2A).
The resin (A) may further have a repeating unit other than the repeating unit represented by the above formula (1A) and the repeating unit represented by the above formula (2A).
Resin (A) may be a precursor of cyclized resin.The precursor of cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin, and is preferably a resin that undergoes a change in chemical structure due to heat to become a cyclized resin, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin.Examples of the precursor of cyclized resin include polyimide precursor, polybenzoxazole precursor, polyamideimide precursor, etc.

The repeating unit represented by formula (1A) will be described.
When resin (A) is a resin having a repeating unit represented by formula (1A), resin (A) is a polyimide, and therefore, in the following description, resin (A) having a repeating unit represented by formula (1A) is also referred to as "polyimide".

X ₁ in formula (1A) represents an organic group, more specifically, an organic group having a valence of 4+a. Since a represents an integer of 0 or more, the following description will be given taking as an example a representing 0 (i.e., a case where X ₁ represents a tetravalent organic group) (when a represents an integer of 1 or more, X ₁ is obtained by substituting a number of -W ₁ -(P ₀₁ ) _m for a number of hydrogen atoms in X ₁ described below).
The tetravalent organic group represented by _X1 is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6). In formulas (5) and (6), * represents a bonding site with -C(=O)- in formula (1A).

In formula (5), R ¹¹² is a single bond or a divalent linking group, and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group), -O-, -CO-, -S-, -SO ₂ -, -NHCO-, or a combination thereof, more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, -O-, -CO-, -S-, and -SO ₂ -, and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, a phenylene group, -O-, -CO-, -S-, and -SO ₂ -.

Specific examples of _X1 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride, etc. The structure corresponding to _X1 may contain only one type of tetracarboxylic acid residue, or may contain two or more types of tetracarboxylic acid residues.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of X ₁ .

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2, 2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2 ,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene These include tetracarboxylic dianhydrides, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

From the viewpoint of film strength, X ₁ is preferably a tetracarboxylic acid residue having 1 to 4 aromatic rings.

In formula (1A), _Y1 represents an organic group, more specifically, an organic group having a valence of 2+b. Since b represents an integer of 0 or more, the following description will be given taking as an example a case where b represents 0 (i.e., a case where _Y1 represents a divalent organic group) (when b represents an integer of 1 or more, _Y1 is obtained by substituting b arbitrary hydrogen atoms of _Y1 described below with _{b -W2-} ( _P02 ) _n ).
Examples of the divalent organic group represented by Y ₁ include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic heterocyclic group preferably contains one or more heteroatoms selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms in the ring members. The number of ring members of the aromatic group is preferably 5 to 20, and more preferably 6 to 15. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom.
Examples of _Y1 include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred. Here, each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

_Y1 is preferably derived from a diamine. Examples of the diamine include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types of diamines may be used.
Specifically, _Y1 is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a group selected from combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ₂ -, and further preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.
In the formula, * represents a bonding site with other structures.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine;
m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl phenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl , 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-di Ethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydro 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane , 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane , 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4 and at least one diamine selected from 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

Also preferably used are diamines having two or more alkylene glycol units in the main chain, as described in paragraphs 0032 to 0034 of WO 2017/038598.

From the viewpoint of flexibility of the obtained film, _Y1 is preferably represented by -Ar-L-Ar-. However, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

From the viewpoint of i-line transmittance, _Y1 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, Y1 is more preferably a divalent organic group represented by formula (61).

In formula (51), R ⁵⁰ to R ⁵⁷ each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom.
Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom.
Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

_Y1 is also preferably a diamine residue having at least two alkylene glycol units in the main chain (a group remaining after removal of the amino groups of the diamine) in order to more effectively suppress the occurrence of warping during firing. It is also preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc.

In formula (1A), P ₀₁ and P ₀₂ each independently represent an organic group containing at least one type (also referred to as "specific group (X)") selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group.
It is believed that the resin (A) having the specific group (X) reduces entanglement of polymers and improves the orientation in the film, thereby lowering the CTE.

The imido group is preferably a group represented by the following formula (PN-1).
The amide group is preferably a group represented by the following formula (PN-2): In formula (PN-2), R ^{1 X1} represents a hydrogen atom or a substituent.
The phenylene ether group is preferably a group represented by the following formula (PN-3): In formula (PN-3), R ^{1 X2} represents a substituent, and k1 represents an integer of 0 to 4.
The benzoxazole group is preferably a group represented by the following formula (PN-4): In formula (PN-4), R ^{1 X3} represents a substituent, and k2 represents an integer of 0 to 3.
The sulfonamide group is preferably a group represented by the following formula (PN-5): In formula (PN-5), R ^{1 X4} represents a hydrogen atom or a substituent.
The group having three or more ester groups is preferably a group represented by the following formula (PN-6) or formula (PN-6-2). In formula (PN-6), ^E1 and ^E2 each independently represent a divalent organic group. k3 represents an integer of 2 or more. In formula (PN-6-2), ^E3 represents a divalent organic group. k31 represents an integer of 3 or more.
The siloxane group is preferably a group represented by the following formula (PN-7): In formula (PN-7), R ^{1 X5} and R ^{1 X6} each independently represent a hydrogen atom or a substituent.
The fluoroalkylene group may be linear or branched. There is no particular limitation on the number of carbon atoms in the fluoroalkylene group, but the number of carbon atoms is preferably 1 to 30. The fluoroalkylene group may be a perfluoroalkylene group. The fluoroalkylene group may have a substituent other than a fluorine atom.
The phenol group is preferably a group represented by the following formula (PN-8): In formula (PN-8), R ^X7 represents a substituent, and k4 represents an integer of 0 to 4.
The phenoxy group is preferably a group represented by the following formula (PN-9): In formula (PN-9), R ^X8 represents a substituent, and k5 represents an integer of 0 to 5.
In the following formulas (PN-1) to (PN-9), * indicates the bonding position to other structures.

The organic groups represented by P ₀₁ and P ₀₂ are not particularly limited except that they contain a specific group (X). The organic groups represented by P ₀₁ and P ₀₂ may be a specific group (X), or may be a group consisting of a specific group (X) and another group. The organic groups represented by P ₀₁ and P ₀₂ may have a repeating unit (may be a polymer chain). The specific group (X ₎ contained in the organic groups represented by P 01 and P ₀₂ may be one type or two or more types.

In formula (1A), W ₁ and W ₂ each independently represent a linking group.
The linking group represented by _W1 and _W2 is not particularly limited, but preferably represents an organic group, such as a carbonyl group, an ester group, an amide group, an alkylene group, an arylene group, a cycloalkylene group, an alkyleneoxy group, an aryleneoxy group, a cycloalkyleneoxy group, and a group formed by combining two or more of these groups. These organic groups may further have a substituent.
The number of carbon atoms in the linking groups represented by W ₁ and W ₂ is not particularly limited, and may be, for example, 1 to 100 carbon atoms.

In formula (1A), a and b each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more. a and b each independently may represent an integer of 0 or more and 100 or less, preferably an integer of 0 or more and 10 or less, and more preferably an integer of 0 or more and 5 or less.
In formula (1A), m and n each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.

It is also preferred that at least one of X ₁ and Y ₁ has an OH group. More specifically, preferred examples of Y ₁ include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and more preferred examples of X ₁ include the above (DAA-1) to (DAA-5).

The polyimide may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
From the viewpoint of the strength and insulating properties of the resulting film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In the present invention, the term "main chain" refers to the relatively longest bonding chain in a resin molecule, and the term "side chain" refers to any other bonding chain.

-Fluorine atom-
From the viewpoint of the strength of the resulting film, it is also preferable that the polyimide contains fluorine atoms.
The fluorine atom is preferably contained in, for example, _X1 or _Y1 , and more preferably contained in _X1 or _Y1 as a fluorinated alkyl group.
The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

-Silicon atom-
From the viewpoint of the strength of the resulting film, it is also preferable that the polyimide contains a silicon atom.
It is more preferable that the silicon atom is contained in, for example, _X1 or _Y1 as an organically modified (poly)siloxane structure.
The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.

- Ethylenically unsaturated bond -
From the viewpoint of the strength of the resulting film, the polyimide preferably has an ethylenically unsaturated bond.
The ethylenically unsaturated bond preferably has radical polymerizability.
An ethylenically unsaturated bond is preferably contained in at least one of _X1 and _Y1 , and more preferably contained as a group having an ethylenically unsaturated bond in at least one of _X1 and _Y1 .
The ethylenically unsaturated bond is more preferably contained in _Y1 , and further preferably contained in _Y1 as a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(═O)O-, -O(C═O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

Among these, R ²¹ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents a bonding site with the oxygen atom to which ^R21 in formula (IV) is bonded.
In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R ²¹ in formula (IV).
In formula (R1), X is preferably an oxygen atom.
In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

In formula (IV), * represents a bonding site with another structure, and is preferably a bonding site with the main chain of the polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

--Polymerizable group other than a group having an ethylenically unsaturated bond--
The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in _Y1 , for example.
The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

- Polarity conversion group -
The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is preferably an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, or the like, and is more preferably an acetal group or a ketal group from the viewpoint of exposure sensitivity.
Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
The polarity conversion group is contained in, for example, X ₁ , Y ₁ , or the terminal of the polyimide.

-Acid value-
When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development"), the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified. For pKa, the value listed in "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan may be referred to.
When the acid group is a polyacid, such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenol hydroxy group-
From the viewpoint of ensuring an appropriate development speed with an alkaline developer, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
The phenolic hydroxy group is preferably contained in, for example, _X1 or _Y1 .
The amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

It is also preferable that the polyimide has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

In order to improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

In order to improve the storage stability of the resin composition, it is also preferable that the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Of these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents.

-Imidization rate (ring closure rate)-
From the viewpoints of the strength, insulating properties, etc. of the resulting film, the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula.
Imidization rate (%)=(peak intensity P1/peak intensity P2)×100

The polyimide may contain only one type of repeating unit represented by formula (1A), or may contain two or more types. In addition to the repeating unit represented by formula (1A), the polyimide may contain other types of repeating units. Examples of other types of repeating units include repeating units represented by formula (2A).

Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized using a known imidization reaction method, or by stopping the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure. Other known methods for synthesizing polyimides can also be applied.
An example of the polyimide precursor is a polyamide having a repeating unit represented by the formula (2A).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
The polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
When the resin composition contains multiple polyimides, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one of the polyimides are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.

The repeating unit represented by formula (2A) will be described.
When the resin (A) is a resin having a repeating unit represented by formula (2A), the resin (A) is a polyamide, and therefore in the following description, the resin (A) having a repeating unit represented by formula (2A) is also referred to as "polyamide". The polyamide may be a polyimide precursor for producing a polyimide having a repeating unit represented by formula (1A).

