TW201817773A - Negative photosensitive resin composition, cured film, method for producing cured film, semiconductor device, method for producing laminate, method for producing semiconductor device, and polyimide precursor - Google Patents

Abstract

Provided is a negative photosensitive composition contains a polyimide precursor, a photopolymerization initiator, and a solvent. The polyimide precursor has a repeating unit represented by formula (1), and a structure represented by "(A)l-L1-*" on at least one terminal. In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R1 is a polymerizable group, and R2 is a monovalent organic group. In the abovementioned structure, A represents a polymerizable group, L1 represents a single bond or an l+1-valent organic group, l represents an integer from 2 to 10, and * represents the binding site with another site.

Description

Negative photosensitive resin composition, hardened film, method for manufacturing hardened film, semiconductor device, method for manufacturing laminated body, method for manufacturing semiconductor device, and polyimide precursor

The present invention relates to a negative photosensitive resin composition, a method for producing a cured film, a method for producing a cured film, a method for producing a semiconductor element, a laminate, a method for producing a semiconductor element, and a polyimide precursor.

Thermosetting resins, such as polyimide resins, which are hardened by cyclization, are excellent in heat resistance and insulation properties, and are therefore used in insulating layers and the like of semiconductor devices. In addition, since polyimide resins have low solubility in solvents, they are also used as follows: they are used in the state of precursors (polyimide precursors) before the cyclization reaction, and after being applied to a substrate or the like, they are heated. The polyfluorene imide precursor is cyclized to form a hardened film.

For example, Patent Document 1 describes a photosensitive resin composition containing (A) a repeating unit represented by the general formula (1) in a main chain, and having photopolymerizable carbon at both ends of the molecule- Polyimide precursors of actinic ray functional groups with carbon double bond substituents and actinic ray functional groups modified at the ends by aminobenzenes or trimellitic acid derivatives, (B) having photopolymerizable functions Based photosensitizers and (C) photopolymerization initiators containing N-aryl-α-amino acids and thioxanthone, wherein the content of the photopolymerization initiator is relative to that of the polyimide precursor 100 The mass part is 7-15 mass parts. [Chemical Formula 1] In the formula, R ¹ is a tetravalent organic group, and R ² is a divalent organic group. [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 2013-76845

However, in Patent Document 1, since it has a polyamic acid structure, it is susceptible to hydrolysis by water. Therefore, the stability over time is low, and further, it is impossible to purify the synthesized resin with water series, so it is difficult to apply it to semiconductor applications requiring high quality. It was also found that the residual film rate of the exposed portion during development of the polyimide precursor described in Patent Document 1 was low. On the other hand, from the viewpoint of reliability requirements at high temperatures, etc., it is expected to increase the glass transition temperature of the film.

An object of the present invention is to solve the above-mentioned problems, and to provide a negative photosensitive resin composition capable of producing a film having a high residual film rate at an exposed portion during development and a high glass transition temperature. Another object is to provide a cured film using the negative photosensitive resin composition, a method for producing a cured film, a method for producing a semiconductor element, a laminate, a method for producing a semiconductor element, and a polyimide precursor.