_X2 in formula (2A) represents an organic group, more specifically, a 2+c-valent organic group. Since c represents an integer of 0 or more, the following description will be given taking as an example a case where c represents 0 (i.e., a case where _X2 represents a divalent organic group) (when c represents an integer of 1 or more, _X2 is obtained by substituting c arbitrary hydrogen atoms of _X2 described below with c _-W3- ( _P03 ) _p ).
The divalent organic group represented by _X2 is preferably a divalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5-1) or formula (6-1). In formulas (5-1) and (6-1), * represents a bonding site with -C(=O)- in formula (2A).

In formula (5-1), R ¹¹² is a single bond or a divalent linking group, and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group), -O-, -CO-, -S-, -SO ₂ -, -NHCO-, or a combination thereof, more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, -O-, -CO-, -S-, and -SO ₂ -, and still more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, a phenylene group, -O-, -CO-, -S-, and -SO ₂ -.

Specific examples of _X2 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride, etc. The structure corresponding to _X2 may contain only one type of tetracarboxylic acid residue, or may contain two or more types of tetracarboxylic acid residues.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of X ₁ in formula (1A).
Specific examples of the tetracarboxylic dianhydride are the same as those described in the description of _X1 .
From the viewpoint of film strength, _X2 is preferably a tetracarboxylic acid residue having 1 to 4 aromatic rings.

In formula (2A), _Y2 represents an organic group, more specifically, an organic group having a valence of 2+d. Since d represents an integer of 0 or more, the following description will be given taking as an example a case where d represents 0 (i.e., a case where _Y2 represents a divalent organic group) (when d represents an integer of 1 or more, _Y2 is obtained by substituting d arbitrary hydrogen atoms of _Y2 described below with d _-W4- ( _P04 ) _q ).
The description, specific examples and preferred range of the divalent organic group represented by _Y2 are the same as those for _Y1 in the above formula (1A).

The explanation, specific examples and preferred ranges of P ₀₃ and P ₀₄ in formula (2A) are the same as those for P ₀₁ and P ₀₂ in formula (1A) described above.
The explanation, specific examples and preferred ranges of _W3 and _W4 in formula (2A) are the same as those of _W1 and _W2 in formula (1A) described above.

In formula (2A), c and d each independently represent an integer of 0 or more. However, at least one of c and d represents an integer of 1 or more. c and d each independently may represent an integer of 0 or more and 100 or less, preferably an integer of 0 or more and 10 or less, and more preferably an integer of 0 or more and 5 or less.
In formula (2A), p and q each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.

At least one of _X2 and _Y2 may have an OH group. More specifically, _Y2 may be a residue of a bisaminophenol derivative.

At least one of _X2 and _Y2 preferably contains a polymerizable group, and both preferably contain a polymerizable group. At least one of _X2 and _Y2 preferably contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. As the radically polymerizable group of the polyamide, a group having an ethylenically unsaturated bond is preferably used.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
In formula (III), * represents a bonding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH ₂ CH(OH)CH ₂ -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH ₂ CH(OH)CH ₂ -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.

At least one of _X2 and _Y2 may have a polarity conversion group such as an acid-decomposable group. The description, specific examples and preferred range of the acid-decomposable group are the same as those for _X1 and _Y1 described above.

It is also preferable that the polyamide has fluorine atoms in its structure. The fluorine atom content in the polyamide is preferably 10% by mass or more, and 20% by mass or less.

In order to improve adhesion to the substrate, the polyamide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.

The polyamide may contain only one type of repeating unit represented by formula (2A), or may contain two or more types. The polyamide may contain other types of repeating units in addition to the repeating unit represented by formula (2A).

One embodiment of the polyamide is one in which the content of repeating units represented by formula (2A) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to the total content, and all repeating units in the polyamide except for the terminals may be repeating units represented by formula (2A).

The weight average molecular weight (Mw) of the polyamide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyamide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The polyamide molecular weight dispersity is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyamide molecular weight dispersity is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
When the resin composition contains multiple polyamides, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one of the polyamides are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyamides as one resin are each within the above ranges.

[Method for producing polyamide]
Polyamides can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine at low temperature, by reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid with a condensing agent or an alkylating agent, by obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, etc. Of the above-mentioned production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, is more preferable.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
In the method for producing a polyamide, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types.
The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.
In the method for producing a polyamide, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.
The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

-End-capping agent-
In the method for producing polyamide, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyamide in order to further improve storage stability. When capping the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability. Examples of preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
In addition, when the amino group at the resin terminal is blocked, it is possible to block it with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. Preferred examples of the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

-Solid precipitation-
The method for producing polyamide may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof to precipitate the polymer component as a solid, and then dried to obtain polyamide. In order to improve the degree of purification, the polyamide may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

Next, preferred embodiments of formula (1A) and formula (2A) will be described.
At least one of P ₀₁ and P ₀₂ in formula (1A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group,
At least one of P ₀₃ and P ₀₄ in formula (2A) preferably contains at least one selected from the group consisting of an imido group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group.

At least one of P ₀₁ and P ₀₂ in formula (1A) has a branched structure;
At least one of P ₀₃ and P ₀₄ in formula (2A) preferably has a branched structure.
The branched structure means a structure in which the polymer chain in the resin (A) is branched. For example, when the resin (A) has a form such as a branched polymer, a graft polymer, a network polymer, a star polymer, or a dendrimer, the resin has a branched structure.
A preferred embodiment of the branched structure is one in which the branched structure is composed of a main chain of the resin (A) and a branched chain bonded to the main chain. In this embodiment, it is more preferred that the formula weight of the branched chain constituting the branched structure is 100 or more.
Another preferred embodiment of the branched structure is that the resin (A) is a network polymer. In this embodiment, it is more preferred that the formula weight of the groups between the branch points of the network structure is 100 or more.

At least one of P ₀₁ and P ₀₂ in formula (1A) has at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1-PA) and repeating units represented by the following formula (2-PA),
At least one of P ₀₃ and P ₀₄ in formula (2A) preferably has at least one type selected from the group consisting of repeating units represented by the following formula (1-PA) and repeating units represented by the following formula (2-PA).

In formula (1-PA) and formula (2-PA),
X _1p , X _2p , Y _1p and Y _2p each independently represent an organic group.
W _1p , W _2p , W _3p and W _4p each independently represent a linking group.
P _01p , P _02p , P _03p and P _04p each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
ap, bp, cp, and dp each independently represent an integer of 0 or more, provided that at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more.
mp, np, pp and qp each independently represent an integer of 1 or more.
When a plurality of _W1p , _W2p , _W3p , _W4p , _P01p , _P02p , _P03p and _P04p are present, they may be the same or different.

The explanations, specific examples and preferred ranges of X _1p , X _2p , Y _1p and Y _2p in formula (1-PA) and formula (2-PA) are the same as those of X ₁ , X ₂ , Y _{1 and Y 2} in formula (1A) and formula ( _2A ) described above.
The explanations, specific examples and preferred ranges of W _1p , W _2p , W _3p and W _4p in formula (1-PA) and formula (2-PA) are the same as those for W ₁ , W ₂ , W ₃ and W ₄ in formula (1A) and formula (2A) described above.
The explanations, specific examples and preferred ranges of P _01p , P _02p , P _03p and P _04p in formula (1-PA) and formula (2-PA) are the same as those for P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ in formula (1A) and formula (2A) described above.
In formula (1-PA) and formula (2-PA), ap, bp, cp, and dp each independently represent an integer of 0 or more. However, at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more. ap, bp, cp, and dp each independently may represent an integer of 0 or more and 100 or less. mp, np, pp, and qp in formula (1-PA) and formula (2-PA) each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less.

When at least one of P ₀₁ and P ₀₂ in formula (1A) has at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA), any hydrogen atom in the structure having at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA) is removed and bonds to at least one of W ₁ and W ₂ in formula (1A).
When at least one of P ₀₁ and P ₀₂ in formula (1A) has at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA), P ₀₁ and P ₀₂ may have other structures (which may or may not be repeating units) in addition to the at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA).
When at least one of _P03 and _P04 in formula (2A) has at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA), any hydrogen atom in the structure having at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA) is removed and bonds to at least one of _W3 and _W4 in formula (2A).
When at least one of P ₀₃ and P ₀₄ in formula (2A) has at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA), P ₀₃ and P ₀₄ may have other structures (which may or may not be repeating units) in addition to at least one selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA).

For example, in the case where a in formula (1A) represents 0, b represents 1, n represents 2, two _P02 have repeating units represented by formula (1-PA) (ap=0, bp=1, np=1), and any one hydrogen atom of _P02p in formula (1-PA) is removed and bonded to _W2 in formula (1A), the repeating unit represented by formula (1A) is represented by the following formula (1A-1-PA).

The definitions, explanations, specific examples, and preferred ranges of each symbol in formula (1A-1-PA) are the same as those in formula (1A) and formula (1-PA) described above.

It is preferable that the resin (A) has at least one crosslinkable group at at least one terminal.
The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.
Since the resin (A) has the specific group (X), there is little entanglement between polymers. However, since the resin (A) has a crosslinkable group at the end, the proportion of crosslinkable groups with less steric hindrance increases, and the crosslinking efficiency increases. This makes it possible to form a film with high exposure curability, and it is considered that the resolution is further improved.

At least one of P ₀₁ and P ₀₂ in formula (1A) has a crosslinkable group;
At least one of P ₀₃ and P ₀₄ in formula (2A) preferably has a crosslinkable group.
The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

It is preferred that at least one of P ₀₁ and P ₀₂ in formula (1A) has a phenol group, and at least one of P ₀₃ and P ₀₄ in formula (2A) has a phenol group.

The resin (A) may be a resin having at least one type selected from the group consisting of the repeating unit represented by the following formula (1) and the repeating unit represented by the following formula (2). In other words, the resin composition of the present invention may be a resin composition containing a resin having at least one type selected from the group consisting of the repeating unit represented by the following formula (1) and the repeating unit represented by the following formula (2).

In formula (1) and formula (2),
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent an organic group.
W ₁ , W ₂ , W ₃ and W ₄ each independently represent a linking group.
_P1 , _P2 , _P3 and _P4 each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
Q ₁ , Q ₂ , Q ₃ and Q ₄ each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
m, n, p and q each independently represent an integer of 1 or more.
When a plurality of _W1 , _W2 , _W3 , _W4 , _P1 , _P2 , _P3 , _P4 , _Q1 , _Q2 , _Q3 and _Q4 are present, they may be the same or different.

The explanations, specific examples and preferred ranges of X ₁ , X ₂ , Y ₁ and Y ₂ in formula (1) and formula (2) are the same as those of X ₁ , X ₂ , Y ₁ and Y ₂ in formula (1A) and formula (2A) described above.
The explanations, specific examples and preferred ranges of W ₁ , W ₂ , W ₃ and W ₄ in formulas (1) and (2) are the same as those for W ₁ , W ₂ , W ₃ and W ₄ in formulas (1A) and (2A) described above.
In formula (1), a and b each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more. a and b each independently may represent an integer of 0 or more and 100 or less, preferably an integer of 0 or more and 10 or less, and more preferably an integer of 0 or more and 5 or less.
In formula (1), m and n each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.
In formula (2), c and d each independently represent an integer of 0 or more. However, at least one of c and d represents an integer of 1 or more. c and d each independently may represent an integer of 0 or more and 100 or less, preferably an integer of 0 or more and 10 or less, and more preferably an integer of 0 or more and 5 or less.
In formula (2), p and q each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.

In formula (1) and formula (2), _P1 , _P2 , _P3 , and _P4 each independently represent an organic group containing at least one type (specific group (X)) selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group.
The imido group is preferably a group represented by the above formula (PN-1).
The amide group is preferably a group represented by the above formula (PN-2).
The phenylene ether group is preferably a group represented by the above formula (PN-3).
The benzoxazole group is preferably a group represented by the above formula (PN-4).
The sulfonamide group is preferably a group represented by the above formula (PN-5).
The group having three or more ester groups is preferably a group represented by the above formula (PN-6) or formula (PN-6-2).
The siloxane group is preferably a group represented by the above formula (PN-7).
The fluoroalkylene group may be linear or branched. There is no particular limitation on the number of carbon atoms in the fluoroalkylene group, but the number of carbon atoms is preferably 1 to 30. The fluoroalkylene group may be a perfluoroalkylene group. The fluoroalkylene group may have a substituent other than a fluorine atom.

The organic group represented by P ₁ , P ₂ , P ₃ and P ₄ is not particularly limited except that it contains a specific group (X). The organic group represented by _{P 1} , P ₂ , P ₃ and P ₄ may be a specific group (X), or may be a group consisting of a specific group (X) and another group. In addition, the organic group represented by P ₁ , P ₂ , P ₃ and P ₄ may have a repeating unit (may be a polymer chain). The specific group (X) contained in the organic group represented by P ₁ , P ₂ , P ₃ and P ₄ may be one type or two or more types.

In formula (1), Q ₁ and Q ₂ each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group, or a hydrogen atom.
The monovalent organic group represented by _Q1 and _Q2 is not particularly limited, and examples thereof include an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an acyl group, a heterocyclic group, an alkenyl group, an alkynyl group, and a group formed by combining two or more of these groups. These organic groups may further have a substituent.
The number of carbon atoms in the monovalent organic group represented by Q ₁ and Q ₂ is not particularly limited, and may be, for example, 1 to 100 carbon atoms.
The halogen atom represented by Q ₁ and Q ₂ is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The explanation, specific examples and preferred ranges of _Q3 and _Q4 in formula (2) are the same as those of _Q1 and _Q2 in formula (1) above.

Next, preferred embodiments of formula (1) and formula (2) will be described.
At least one of _P1 and _P2 in formula (1) contains at least one selected from the group consisting of an imide group, an amide group, and a phenylene ether group,
At least one of _P3 and _P4 in formula (2) preferably contains at least one type selected from the group consisting of an imide group, an amide group, and a phenylene ether group.

At least one of _P1 and _P2 in formula (1) has a branched structure;
At least one of _P3 and _P4 in formula (2) preferably has a branched structure.
The branched structure is as described above.
A preferred embodiment of the branched structure is one in which the branched structure is composed of a main chain of the resin (A) and a branched chain bonded to the main chain. In this embodiment, it is more preferred that the formula weight of the branched chain constituting the branched structure is 100 or more.
Another preferred embodiment of the branched structure is that the resin (A) is a network polymer. In this embodiment, it is more preferred that the formula weight of the groups between the branch points of the network structure is 100 or more.

At least one of _P1 and _P2 in formula (1) has at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1-P) and repeating units represented by the following formula (2-P),
At least one of _P3 and _P4 in formula (2) preferably has at least one type selected from the group consisting of repeating units represented by the following formula (1-P) and repeating units represented by the following formula (2-P).

In formula (1-P) and formula (2-P),
X _1p , X _2p , Y _1p and Y _2p each independently represent an organic group.
W _1p , W _2p , W _3p and W _4p each independently represent a divalent organic group.
P _1p , P _2p , P _3p and P _4p each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, a fluoroalkyl group and a fluoroalkylene group.
Q _1p , Q _2p , Q _3p and Q _4p each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
ap, bp, cp, and dp each independently represent an integer of 0 or more, provided that at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more.
mp, np, pp and qp each independently represent an integer of 1 or more.
When multiple _W1p , _W2p , _W3p , _W4p , _P1p , _P2p , _P3p , _P4p , _Q1p , _Q2p , _Q3p and _Q4p are present, they may be the same or different.

The explanations, specific examples and preferred ranges of X _1p , X _2p , Y _1p and Y _2p in formula (1-P) and formula (2-P) are the same as those of X ₁ , X ₂ , Y 1 and Y ₂ in formula (1) and formula ( ₂ ) above.
The explanations, specific examples and preferred ranges of W _1p , W _2p , W _3p and W _4p in formula (1-P) and formula (2-P) are the same as those for W ₁ , W ₂ , W ₃ and W ₄ in formula (1) and formula (2) described above.
The explanations, specific examples and preferred ranges of P _1p , P _2p , P _3p and P _4p in formula (1-P) and formula (2-P) are the same as those for P ₁ , P ₂ , P ₃ and P ₄ in formula (1) and formula (2) above.
The explanations, specific examples and preferred ranges of Q _1p , Q _2p , Q _3p and Q _4p in formula (1-P) and formula (2-P) are the same as those for Q ₁ , Q ₂ , Q ₃ and Q ₄ in formula (1) and formula (2) above.
In formula (1-P) and formula (2-P), ap, bp, cp, and dp each independently represent an integer of 0 or more. However, at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more. ap, bp, cp, and dp each independently may represent an integer of 0 or more and 100 or less. mp, np, pp, and qp in formula (1-P) and formula (2-P) each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less.

When at least one of _P1 and _P2 in formula (1) has at least one type selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P), any hydrogen atom in the structure having at least one type selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P) is removed and bonds to at least one of _W1 and _W2 in formula (1).
When at least one of _P1 and _P2 in formula (1) has at least one selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P), _P1 and _P2 may have another structure (which may or may not be a repeating unit) in addition to the at least one selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P).
When at least one of _P3 and _P4 in formula (2) has at least one selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P), any hydrogen atom in the structure having at least one selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P) is removed and bonds to at least one of _W3 and _W4 in formula (2).
When at least one of _P3 and _P4 in formula (2) has at least one selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P), _P3 and _P4 may have another structure (which may or may not be a repeating unit) in addition to the at least one selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P).

It is preferable that the resin (A) has at least one crosslinkable group at at least one terminal.
The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

At least one of _Q1 and _Q2 in formula (1) has a crosslinkable group;
In formula (2), it is preferred that at least one of _Q3 and _Q4 has a crosslinkable group.
The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

It is preferred that P ₁ , P ₂ , Q ₁ and Q ₂ in formula (1) satisfy at least one of the following (i) and (ii), and P ₃ , P ₄ , Q ₃ and Q ₄ in formula (2) satisfy at least one of the following (iii) and (iv).
(i): _P1 represents a phenylene ether group and _Q1 represents a hydrogen atom.
(ii): _P2 represents a phenylene ether group, and _Q2 represents a hydrogen atom.
(iii): _P3 represents a phenylene ether group, and _Q3 represents a hydrogen atom.
(iv): _P4 represents a phenylene ether group, and _Q4 represents a hydrogen atom.

[Content]
The content of the resin (A) in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin (A) in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only one type of resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

It is also preferable that the resin composition of the present invention contains at least two types of resins.
Specifically, the resin composition of the present invention may contain a total of two or more types of resin (A) and the other resins described below, or may contain two or more types of resin (A), but it is preferable that the resin composition contains two or more types of resin (A).
When the resin composition of the present invention contains two or more types of resin (A), it is preferable that the resin composition contains, for example, two or more types of polyamide having different dianhydride-derived structures (X ₂ in formula (2A)).

<Other resins>
The resin composition of the present invention may contain resin (A) and another resin different from resin (A) (hereinafter, simply referred to as "another resin").
Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and polybenzoxazoles.
For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of or in addition to the polymerizable compound described later, by adding a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of polymerizable groups per 1 g of resin is 1×10 ⁻³ mol/g or more) to the resin composition, the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
The content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
As a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

<Polymerizable Compound>
The resin composition of the present invention preferably contains a polymerizable compound (crosslinking agent).
The polymerizable compound may include a radical crosslinking agent or other crosslinking agents.

[Radical Crosslinking Agent]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.

Preferable radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.

The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. Oligomer types of these can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers. Examples of such esters include UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME 400 (manufactured by NOF Corp.).

As radical crosslinking agents, urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. As radical crosslinking agents, compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

As the radical crosslinking agent, a radical crosslinking agent having at least one bond selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.
In the present invention, the urea bond is a bond represented by *-NR ^N -C(=O)-NR ^N -*, where each R ^N independently represents a hydrogen atom or a monovalent organic group, and each * represents a bonding site with a carbon atom.
In the present invention, a urethane bond is a bond represented by *--O--C(.dbd.O)-- ^NR.sub.N --*, where ^R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
When the resin composition contains the crosslinking agent U, the chemical resistance, resolution, and the like may be improved.
The mechanism by which the above-mentioned effect is obtained is unclear; however, it is considered that, for example, a part of the crosslinking agent U is thermally decomposed during curing by heating or the like, thereby generating amines, etc., and the above amines, etc. promote the cyclization of the precursor of the cyclized resin, such as a polyimide precursor.
The crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
When the crosslinking agent U has no urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
When crosslinking agent U has no urea bond, the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

The radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
When the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
The radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g/mol.
From the viewpoint of chemical resistance of the cured product, the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, even more preferably 220 g/mol or more, even more preferably 230 g/mol or more, even more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
From the viewpoint of developability, the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, further preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
In particular, the polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g/mol, and more preferably from 220 to 400 g/mol.

The crosslinking agent U preferably has a structure represented by the following formula (U-1):

In formula (U-1), R ^U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR ^N -, R ^N is a hydrogen atom or a monovalent organic group, Z ^U1 is an m-valent organic group, Z ^U2 is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

R ^U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
R 3 ^N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
Z ^U1 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group in which two or more of these are bonded together, and more preferably a hydrocarbon group, or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -.
The above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. The above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof. R ^N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
Z ^U2 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group in which two or more of these are bonded together, and more preferably a hydrocarbon group, or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -.
The hydrocarbon group includes the same as those exemplified for ^ZU1 , and preferred embodiments are also the same.
X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and further preferably 1 or 2.

It is also preferred that the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
From the viewpoint of the chemical resistance of the obtained cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.
The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
The amide group refers to a bond represented by -C(=O)-NR ^N -, where R ^N is as described above. When crosslinking agent U has an amide group, crosslinking agent U can contain it, for example, as a group represented by R-C(=O)-NR ^N -*, or a group represented by *-C(=O)-NR ^N -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
The crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group. An embodiment having only one such structure in the molecule is also preferred.
The hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U. From the viewpoint of chemical resistance, however, it is also preferable that the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
In particular, when the crosslinking agent U contains only one radically polymerizable group, it is preferable that the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
When the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable. As the hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned. In addition, a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
When the crosslinking agent U contains an amide group and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. In addition, examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a bond between these groups. A preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above. In addition, in the above embodiment, the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that the crosslinking agent U has a hydroxy group.