As a result of intensive research by the present inventors, it has been found that the above-mentioned problems can be achieved by providing polymerizable groups on both sides of the terminal and side chains of the polyimide precursor, and the present invention has been completed. Accordingly, the present invention provides the following. <1> A negative photosensitive resin composition comprising a polyimide precursor, a photopolymerization initiator, and a solvent, the polyimide precursor having a repeating unit represented by formula (1), and at least One end has a structure represented by Formula (2), [Chemical Formula 2] In the formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ is a polymerizable group, R ² is a monovalent organic group, (A) _l -L- * (2) Formula (2) Here, A represents a polymerizable group, L represents a single bond or an l + 1-valent organic group, l represents an integer of 2 to 10, and * represents a bonding site with another site. <2> The negative photosensitive resin composition according to <1>, wherein l in the formula (2) is an integer of 2 to 5. <3> The negative photosensitive resin composition according to <1> or <2>, wherein R ² is a polymerizable group. <4> The negative-type photosensitive resin composition according to any one of <1> to <3>, wherein each of the polymerizable groups of the polyfluorene imide precursor contains a carbon-carbon unsaturated group independently Double bond group. <5> The negative photosensitive resin composition according to any one of <1> to <4>, wherein the structure represented by the formula (2) is a structure represented by the formula (3) or (4), [Chemical Formula 3] In formula (3), R ³ represents a hydrogen atom or a methyl group, Z represents an oxygen atom or NH, L ² represents a single bond or an m + 1-valent organic group, m represents an integer of 2 to 10, and * represents a bond with another site A junction site. In the formula (4), L ³ represents a single bond or an n + 1-valent organic group, n represents an integer of 2 to 10, and * represents a junction site with another site. <6> The negative-type photosensitive resin composition according to any one of <1> to <5>, wherein the polyimide precursor contains the polyimide precursor in a repeating unit constituting the polyimide precursor. In the structure represented by -COOR, the ratio of the structure of the group containing a polymerizable group in R is 30% or more, where R is a substituent. <7> The negative photosensitive resin composition according to any one of <1> to <6>, further comprising a polyfunctional radical polymerizable monomer. <8> The negative photosensitive resin composition according to any one of <1> to <7>, further comprising a hot alkali generator. <9> The negative photosensitive resin composition according to any one of <1> to <8>, wherein the photopolymerization initiator is at least one selected from an oxime compound and a metallocene compound. <10> The negative photosensitive resin composition according to any one of <1> to <9>, which is a negative photosensitive resin composition for forming an interlayer insulating film for a redistribution layer. <11> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <10>. <12> The cured film according to <11>, wherein the film thickness of the cured film is 1 to 30 μm. <13> A method for producing a cured film, comprising: a process for forming a photosensitive resin composition layer; applying the negative photosensitive resin composition according to any one of <1> to <10> to a substrate; Layered; an exposure process that exposes the negative photosensitive resin composition layer; and a development process that develops the exposed photosensitive resin composition layer. <14> The method for producing a cured film according to <13>, which comprises a heating process of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development process. <15> A semiconductor device having the cured film according to <11> or <12>. <16> A method for producing a laminated body, comprising the method for producing a cured film according to <13> or <14>. <17> A method for manufacturing a semiconductor device, including the method for manufacturing a cured film according to <13> or <14>. <18> A polyimide precursor having a repeating unit represented by formula (1), and having a structure represented by formula (2) at at least one end, [Chemical Formula 4] In the formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ is a polymerizable group, R ² is a monovalent organic group, (A) _l -L- * (2) Formula (2) Here, A represents a polymerizable group, L represents a single bond or an l + 1-valent organic group, l represents an integer of 2 to 10, and * represents a bonding site with another site. <19> The polyfluorene imide precursor according to <18>, wherein R ² is a polymerizable group. <20> The polyimide precursor according to <18> or <19>, wherein A in the formula (2) is a group containing a carbon-carbon unsaturated double bond. <21> The polyfluorene imide precursor according to any one of <18> to <20>, wherein l in the formula (2) is an integer of 2 to 5. [Inventive effect]

According to the present invention, it is possible to provide a negative-type photosensitive resin composition capable of producing a film having a high residual film ratio in an exposed portion during development and a high glass transition temperature. In addition, it is possible to provide a cured film using the negative photosensitive resin composition, a method for producing a cured film, a method for producing a semiconductor element, a laminate, a method for producing a semiconductor element, and a polyimide precursor.