From the viewpoint of compatibility with the specific resin, the crosslinking agent U preferably contains an aromatic group.
The aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
The aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
The aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.

The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
When the crosslinking agent U contains two or more urea bonds or urethane bonds in total, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
In this specification, the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[Axis of symmetry]
It is also preferred that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
The fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound. In addition, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry.
It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.

[Molecular weight]
The molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.

The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group or an amino group.

Specific examples of cross-linking agent U are shown below, but cross-linking agent U is not limited to these.

From the viewpoints of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the resin composition.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as necessary.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
In the resin composition of the present invention, from the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
Other examples of the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0 mass% and not more than 60 mass% based on the total solid content of the resin composition. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and even more preferably 30 mass% or less.

The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.

[Other crosslinking agents]
The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
The other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred.In addition, as the other crosslinking agent, a compound having a total of two or more acyloxymethyl groups, a methylol group, an ethylol group, and an alkoxymethyl group is preferred.Among them, a compound having two or more acyloxymethyl groups, a compound having two or more methylol groups, a compound having two or more ethylol groups, or a compound having two or more alkoxymethyl groups is more preferred.
Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used.The methylol groups of these compounds may be self-condensed to produce an oligomer.
As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine.
The alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the compound is preferably 1,500 or less, and more preferably 180 to 1,200.

R ₁₀₀ represents an alkyl group or an acyl group.
R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

In the formula, X represents a single bond or a divalent organic group, each of _R104 independently represents an alkyl group or an acyl group, and _R103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by ^-C ( ^R4 ) _2COOR5 (each of ^R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ^R5 represents a group that is eliminated by the action of an acid)).
Each R ₁₀₅ independently represents an alkyl group or an alkenyl group; each of a, b, and c independently represents 1 to 3; d represents 0 to 4; e represents 0 to 3; f represents 0 to 3; a+d is 5 or less; b+e is 4 or less; and c+f is 4 or less.
Examples of R ⁵ in a group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C(R ⁴ ) ₂ COOR ⁵ include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, and _{R 36} and R ₃₇ may be bonded to each other to form a ring.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
The alkyl group may be either linear or branched.
The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.
The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
These groups may further have known substituents.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The group that decomposes under the action of an acid to generate an alkali-soluble group, or the group that is eliminated under the action of an acid, is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

Furthermore, as a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. The preferred aspects of the above compounds are the same as the preferred aspects of the crosslinking agent U described above, except that the polymerizable group is not a radically polymerizable group but is at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.

Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures. Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds has been changed to an acyloxymethyl group. Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.

The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method.
From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea;
propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
Examples thereof include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies below) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

The resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

-Epoxy compound (compound having an epoxy group)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200° C. or less, and does not undergo a dehydration reaction due to the crosslinking, so that the film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the resin composition at low temperature and suppressing warpage.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. A polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark, the same applies below) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark, the same applies below) BEO-20E, Likaresin BEO-60E, Likaresin HBE-100, Likaresin DME-100, Likaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Celoxide (registered trademark, the same applies below) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead (registered trademark, the same applies below) GT401, Epolead PB4700, Epolead PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 00-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also preferably used.

In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

In the above structure, it is preferable that n is 1 to 2 and m is 3 to 7 in order to achieve both heat resistance and improved elongation.

--Oxetane compound (compound having an oxetanyl group)--
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

-Benzoxazine compound (compound having a benzoxazolyl group)-
Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (all trade names, manufactured by Shikoku Kasei Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more types.

The content of the other crosslinking agent is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator (also referred to as "initiator"). The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator.
The photopolymerization initiator may be a photoradical polymerization initiator or a photoacid generator.

(Photoradical polymerization initiator)
The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

Any known compound can be used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenones, α-hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, please refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015/199219 A, the contents of which are incorporated herein by reference. Further examples include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP 6301489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018/221177 A, the photopolymerization initiators described in WO 2018/110179 A, the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 A, the contents of which are incorporated herein by reference.

Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

α-Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used. The contents of this specification are incorporated herein.

As a photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it becomes possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP-A-2000-066385, compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, Examples of the compounds include those described in WO 6065596, WO 2015/152153, WO 2017/051680, JP 2017-198865, WO 2017/164127, paragraphs 0025 to 0038, and WO 2013/167515, the contents of which are incorporated herein by reference.

Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), Examples include TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831 and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, an oxime compound having the following structure can also be used.

As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
In addition, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. The electron-withdrawing group of the aromatic ring group Ar ^OX1 includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and further preferably an alkoxy group, an alkylsulfanyl group, or an amino group.

The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and is more preferably a compound represented by formula (OX2).

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
R ^X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group;
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, it is preferable that R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are each a hydrogen atom.

Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.

As the photoradical polymerization initiator, the compounds described in paragraphs [0175] to [0179] of WO 2021/020359 and the compounds described in paragraphs [0048] to [0055] of WO 2015/125469 can also be used, the contents of which are incorporated herein by reference.

As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in JP-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No. 34963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

When the resin composition contains a photopolymerization initiator, the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

(Photoacid generator)
The polymerization initiator may be a photoacid generator.
The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light having a wavelength of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. The photoacid generator is preferably capable of generating an acid by being exposed to light, either alone or in combination with a sensitizer.
Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

Examples of photoacid generators include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, and onium salt compounds.
From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.

Quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and/or sulfonamide-bonded to a polyhydroxy polyamino compound. Although not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds need to be substituted with quinone diazide, it is preferable that, on average, 40 mol% or more of the total functional groups are substituted with quinone diazide. By incorporating such quinone diazide compounds, it is possible to obtain a resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.

Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOC P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-P CHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriM L-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP -PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Asahi Yu Examples of suitable phenols include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolac resins.

Specific examples of amino compounds include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

Specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

Among these, it is preferable that the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.

The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of resin. By setting the content of the quinone diazide compound within this range, it is possible to obtain contrast between exposed and unexposed areas, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably a compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105).

In formula (OS-1), ^X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of ^X3s are present, they may be the same or different. The alkyl group and alkoxy group in ^X3 may have a substituent. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.
m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, multiple ^X3s may be the same or different.
R ³⁴ represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), a compound in which m3 is 3, ^X3 is a methyl group, the substitution position of ^X3 is the ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs [0064] to [0068] of JP2011-209692A and paragraphs [0158] to [0167] of JP2015-194674A, the contents of which are incorporated herein by reference.

In formulae (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^s2 , which may be present in plurality, each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom; R ^s6 , which may be present in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 0 to 6.
The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R ^s1 may have a substituent.

R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. Of the R ^s2 which may be present in two or more, it is preferable that one or two are an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remaining are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent.
Xs represents O or S, and is preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.
The alkyl group (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.
ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The compound represented by formula (OS-103) is preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by formula (OS-104) is preferably a compound represented by the following formula (OS-107), and the compound represented by formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).

In formulae (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^t7 represents a hydrogen atom or a bromine atom; R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; and R ^t2 represents a hydrogen atom or a methyl group.

R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the above oxime sulfonate compound, the stereochemical structure of the oxime (E, Z) may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by Formulae (OS-103) to (OS-105) include the compounds described in paragraphs [0088] to [0095] of JP-A-2011-209692 and paragraphs [0168] to [0194] of JP-A-2015-194674, the contents of which are incorporated herein by reference.

Other preferred embodiments of compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formulae (OS-101) and (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. R ^u9 is preferably a cyano group or an aryl group, and more preferably a cyano group, a phenyl group, or a naphthyl group.
R ^u2a represents an alkyl group or an aryl group.
Xu represents —O—, —S—, —NH—, —NR ^u5 —, —CH ₂ —, —CR ^u6 H— or —CR ^u6 R ^u7 —, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. Two of ^{R u1} to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring with the benzene ring. ^{R u1 to R u4 are} preferably a hydrogen atom, a halogen atom, or an alkyl group. At least two of R ^u1 to R ^u4 may be bonded to each other to form an aryl group. In particular, it is preferable that R u1 to R u4 are all hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.

The compound containing at least one oxime sulfonate group is more preferably a compound represented by formula (OS-102).
In the oxime sulfonate compound, the stereochemical structures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs [0102] to [0106] of JP-A-2011-209692 and paragraphs [0195] to [0207] of JP-A-2015-194674, the contents of which are incorporated herein by reference.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferable.

Commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Industries, Ltd.), etc.

Furthermore, compounds represented by the following structural formula are also preferred examples.

Examples of organic halogenated compounds include the compounds described in paragraphs 0042 to 0043 of JP 2015-087409 A, the contents of which are incorporated herein by reference.

The content of the photoacid generator is preferably 0.1 to 20 mass%, more preferably 0.5 to 18 mass%, even more preferably 0.5 to 10 mass%, still more preferably 0.5 to 3 mass%, and even more preferably 0.5 to 1.2 mass%, based on the total solid content of the resin composition.
The photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range.
It is also preferable to use a sensitizer in combination in order to impart photosensitivity to a desired light source.

[Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate Examples of such an alkyl ether include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
Other sensitizing dyes may also be used.
For details about the sensitizing dye, the description in paragraphs [0161] to [0163] of JP2016-027357A can be referred to, the contents of which are incorporated herein by reference.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %. The sensitizer may be used alone or in combination of two or more types.

[Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of the chain transfer agent include compounds having -S-S-, -SO ₂ -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization. These donate hydrogen to a low activity radical to generate a radical, or are oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

The chain transfer agent may also be the compound described in paragraphs 0152-0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.

<Base Generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include a thermal base generator and a photobase generator.
In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator is not particularly limited, and a known base generator can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ each independently represent an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not hydrogen atoms at the same time. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a carbon atom of a hydrocarbon group. Therefore, when the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, when it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

In formula (B1) and formula (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and it is preferable that a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent. ^{Rb 1} and Rb ² may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. ^Rb1 and ^Rb2 are preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

Rb ³ is an alkyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), an alkenyl group (having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), an arylalkyl group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), an arylalkenyl group (having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), an alkoxyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryloxy group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyloxy group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. ^Rb3 may further have a substituent.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2):

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent. Among these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are each a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group.
Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the linking chain path is 3 or more. Furthermore, ^R and ^R each independently represent a monovalent organic group.

In this specification, the term "linking chain" refers to the chain of atoms on the path between two atoms or groups of atoms to be linked, which links these objects in the shortest possible way (with the smallest number of atoms). For example, in the compound represented by the formula below, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms that make up the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4.

The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly proceeding with the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020/066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018/038002.

It is also preferable that the base generator contains a compound represented by the following formula (N1):

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that is the shortest path between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and are preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include aliphatic hydrocarbon groups (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) and aromatic hydrocarbon groups (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and are preferably aliphatic hydrocarbon groups. When aliphatic hydrocarbon groups are used as R ^N1 and R ^N2 , the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, the aromatic ring, or the substituent. Particularly, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a linear or branched chain alkyl group, a cyclic alkyl group, a group containing a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
The group containing a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group containing a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched.
Among these, from the viewpoint of increasing the boiling point of the decomposition product base described below, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in a formulation in which importance is placed on adhesion when laminating with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

R ^N1 and R ^N2 may be linked together to form a cyclic structure. The cyclic structure may have an oxygen atom or the like in the chain. The cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic or condensed ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring, and is preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.
The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and preferably includes a protecting group which is decomposed by an acid.
Specific examples of the protective group include linear or cyclic alkyl groups, and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Examples of linear alkyl groups having an oxygen atom in the chain include an alkyloxyalkyl group, and preferred examples include a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom other than carbon atom in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group containing a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Groups containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylene alkyl groups) preferably have 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

Specifically, the linking group L is preferably a straight-chain or branched chain alkylene group, a cyclic alkylene group, a group containing a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a straight-chain or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms.
The group containing a combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, and still more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, and more preferably has 1 to 4 C═C bonds, and even more preferably has 1 or 2 C═C bonds.
The arylene group preferably has 6 to 22 carbon atoms, more preferably has 6 to 18 carbon atoms, and further preferably has 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably has 7 to 19 carbon atoms, and further preferably has 7 to 11 carbon atoms.
Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cisvinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

Base generators include, but are not limited to, the following compounds:

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.

Specific examples of ammonium salts include, but are not limited to, the following compounds:

Specific examples of iminium salts include, but are not limited to, the following compounds:

When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

<Solvent>
The resin composition of the present invention preferably contains a solvent.
The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

Esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate, Suitable examples of the alkyl esters of oxypropionates include alkyl esters of oxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

Preferable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As an example of a sulfoxide, dimethyl sulfoxide is preferred.

Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

From the standpoint of improving the properties of the coating surface, it is also preferable to mix two or more types of solvents.

In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is also one of the preferred embodiments of the present invention.
In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as a specific resin contained in the resin composition, and the like.
Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[Silane coupling agent]
Examples of silane coupling agents include compounds described in paragraph 0316 of International Publication No. 2021/112189 and compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based adhesion promoter]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the lower limit above, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the upper limit above, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine. The contents of this specification are incorporated herein.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.

The polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total is within the above range.

<Acid Scavenger>
The resin composition of the present invention preferably contains an acid scavenger in order to reduce the performance change over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable, and a secondary amine, a tertiary amine, and an ammonium salt are more preferable.
Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and/or an ether bond, aniline derivatives having a hydroxyl group and/or an ether bond, etc. When the acid scavenger has an onium structure, it is preferred that the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylsulfonium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N- Examples include methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, and aminoalkylmorpholine.

The acid scavenger may be used alone or in combination of two or more types. The composition according to the present invention may or may not contain an acid scavenger, but if it does contain one, the content of the acid scavenger is preferably 0.001 to 10 mass %, and more preferably 0.01 to 5 mass %, based on the total solid content of the composition.

The ratio of the acid generator to the acid scavenger is preferably acid generator/acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time until heat treatment after exposure, the molar ratio is preferably 300 or less. The acid generator/acid scavenger (molar ratio) is preferably 5.0 to 200, and more preferably 7.0 to 150.

<Other additives>
The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other polymer compounds, light absorbers, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained. By appropriately incorporating these components, it is possible to adjust the properties of the film properties, etc. These components can be referred to, for example, in the descriptions in paragraphs 0183 and after of JP-A-2012-003225 (corresponding to paragraph 0237 of US Patent Application Publication No. 2013/0034812), and in paragraphs 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, the contents of which are incorporated herein. When these additives are blended, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[Surfactant]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) when the coating liquid composition is prepared can be further improved, and the uniformity of the coating thickness and liquid saving can be further improved. In other words, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and improving the coatability of the surface to be coated. This makes it possible to more suitably form a uniform film with minimal thickness unevenness.

Examples of fluorosurfactants include compounds described in paragraph 0328 of WO 2021/112189, the contents of which are incorporated herein by reference.
As the fluorine-based surfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, and more preferably from 5,000 to 30,000.
As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein by reference. In addition, examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine surfactants with a fluorine content within this range are effective in terms of uniformity of the coating film thickness and liquid saving, and also have good solubility in the composition.

Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021/112189, the contents of which are incorporated herein by reference.

The surfactant may be used alone or in combination of two or more kinds.
The content of the surfactant is preferably from 0.001 to 2.0% by mass, and more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably within the above range.

[Thermal Polymerization Initiator]
Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. The addition of a thermal radical polymerization initiator can also advance the polymerization reaction of a resin and a polymerizable compound, thereby improving the solvent resistance. In addition, a photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[Inorganic particles]
Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm.
The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
When the above measurements are difficult, the measurements can also be made by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.

[Ultraviolet absorber]
Examples of the ultraviolet absorbing agent include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbing agents.
Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021/112189, the contents of which are incorporated herein by reference.

The ultraviolet absorbing agents may be used alone or in combination of two or more.
When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 mass % or more and 1 mass % or less, and more preferably 0.01 mass % or more and 0.1 mass % or less, based on the total solid mass of the resin composition.

[Organotitanium Compounds]
By including an organotitanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organotitanium compound are shown below in I) to VII):
I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and provide a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.
II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like.
III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. If the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern will be better, and if it is 10 parts by mass or less, the storage stability of the composition will be superior.

[Antioxidants]
By including an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to the metal material. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. Specific examples of the antioxidant include the compounds described in paragraphs 0348 to 0357 of WO 2021/112189, the contents of which are incorporated herein by reference.

The content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easier to obtain the effect of improving the elongation properties and adhesion to metal materials even in a high-temperature and high-humidity environment, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[Anti-aggregation agent]
The anti-agglomerating agent may, for example, be sodium polyacrylate.

The anti-aggregating agents may be used alone or in combination of two or more.
When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total solid content mass of the resin composition.

[Phenol compounds]
Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

The phenol-based compounds may be used alone or in combination of two or more.
When the resin composition contains a phenol-based compound, the content of the phenol-based compound is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.

[Other polymer compounds]
Examples of the other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof, etc. The other polymer compounds may be modified by introducing a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group.

The other polymer compounds may be used either individually or in combination of two or more.
When the resin composition contains other polymer compounds, the content of the other polymer compounds is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.

[Light absorber]
The resin composition of the present invention may further contain a light absorber (a compound whose absorbance at the exposure wavelength decreases upon exposure).
Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.

In addition, it is also a preferred embodiment of the present invention to include a photochromic compound as a light absorbing agent. A photochromic compound is a compound whose absorption spectrum changes as a result of the molecular geometric structure being changed by the absorption of light. Specific examples of photochromic compounds are shown below, but the present invention is not limited to these.

The light absorber is preferably at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

When the resin composition of the present invention contains a light absorber, the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

<Characteristics of Resin Composition>
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 ^{mm 2} /s is preferable, 2,000 mm ² /s to 10,000 ^{mm 2} /s is more preferable, and 2,500 mm ² /s to 8,000 ^{mm 2} /s is even more preferable. If it is within the above range, it is easy to obtain a coating film with high uniformity. If it is ^{1,000 mm 2} /s or more, it is easy to apply it with a film thickness required for, for example, a rewiring insulating film, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface condition is obtained.

When the dissolution rate of a film formed from the resin composition of the present invention in γ-butyrolactone is measured before and after exposure at 100 mJ/ ^cm2 , the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is preferably 0.5 μm/sec or more, more preferably 0.6 μm/sec or more, and even more preferably 0.8 μm/sec or more. A value of 0.5 μm/sec or more is preferable because it results in a large dissolution contrast and improved resolution.

When the dissolution rate of the film formed from the resin composition of the present invention in an aqueous tetramethylammonium hydroxide solution is measured before and after exposure at 100 mJ/ ^cm2 , the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is preferably 0.5 μm/sec or more. The value of 0.5 μm/sec or more is preferable because it results in a large dissolution contrast and improved resolution. The concentration of tetramethylammonium hydroxide in the aqueous tetramethylammonium hydroxide solution may be, for example, 2.38% by mass.

<Restrictions on substances contained in resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

In addition, methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.Among them, those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

A conventionally known container can be used as the container for the resin composition of the present invention. As the container, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure of six types of resin, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention. An example of such a container is the container described in JP 2015-123351 A.

<Cured Product of Resin Composition>
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing a resin composition.
The resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film-like, rod-like, spherical, pellet-like, etc. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated by the following formula.
Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) x 100

<Characteristics of the cured product of the resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
The breaking elongation of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

<Preparation of Resin Composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be a conventionally known method.
Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

In order to remove foreign matter such as dust and fine particles from the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene). The filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As an example of a connection mode, an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage may be connected in series. In addition, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
After filtration using a filter, the resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.

(Method for producing the cured product)
The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.
It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
It is particularly preferable that the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
The method for producing a cured product preferably includes the film-forming step and a step of heating the film.
Each step will be described in detail below.

<Film formation process>
The resin composition of the present invention can be used in a film-forming process in which the resin composition is applied onto a substrate to form a film.
The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.

[Substrate]
The type of substrate can be appropriately determined according to the application, and is not particularly limited. Examples of substrates include semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs). The substrate is preferably a semiconductor-prepared substrate, more preferably a silicon substrate, a Cu substrate, or a mold substrate.
These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
The shape of the substrate is not particularly limited, and may be circular or rectangular.
The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and preferably, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
As the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured material) or to the surface of a metal layer, the resin layer or metal layer serves as the substrate.

The resin composition is preferably applied to a substrate by coating.
Specific examples of the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred. A film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the resin composition according to the means to be applied. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of the spin coating method, for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
As for the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
Also, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
A pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
After the film-forming step (layer-forming step), the above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably carried out after the film-forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. Drying may be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

<Exposure process>
The film may be subjected to an exposure step to selectively expose the film to light.
The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light.
Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
The amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm ² , and more preferably 200 to 8,000 mJ/cm ² , calculated as exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

In terms of the light source, the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), _F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm, third harmonic 355 nm, etc. of YAG laser. For the resin composition of the present invention, exposure by a high pressure mercury lamp is particularly preferred, and exposure by i-line is more preferred from the viewpoint of exposure sensitivity.
The exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.

<Post-exposure baking process>
The film may be subjected to a step of heating after exposure (post-exposure baking step).
That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
The post-exposure baking step can be carried out after the exposure step and before the development step.
The heating temperature in the post-exposure baking step is preferably from 50°C to 140°C, and more preferably from 60°C to 120°C.
The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
The rate of temperature rise may be appropriately changed during heating.
The heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used.
It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

<Developing process>
After exposure, the film may be subjected to a development step in which the film is developed with a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern.
Development removes one of the exposed and unexposed areas of the film to form a pattern.
Here, development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.

[Developer]
The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

When the developer contains an organic solvent, the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent. The contents of this specification are incorporated herein. In addition, examples of alcohols that are suitable include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The content may be 100% by mass.