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. Regarding the label of a group (atomic group) in this specification, the unrecorded and unsubstituted labels include both a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, the drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for the exposure, actinic rays such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams, or radiation are generally mentioned. In the present specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In this specification, "(meth) acrylate" means either or both "acrylate" and "methacrylate", and "(meth) acrylic" means "acrylic" and "methacrylic" Either or both, "(meth) acrylfluorenyl" means either or both of "acrylfluorenyl" and "methacrylfluorenyl". In this specification, the term "process" is not only an independent process, but even if it cannot be clearly distinguished from other processes, if the expected effect of the process can be achieved, it is also included in this term. In the present specification, the solid content concentration refers to the mass percentage of components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25 ° C. In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are measured based on gel permeation chromatography (GPC), and are defined as styrene conversion values. In this specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and a protective column TSKguardcolumn SuperAW-H ､ TSK SuperAWM-H (TOSOH CORPORATION) System). Unless otherwise stated, the eluent was measured by N-methyl-2-pyrrolidone (NMP). In addition, unless otherwise specified, the detection is performed by a detector using a differential refractive index (RI).

<Negative photosensitive resin composition> The negative photosensitive resin composition of the present invention (hereinafter also referred to as the composition of the present invention) includes a polyimide precursor photopolymerization initiator and a solvent, and a polyimide precursor The object has a repeating unit represented by the formula (1) described later, and has a structure represented by the formula (2) described later on at least one end.

The composition according to the present invention can be a negative photosensitive resin composition having excellent resolution. The mechanism by which such an effect can be obtained is estimated as follows. According to the study by the present inventors, it was found that the glass transition temperature (Tg) can be increased by introducing a polymerizable group at the terminal of the polyfluorene imide precursor. So far, because a polymerizable group can be introduced at a high density, a polyfluorene imide precursor usually introduces a polymerizable group into a side chain. However, it was found that if a polymerizable group is introduced into the side chain of the polyfluorene imide precursor, the polymerizable group of the side chain may be detached when the polyfluorine imide precursor is cyclized. On the other hand, if a polymerizable group is introduced into the terminal of the polyfluorene imide precursor, the polymerizable group will not be detached even if cyclization is performed. However, it was found that when a polymerizable group is introduced only at the end of the main chain, the resolution during development is deteriorated. In particular, it was found that the residual film rate of the exposed portion during development was significantly lower. Then, a polymerizable group was introduced into the terminal of the polyfluorene imide precursor, and a polymerizable group was also introduced into the side chain boldly, thereby achieving a balance between good resolution and high Tg. In particular, in the present invention, even if the molecular weight of the polyfluorene imide precursor is large, good resolution can be achieved. Furthermore, with the configuration of the present invention, it is also possible to reduce the residual film rate of the unexposed portion during development. The reason for this is presumably because the unreacted polymerizable group located on the side chain is based on a person that promotes the dissolution of the polyfluorene imide precursor into the developer.

In the composition of the present invention, the lower limit value of the glass transition temperature measured by the method described in the examples described later is preferably 226 ° C or higher, more preferably 228 ° C or higher, and more preferably 230 ° C or higher. . As long as the glass transition temperature is the above value or higher, reliability can be expected to be improved during high-temperature processes such as a vapor deposition process process for forming a metal wiring or a bonding process between electrodes. The upper limit value of the glass transition temperature is not particularly limited, and for example, desired performance can be sufficiently exhibited even at 350 ° C or lower.

In the composition of the present invention, the residual film rate of the exposed portion is preferably 50% or more, more preferably 70% or more, and more preferably 90% or more. The residual film rate in the exposed portion is a value defined by the following. For details of the measurement method, refer to the description of the examples described later. Residual film rate in the exposed area (%) = [Film thickness after development in the exposed area / Film thickness before development in the unexposed area] × 100

In the composition of the present invention, the residual film rate after thermal curing is preferably 70% or more, more preferably 80% or more, and more preferably 85% or more. The residual film rate after heat curing is a value defined by the following. For details of the measurement method, refer to the description of the examples described later. Residual film rate after heat curing (%) = [Film thickness after heat curing / Film thickness before heat curing] × 100

Hereinafter, each component of the composition of the present invention will be described in detail.