When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates the pattern, the performance of the pattern, such as breaking elongation, may be improved.

As the basic compound, from the viewpoint of reliability when it remains in the cured film (adhesion to a substrate when the cured product is further heated), an organic base is preferred.
As the basic compound, a basic compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, or the like is preferable. In order to promote the imidization reaction, a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferable, a secondary amine, a tertiary amine, or an ammonium salt is more preferable, a secondary amine or a tertiary amine is further more preferable, and a tertiary amine is particularly preferable.
From the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferable for the basic compound to be one that is unlikely to remain in the cured film (obtained cured product), and from the viewpoint of promoting cyclization, it is preferable for the basic compound to be one that is unlikely to decrease in the amount remaining before heating due to vaporization, etc.
Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.
For example, when the boiling point of the organic solvent is 100° C., the basic compound used preferably has a boiling point of 80° C. or higher, and more preferably has a boiling point of 100° C. or higher.
The developer may contain only one kind of basic compound, or may contain two or more kinds of basic compounds.

Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

The preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the composition described above. In particular, it is preferred that the base generator is a thermal base generator.

When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
When the basic compound or base generator is a solid in the environment in which the developer is used, the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the developer.
The developer may contain at least one of a basic compound and a base generator, or may contain two or more of them. When at least one of a basic compound and a base generator is two or more, the total amount of them is preferably within the above range.

The developer may further comprise other components.
Examples of other components include known surfactants and known defoamers.

[Method of Supplying Developer]
The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.

In the development process, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Also, a method may be adopted in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[Rinse solution]
When the developer is an alkaline aqueous solution, the rinse liquid may be, for example, water. When the developer is an organic solvent-containing developer, the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).

When the rinsing liquid contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent.
The organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably has a lower solubility for the pattern than the organic solvent contained in the developer.

When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more kinds. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, propylene glycol monomethylether acetate (PGMEA), or propylene glycol monomethylether (PGME), more preferably cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.

The rinse liquid may contain at least one of a basic compound and a base generator.
Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinsing liquid contains an organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention.
Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments thereof are also the same.
The basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.

When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
When the basic compound or base generator is a solid in the environment in which the rinse liquid is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the rinse liquid.
When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds. When at least one of the basic compound and the base generator contains two or more kinds, the total amount thereof is preferably within the above range.

The rinse solution may further contain other ingredients.
Examples of other components include known surfactants and known defoamers.

[Method of Supplying Rinse Liquid]
The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
The method of supplying the rinsing liquid in the rinsing step may be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.

The development process may include a step of contacting the pattern with a processing liquid after the treatment with the developer or after the pattern is washed with a rinsing liquid. Also, a method may be adopted in which the processing liquid is supplied before the developer or rinsing liquid in contact with the pattern is completely dried.

The treatment liquid includes a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the above-mentioned rinse solution.
The method of supplying the processing liquid to the pattern can be the same as the above-mentioned method of supplying the rinsing liquid, and the preferred embodiments are also the same.

The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
In addition, when the basic compound or base generator is a solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the treatment liquid.
When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds. When at least one of the basic compound and the base generator contains two or more kinds, the total amount thereof is preferably within the above range.

<Heating process>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step.
The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step.
In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the crosslinking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator through heating.

The heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the starting temperature to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature rise rate at 1° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate at 12° C./min or less, it is possible to alleviate the residual stress of the cured product.
In addition, in the case of an oven capable of rapid heating, the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher.
The upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, and even more preferably 240° C. or less.

Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to perform the process while irradiating ultraviolet rays as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C.
Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.

From the viewpoint of preventing decomposition of the specific resin, the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

<Post-development exposure step>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light instead of or in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted.
In the post-development exposure step, it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
The exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , and more preferably 100 to 15,000 mJ/cm ² , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity.
The post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

<Metal Layer Forming Process>
The pattern obtained by the development step (preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably subjected to at least one of a heating step and a post-development exposure step).

The metal layer can be made of any existing metal type without any particular limitations, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible. More specifically, examples of the method include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating. A preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.

The thickness of the metal layer at its thickest point is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

<Applications>
Examples of the field of application of the method for producing the cured product of the present invention or the cured product include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd. "High-performance and Applied Technology of Polyimides" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association/editor "Latest Polyimides Basics and Applications" NTS, August 2010.

The method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.

(Laminate and method for manufacturing laminate)
The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
The laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

In other words, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
As the laminate, for example, a laminate having at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example.
The layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Lamination process>
The method for producing the laminate of the present invention preferably includes a lamination step.
The lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order. However, at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated. In addition, after at least one of (d) the heating process and the post-development exposure process, (e) a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.

If a further lamination step is performed after the lamination step, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
For example, a structure of 2 to 20 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
The layers may be the same or different in composition, shape, film thickness, etc.

In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer. Specifically, the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be laminated alternately.

(Surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
The surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved.
It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.

(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
As specific examples of semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these are incorporated herein by reference.

(resin)
The present invention also relates to the above-mentioned resin (A). The resin (A) has been described above.

The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Synthesis Example of Resin (A)>
(Synthesis of A-1)
20.0 g (38.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 5.41 g (25.0 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl were dissolved in 125 ml of NMP and stirred at 200°C for 3 hours in a nitrogen atmosphere to obtain polyimide (pA-1). When GPC was measured at this point, Mn was 2,800.
Next, 1.58 g (4.5 mmol) of 1,3,5-tris(4-aminophenyl)benzene and 1.48 g (13.6 mmol) of 4-aminophenol were added to the solution containing the polyimide (pA-1), and the mixture was stirred at 200° C. for 3 hours under a nitrogen atmosphere to obtain polyimide (qA-1). When GPC was measured at this point, it was found that Mn was 8,000 and that one polymer had an average of 1.0 branch structure (branch structure with triphenylbenzene as a branch point).
The solution containing the obtained polyimide (qA-1) was brought to room temperature, and 0.42 g of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 14.6 g of 4-chloromethylstyrene, 15.9 g of potassium carbonate, and 1.91 g of potassium iodide were added, and the mixture was stirred at 90° C. for 14 hours. 375 ml of THF was added to the obtained polyimide solution, and salts were removed by filtration. The obtained filtrate was dropped into 1500 ml of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40° C. for 1 day to obtain polyimide (A-1) as a powder. The Mn and Mw of the obtained A-1 were measured, and found to be Mn=8,000 and Mw=22,000.

(Synthesis of A-2)
20.0g (64.5mmol) of 4,4'-oxydiphthalic dianhydride, 16.3g (125mmol) of 2-hydroxyethyl methacrylate, 0.39g (1.93mmol) of 1,12-dodecanediol, and 0.55g of TEMPO were dissolved in 60ml of diglyme, and 39.2g (284mmol) of pyridine was added and stirred at 60°C for 4 hours. The mixture was then cooled to 0°C, and 15.34g (129mmol) of thionyl chloride was added dropwise over 15 minutes, and the mixture was stirred for 1 hour to obtain a white precipitate of pyridinium hydrochloride. Then, 10.3g (51.6mmol) of 4,4'-diaminodiphenyl ether dissolved in 75ml of NMP was added dropwise over 30 minutes. The mixture was stirred at room temperature for 1 hour, and 8ml of ethanol was added and stirred for another 1 hour. The resulting solution was added dropwise to 1500ml of water to precipitate a polymer. The polymer collected by filtration was dried at 40° C. under reduced pressure for 1 day to obtain polyamide (A-2) as a powder. The Mn and Mw of the obtained A-2 were measured to be Mn=12,000 and Mw=28,000. A-2 is also a polyimide precursor.

(Synthesis of A-3)
18.0 g (58.0 mmol) of 4,4'-oxydiphthalic dianhydride, 17.0 g (46.4 mmol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), and 2.53 g (23.2 mmol) of 4-aminophenol were dissolved in 100 ml of NMP and stirred at 200°C for 3 hours in a nitrogen atmosphere to obtain polyimide (pA-3).
The solution containing the obtained polyimide (pA-3) was brought to room temperature, and 20.2 g of 4-((t-butoxycarbonyl)oxy)benzyl 4-methylbenzenesulfonate, 24.0 g of potassium carbonate, and 2.89 g of potassium iodide were added, followed by stirring at 90° C. for 14 hours. 300 ml of THF was added to the obtained polyimide solution, and salts were removed by filtration. The obtained filtrate was dropped into 1500 ml of methanol to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40° C. for 1 day, yielding polyimide (A-3) as a powder. The Mn and Mw of the obtained A-3 were measured, revealing that Mn=6,400 and Mw=13,000.

(Synthesis of A-4)
Polyimide (A-4) was obtained under the same conditions as in the synthesis of A-3, except that N,N'-[[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis[1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxamide] was used instead of 4,4'-oxydiphthalic dianhydride, and 4-hydroxymethylphenol was used instead of 4-((t-butoxycarbonyl)oxy)benzyl 4-methylbenzenesulfonate. The Mn and Mw of the obtained A-4 were measured to find that Mn was 7,800 and Mw was 19,000.

(Synthesis of A-5)
10.0 g (32.2 mmol) of 4,4'-oxydiphthalic dianhydride and 2.27 g (70.9 mmol) of methanol were dissolved in 50 ml of diglyme, and 18.7 g (135 mmol) of pyridine was added and stirred at 60°C for 4 hours. The mixture was then cooled to 0°C, and 8.44 g (70.9 mmol) of thionyl chloride was added dropwise over 15 minutes, and the mixture was stirred for 1 hour to obtain a white precipitate of pyridinium hydrochloride. Then, 6.27 g (29.0 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl dissolved in 50 ml of NMP was added dropwise over 30 minutes. The mixture was stirred at room temperature for 1 hour, and 8 ml of ethanol was added and stirred for another 1 hour. The obtained solution was dropped into 1000 ml of water to precipitate a polymer. The polymer collected by filtration was dried at 40°C under reduced pressure for 1 day to obtain polyamide (pA-5) as a powder.
Next, 113 g (290 mmol) of dodecafluorosuberic acid, 60.8 g (232 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and 4.99 g (58.0 mmol) of methacrylic acid were dissolved in 300 ml of THF, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was added and stirred at room temperature for 6 hours. Polyamide (pA-5) was added thereto and stirred for another 6 hours. The obtained solution was dropped into 3000 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40° C. for 1 day to obtain polyamide (A-5) as a powder. The Mn and Mw of the obtained A-5 were measured, and found to be Mn=13,500 and Mw=32,000.

(Synthesis of A-6)
12.0 g (38.7 mmol) of 4,4'-oxydiphthalic dianhydride, 5.02 g (23.2 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, 0.73 g (5.80 mmol) of 2,4,6-triaminopyrimidine, and 2.11 g (19.3 mmol) of 4-aminophenol were dissolved in 125 ml of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain polyimide (pA-6).
Next, 0.35 g of TEMPO and 7.60 g of triethylamine were added to the solution containing the polyimide (pA-6), and the mixture was cooled to 0°C. Then, 6.87 g (65.8 mmol) of methacryl chloride was added dropwise over 15 minutes, and the mixture was stirred for 1 hour to obtain a white precipitate of triethylamine hydrochloride. The resulting solution was added dropwise to 1500 ml of water to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (qA-6) as a powder.
0.35 g (5.80 mmol) of 2-aminoethanol, 0.57 g (5.80 mmol) of maleic anhydride, and 0.01 g of TEMPO were dissolved in NMP, stirred at room temperature for 2 hours, and then stirred at 120° C. for 1 hour. The mixture was then cooled to room temperature, and 8.01 g (58.0 mmol) of 4-hydroxybenzoic acid and 26.7 g (139 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added, followed by stirring for 10 hours. The resulting solution was added dropwise to 2000 ml of water, filtered, and the precipitate was collected and dried at 40° C. under reduced pressure for 1 day to obtain polyester (rA-6).
Polyester (rA-6), 10.0 g of pyridine, and 0.35 g of TEMPO were dissolved in 100 g of NMP, and the mixture was cooled to 0° C., after which 0.69 g (5.82 mmol) of thionyl chloride was added dropwise over 15 minutes and stirred for 1 hour to obtain a white precipitate of pyridinium hydrochloride. A solution of polyimide (qA-6) dissolved in 200 g of NMP was added dropwise over 30 minutes and stirred for 3 hours. The obtained solution was added dropwise to 1500 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40° C. for 1 day to obtain polyimide (A-6) as a powder. The Mn and Mw of the obtained A-6 were measured to find that Mn=4,500 and Mw=9,500.

(Synthesis of A-7)
15.0g (68.8mmol) of pyromellitic anhydride and 4.41g (138mmol) of methanol were dissolved in 60ml of diglyme, and 41.8g (303mmol) of pyridine was added and stirred at 60°C for 4 hours. Next, the mixture was cooled to 0°C, and 16.4g (138mmol) of thionyl chloride was added dropwise over 15 minutes and stirred for 1 hour to obtain a white precipitate of pyridinium hydrochloride. Next, 14.9g (138mmol) of 1,4-phenylenediamine dissolved in 60ml of NMP was added dropwise over 30 minutes and stirred at room temperature for 1 hour. The obtained solution was dropped into 1500ml of water to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain a powder polyamide (pA-7). When GPC was measured at this point, Mn was 450.
Next, the obtained polyamide (pA-7) was dissolved in 60 g of cyclohexanone, and 11.6 g (22.9 mmol) of 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione dissolved in 30 ml of cyclohexanone was added dropwise at room temperature over 30 minutes. The mixture was further stirred for 1 hour, and the precipitated solid was collected by filtration to obtain polyamide (qA-7) having a branched structure. When GPC was measured at this point, it was found that Mn=1,900 and that one polymer had an average of 1.0 branched structure (branched structure with a structure derived from 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione as a branch point).
Next, 469 g (1.51 mol) of 4,4'-oxydiphthalic dianhydride, 149 g (688 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, 8.61 (68.8 mmol) of 2,4,6-triaminopyrimidine, and 165 g (1.51 mol) of 4-aminophenol were dissolved in 3000 ml of NMP and stirred at 200°C for 4 hours under a nitrogen atmosphere. Next, the mixture was cooled to 0°C, and then 0.80 g of TEMPO and 140 g of triethylamine were added, and 144 g (1.38 mmol) of methacrylic chloride was added dropwise over 30 minutes and stirred for 1 hour to obtain a white precipitate of triethylamine hydrochloride. The obtained solution was dropped into 5000 ml of water to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (rA-7) as a powder. At this stage, GPC measurement revealed that Mn was 700.
Next, 15.0 g (68.8 mmol) of pyromellitic anhydride and 2.20 g (68.8 mmol) of methanol were dissolved in 60 ml of diglyme, and 38.0 g (275 mmol) of pyridine was added and stirred at 60 ° C. for 4 hours. Next, the mixture was cooled to 0 ° C., and then 16.4 g (137 mmol) of thionyl chloride was added dropwise over 15 minutes, and the mixture was stirred for 1 hour to obtain a white precipitate of pyridinium hydrochloride. A solution obtained by dissolving polyamide (qA-7) in 150 g of NMP was added dropwise over 1 hour to the obtained white precipitate of pyridinium hydrochloride, and the mixture was stirred for 1 hour while maintaining the temperature at 0 ° C. The obtained solution was then added dropwise over 1 hour to a solution obtained by dissolving polyimide (rA-7) in 2000 ml of NMP, and the mixture was stirred at room temperature for 2 hours. The obtained solution was added dropwise to 8000 ml of water to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40° C. for 1 day to obtain a powdered polyimide (A-7). Measurements of Mn and Mw of the resulting A-7 revealed that Mn=24,000 and Mw=68,000, and each polymer had an average of 1.0 branched structure (branched structure with a structure derived from 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione as a branch point).

(Synthesis of B-1)
20.0g (64.5mmol) of 4,4'-oxydiphthalic dianhydride, 19.0g (64.5mmol) of 4,4'-biphthalic anhydride, and 19.6g (129mmol) of hydroxyethyl methacrylate were dissolved in 100ml of γ-butyrolactone, and 39.2g (142mmol) of pyridine was added and stirred at room temperature for 20 hours. Next, the mixture was cooled to 0°C, and then 26.6g (129mmol) of N,N'-dicyclohexylcarbodiimide dissolved in 60ml of γ-butyrolactone was added dropwise over 15 minutes and stirred at room temperature for 1 hour. Next, 23.3g (116mmol) of 4,4'-diaminodiphenyl ether dissolved in 100ml of NMP was added dropwise over 30 minutes and stirred for 24 hours. The obtained solution was added dropwise to 1500ml of water to precipitate a polymer. The polymer collected by filtration was dried at 40° C. under reduced pressure for 1 day to obtain polyamide (B-1) as a powder. The Mn and Mw of the obtained B-1 were measured to be Mn=12,000 and Mw=25,000.

(Synthesis of B-2)
15.5g (60.1mmol) of 4,4'-diphenyletherdicarboxylic acid was dissolved in 90g of NMP, and the flask was cooled to 5°C. Then, 14.3g (120mmol) of thionyl chloride was dropped and reacted for 30 minutes to obtain a solution of 4,4'-diphenyletherdicarboxylic acid dichloride. Next, in a separate flask, 19.8g (54.1mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane was dissolved in 90g of NMP. Then, while maintaining the temperature at 0-5°C, the 4,4'-diphenyletherdicarboxylic acid dichloride solution was dropped over 30 minutes and stirred for 3 hours. Next, the resin solution was dropped into 2000ml of water to precipitate a precipitated polymer. The polymer collected by filtration was dried under reduced pressure at 45°C for 1 day to obtain polyamide (B-2). The Mn and Mw of the resulting B-2 were measured, and were found to be Mn=11,000 and Mw=23,000.

<Examples and Comparative Examples>
In each of the Examples and Comparative Examples, the components shown in Tables 1 and 2 below were mixed to obtain a resin composition.
Specifically, the content of each component other than the solvent shown in Tables 1 and 2 was the amount (parts by mass) shown in the "parts by mass" row.
When two or more compounds were used as each component, the "type" and "parts by mass" were listed separated by "/". In these columns, the order of listing separated by "/" corresponds to each other.
The amount of the solvent used was adjusted so that the solid content concentration was as shown in the "Solid content concentration (mass %)" in Tables 1 and 2.
The "type" and "mass ratio" of the solvents used are shown in Tables 1 and 2. The "mass ratio" of the solvent is the content (mass %) of each type of solvent relative to the total solvent.
In Tables 1 and 2, the notation "-" indicates that the resin composition does not contain the corresponding component.
The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter having a pore width of 0.5 μm.

Details of each ingredient listed in the table above are as follows:

<Resin>
The structure of the compound used as the resin is shown below.

A-1 is a resin (polyimide) having the groups represented by the above formulae A-1(1) to A-1(4) in the amounts (mol %) shown below each structural formula. The amounts of the groups represented by the formulae A-1(1) to A-1(4) are the proportions (mol fractions) of each group relative to the total amount (100 mol %) of the groups represented by the formulae A-1(1) to A-1(4).
In the above formula, *a and *b represent bonding positions, provided that *a and *b are bonded.
A-1 has a branched structure composed of a main chain and a branched chain having a formula weight of 100 or more bonded to the main chain.
The repeating unit in A-1 formed by bonding a group represented by formula A-1(1) and a group represented by formula A-1(3) corresponds to the repeating unit represented by formula (1A) above.

A-2 is a resin (polyamide) in which repeating units bracketed in [ ] are randomly bonded to each other, as represented by the above formula A-2(1). A-2 is also a polyimide precursor.
In the above formula, *a and *b represent bonding positions. *a and *b are bonded. *a in formula A-2(1) is bonded to *b of the group represented by formula A-2(2) or the group represented by formula A-2(3).
The contents (mol%) of the group represented by formula A-2(2) and the group represented by formula A-2(3) are shown below each structural formula. The contents of each group are the proportions (mol fractions) of each group relative to the total content (100 mol%) of the group represented by formula A-2(2) and the group represented by formula A-2(3).
A-2 is a network polymer and has a branched structure. The formula weight of the groups between the branching points of the network structure of A-2 is 100 or more.

A-3 is a resin (polyimide) with a main chain made up of repeating units bracketed in [ ]. A-3 has a branched structure made up of a main chain and a branched chain with a formula weight of 100 or more bonded to the main chain. A-3 has a crosslinkable group represented by formula (EC2) and a crosslinkable group represented by formula (EC2a) at its terminals. In the above formula, *a to *d represent bonding positions. The repeating units are bonded to each other at *a and *b. The crosslinkable group represented by formula (EC2) is bonded to *a at *c. The crosslinkable group represented by formula (EC2a) is bonded to *b at *d.

A-4 is a resin (polyimide) with a main chain made up of repeating units bracketed in [ ]. A-4 has a branched structure made up of a main chain and a branched chain with a formula weight of 100 or more bonded to the main chain. A-4 has a crosslinkable group represented by formula (EC3) and a crosslinkable group represented by formula (EC3a) at its terminals. In the above formula, *a to *d represent bonding positions. The repeating units are bonded to each other at *a and *b. The crosslinkable group represented by formula (EC3) is bonded to *a at *c. The crosslinkable group represented by formula (EC3a) is bonded to *b at *d. Each x independently represents a natural number.

A-5 is a resin (polyamide) with a main chain made up of repeating units enclosed in [ ]. A-5 is also a polyimide precursor. A-5 has a branched structure made up of a main chain and branched chains bonded to the main chain with a formula weight of 100 or more. Each x independently represents a natural number.

A-6 is a resin (polyimide) having the groups represented by the above formulae A-6(1) to A-6(4) in the amounts (mol%) shown below each structural formula. The amounts of the groups represented by the formulae A-6(1) to A-6(4) are the proportions (mol fractions) of each group relative to the total amount (100 mol%) of the groups represented by the formulae A-6(1) to A-6(4).
In the above formula, *a and *b represent bonding positions, provided that *a and *b are bonded, and each x independently represents a natural number.
A-6 has a branched structure composed of a main chain and a branched chain having a formula weight of 100 or more bonded to the main chain.
The repeating unit in A-6 formed by bonding a group represented by formula A-6(1) and a group represented by formula A-6(3) corresponds to the repeating unit represented by formula (1A) above.

A-7 is a resin (polyamideimide) having the groups represented by the above formulae A-7(1) to A-7(5) in the amounts (mol%) shown below each structural formula. The amounts of the groups represented by the formulae A-7(1) to A-7(5) are the proportions (mol fractions) of each group relative to the total amount (100 mol%) of the groups represented by the formulae A-7(1) to A-7(5).
In the above formula, *a to *d represent bonding positions, with the proviso that *a is bonded to *b, and *c is bonded to *d. Each x independently represents a natural number.
A-7 is a network polymer and has a branched structure. The formula weight of the groups between the branching points of the network structure of A-7 is 100 or more.
The repeating unit in which a group represented by formula A-7(3) bonded to a group represented by formula A-7(1) is bonded at *c to three *d in the group represented by formula A-7(4) in A-7 corresponds to the repeating unit represented by formula (1A) and the repeating unit represented by formula (1A-1-PA).

B-1 is a resin (polyamide) in which repeating units enclosed in [ ] are randomly bonded together. The content of each repeating unit is 50 mol%. In the above formula, *a to *d represent the bonding positions. Repeating units are bonded together at *a or *c and *b or *d.

B-2 is a resin (polyamide) with a main chain made up of repeating units enclosed in [ ]. In the above formula, *a and *b represent bonding positions. Repeating units are bonded to each other at *a and *b.

<Initiator>
The structural formula of the compound used as the initiator is shown below.

<Crosslinking Agent>
The structural formula of the compound used as the crosslinking agent is shown below, where Pr represents an n-propyl group.

<Silane coupling agent>
The structural formula of the compound used as the silane coupling agent is shown below.

<Migration Inhibitor>
The structural formula of the compound used as the migration inhibitor is shown below.

<Thermal Base Generator>
The structural formula of the compound used as the thermal base generator is shown below.

<Light absorber>
The structural formula of the compound used as the light absorber is shown below.

G-1 and G-2 are listed in the "Additives" column in Tables 1 and 2.

<Solvent>
The solvents used are shown below.
DMSO: dimethyl sulfoxide GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone

<Developer>
The developers used are shown below.
S-1: Cyclopentanone S-2: 2.38% by mass aqueous solution of tetramethylammonium hydroxide

<Rinse solution>
As the rinse liquid, water or PGMEA was used.

[Measurement of dissolution rate difference]
Each resin composition was applied onto a silicon wafer by spin coating to form a coating film. The silicon wafer provided with the obtained coating film was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer (film) having a thickness of 10 μm on the silicon wafer. Before and after exposure to light at 100 mJ/ ^cm2 , the obtained film was immersed in γ-butyrolactone or an aqueous solution of tetramethylammonium hydroxide (the concentration of tetramethylammonium hydroxide was 2.38% by mass) for 15 seconds. In the examples and comparative examples in which the developer described in the "Developer" column of Tables 1 and 2 was S-1, γ-butyrolactone was used, and in the examples and comparative examples in which the developer was S-2, an aqueous solution of tetramethylammonium hydroxide was used. After immersion, the wafer was rotated at 2000 rpm for 10 seconds, and the thickness of the film after immersion was measured at 10 points on the coating surface with an ellipsometer (KT-22 manufactured by Foothill Co., Ltd.) and calculated as the arithmetic average value. The dissolution rate (μm/sec) was measured from the film thickness measured above and the film thickness before immersion of 10 μm. The "difference in dissolution rate" was calculated by subtracting the dissolution rate after exposure from the dissolution rate before exposure. The results are shown in the "difference in dissolution rate" column of Tables 1 and 2.

<Evaluation>
The evaluation was carried out as follows, and the results are shown in Tables 1 and 2 above.

[Measurement of CTE (coefficient of thermal expansion)]
Each resin composition was applied onto a silicon wafer by spin coating to form a coating film. The silicon wafer with the obtained coating film was dried on a hot plate at 100° C. for 5 minutes to obtain a film of uniform thickness on the silicon wafer. The thickness of each film was 5 μm.
The film was heated at a heating rate of 10° C./min, heated at 230° C. for 180 minutes, and cured to obtain a cured product (cured film).
The above cured product was immersed in a 4.9 mass % aqueous solution of hydrofluoric acid, peeled off from the silicon wafer, and then punched out using a punching machine into test pieces measuring 50 mm in length, 20 mm in width, and 15 μm in thickness.
The CTE of the prepared test specimens at 25° C. to 125° C. was measured using a TMA450 (TA Instruments).
The temperature increase and decrease conditions during the evaluation were as follows (1) to (4).
(1) Heat the sample from room temperature (23° C.) to 130° C. at a rate of 5° C./min.
(2) The temperature is decreased from 130° C. to 10° C. at a rate of 5° C./min.
(3) Ramp the temperature from 10° C. to 220° C. at a rate of 5° C./min.
(4) Allow to cool naturally to room temperature.
The elongation (displacement) of the sample was measured during the temperature increase and decrease processes of (1) to (4) above, and the CTE was calculated by dividing the elongation (displacement) of the sample at 25° C. and 125° C. in process (3) by the temperature.
(Example: If the length of the sample at 25°C is 50 mm and the length of the sample at 125°C is 50.2 mm, the displacement is calculated as 0.4% = 4000 ppm, and the CTE is calculated as 4000/(125-25) = 40 ppm/°C.)

[Resolution]
Each resin composition was applied by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on the surface, and dried on a hot plate at 110°C for 3 minutes to form a resin composition layer having a film thickness of 5 μm after film formation. The resin composition layer was then exposed using a stepper (FPA-3000 i5 (Canon Corporation)). Exposure was performed at a wavelength of 365 nm and 100 mJ/ ^cm2 through a mask in which a hole pattern with a diameter of 0.5 to 20 μm was formed at 1 μm intervals. The exposed film obtained was heated on a hot plate at the temperature and time described in the "Post-exposure heating" column in Tables 1 and 2, as necessary. "120°C 1 min" in Tables 1 and 2 indicates that the film was heated at a temperature of 120°C for 1 minute.
The resist was then developed for 15 seconds with a developer shown in the "Developer" column of Tables 1 and 2, rinsed for 30 seconds with a rinse shown in the "Rinsing Solution" column of Tables 1 and 2, and then heated at a heating rate of 10°C/min in a nitrogen atmosphere until it reached 230°C, at which point it was heated at 230°C for 1 hour to obtain a hole pattern. The smallest size of the hole patterns that were formed is shown in the "Resolution" column of Tables 1 and 2. The smaller the diameter of the hole pattern that can be formed, the better the resolution.

The results shown in Tables 1 and 2 show that the resin compositions of the examples of the present invention are capable of forming films with excellent resolution and small CTE. In addition, it was found that the resins used in the examples are capable of forming films with excellent resolution and small CTE.

The present invention provides a resin composition that can form a film with excellent resolution and a small CTE.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Patent Application No. 2023-188358) filed on November 2, 2023, the contents of which are incorporated herein by reference.

Claims (18)

A resin composition comprising a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (2A):

In formula (1A) and formula (2A),
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent an organic group.
W ₁ , W ₂ , W ₃ and W ₄ each independently represent a linking group.
P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
m, n, p and q each independently represent an integer of 1 or more.
When a plurality of W ₁ , W ₂ , W ₃ , W ₄ , P ₀₁ , P ₀₂ , P ₀₃ and P ₀₄ are present, they may be the same or different. A resin composition comprising a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):

In formula (1) and formula (2),
X ₁ , X ₂ , Y ₁ and Y ₂ each independently represent an organic group.
W ₁ , W ₂ , W ₃ and W ₄ each independently represent a linking group.
_P1 , _P2 , _P3 and _P4 each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
Q ₁ , Q ₂ , Q ₃ and Q ₄ each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
m, n, p and q each independently represent an integer of 1 or more.
When a plurality of _W1 , _W2 , _W3 , _W4 , _P1 , _P2 , _P3 , _P4 , _Q1 , _Q2 , _Q3 and _Q4 are present, they may be the same or different. At least one of P ₀₁ and P ₀₂ in the formula (1A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group,
The resin composition according to claim 1, wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group. At least one of P ₀₁ and P ₀₂ in the formula (1A) has a branched structure;
The resin composition according to claim 1, wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) has a branched structure. At least one of P ₀₁ and P ₀₂ in the formula (1A) has at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-PA) and a repeating unit represented by the following formula (2-PA),
At least one of P ₀₃ and P ₀₄ in the formula (2A) has at least one selected from the group consisting of a repeating unit represented by the following formula (1-PA) and a repeating unit represented by the following formula (2-PA). The resin composition according to claim 1.

In formula (1-PA) and formula (2-PA),
X _1p , X _2p , Y _1p and Y _2p each independently represent an organic group.
W _1p , W _2p , W _3p and W _4p each independently represent a linking group.
P _01p , P _02p , P _03p and P _04p each independently represent an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group and a fluoroalkylene group.
ap, bp, cp, and dp each independently represent an integer of 0 or more, provided that at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more.
mp, np, pp and qp each independently represent an integer of 1 or more.
When a plurality of _W1p , _W2p , _W3p , _W4p , _P01p , _P02p , _P03p and _P04p are present, they may be the same or different. The resin composition according to claim 1, wherein the resin has at least one crosslinkable group at at least one end. At least one of P ₀₁ and P ₀₂ in the formula (1A) has a crosslinkable group,
The resin composition according to claim 1, wherein at least one of P ₀₃ and P ₀₄ in the formula (2A) has a crosslinkable group. The resin composition according to claim 6, wherein the crosslinkable group includes at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group. The resin composition according to claim 1, wherein at least one of P ₀₁ and P ₀₂ in the formula (1A) has a phenol group, and at least one of P ₀₃ and P ₀₄ in the formula (2A) has a phenol group. The resin composition according to claim 1, further comprising a polymerization initiator. The resin composition according to claim 1, further comprising a polymerizable compound. The resin composition according to claim 1, further comprising a light absorbing agent. The resin composition according to claim 12, wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds. The resin composition according to claim 1, wherein when a dissolution rate of the film formed from the resin composition is measured in gamma-butyrolactone before and after exposure to light at 100 mJ/ ^cm2 , the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm/sec or more. When a film formed from the resin composition is exposed to light at 100 mJ/ ^cm2 and the dissolution rate of the film in an aqueous tetramethylammonium hydroxide solution is measured before and after the film is exposed to light, the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm/sec or more. The resin composition according to claim 1. The resin composition according to claim 1, wherein the resin has a repeating unit represented by formula (1A) and a repeating unit represented by formula (2A). The resin composition according to any one of claims 1 to 16, which is used to form an insulating film. The resin composition according to any one of claims 1 to 16, which is used to form an interlayer insulating film for a redistribution layer.