<<< Polyimide precursor> The composition of the present invention contains a polyimide precursor having a repeating unit represented by the formula (1) described later and having a structure represented by the formula (2) at at least one terminal. Thing. The polyfluorene imide precursor is also a polyfluorene imide precursor of the present invention. [Chemical Formula 5] In the formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ is a polymerizable group, R ² is a monovalent organic group, (A) _l -L- * (2) Formula (2) Here, A represents a polymerizable group, L represents a single bond or an l + 1-valent organic group, l represents an integer of 2 to 10, and * represents a bonding site with another site.

Examples of the divalent organic group represented by X in the formula (1) include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched fat having 2 to 20 carbon atoms. Groups, cyclic aliphatic groups with 3 to 20 carbons, aromatic groups with 6 to 20 carbons, or groups containing combinations thereof are preferred, and groups containing 6 to 20 aromatic groups are Better. A particularly preferred embodiment includes a group represented by "-Ar-L-Ar-". Among them, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO _2- , or -NHCO- and Including a combination of two or more of the above. Ar is preferably phenylene. L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S-, or -SO ₂ -which may be substituted with a fluorine atom. Among them, it is preferable that the aliphatic hydrocarbon group is an alkylene group.

The divalent organic group represented by X in the formula (1) is preferably a group derived from a diamine. Examples of the diamine used in the production of the polyfluorene imide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. The diamine may be used alone or in combination of two or more. Specifically, the divalent organic group represented by X is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or A diamine including a combination thereof is preferable, and a diamine including an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following aromatic groups.

[Chemical Formula 6] In the above aromatic group, A is a single bond or is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted by a fluorine atom, -O-, -C (= O)-, -S-, -S (= O ) _2- , -NHCO- and combinations thereof are preferred, and are single bonds or selected from the group consisting of 1 to 3 carbonized alkylene groups, -O-, -C (= O) which may be substituted by fluorine atoms. -, -S-, -SO ₂ -are more preferably selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -C (CF ₃ ) ₂ -and -C ( The divalent group in the CH ₃ ) ₂ -group is further preferred.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine ring Hexane or 1,4-diaminocyclohexane, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane or 1,4-bis ( Aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenylphosphonium and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 ' -Dimethyl-4 , 4'-diaminobiphenyl, 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) fluorene, bis (4-amino-3-hydroxyphenyl)碸, 4,4'-diamino p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] 碸, Bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) Benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphosphonium, 1,3-bis (4-aminophenylbenzene) Oxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-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-aminobenzene 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-dihydroxy-4,4'-diaminobiphenyl, 9 , 9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylfluorene, 3,3 ', 5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanidine Amine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisilazane , 2,7-diaminophosphonium, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzidineaniline, esters of diaminobenzoic acid , 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane Alkane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradefluorofluoroheptane, 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-aminophenylbenzene) (Oxy) -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 -Amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylphosphonium, 2,2- Bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diamine Benzene, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 At least one diamine among ', 5,5', 6,6'-hexafluorobenzidine and 4,4 '' '-diaminotetraphenyl.

Diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemical Formula 7]

[Chemical Formula 8]

In addition, as a preferable example, a diamine having at least two or more alkylene glycol units in the main chain may be mentioned. A diamine containing one or more of two or more ethylene glycol chains and propylene glycol chains in total in one molecule is preferred, and a diamine containing no aromatic ring is more preferred. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are the product names, manufactured by HUNTSMAN), 1- (2- (2- (2-aminopropyloxy) Group) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propane-2-yl) oxy) propane-2-amine, etc., but It is not limited to these. JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( (Registered trademark) EDR-176 structure.

[Chemical Formula 9]

In the above, x, y, and z are average values.

From the viewpoint of the i-ray transmittance, it is also preferable that the divalent organic group represented by X in the formula (1) is a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferred from the viewpoint of i-ray transmittance and ease of availability. Formula (51) [Chemical Formula 10] In Formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group. Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and 1 to 10 carbon atoms (preferably 1 to 10 carbon atoms). 6) Fluorinated alkyl, etc. Formula (61) [Chemical Formula 11] In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group. Examples of the diamine compound imparting a structure of the formula (51) or (61) include 2,2'-dimethyl-4,4'-diaminobiphenyl and 2,2'-bis (trifluoromethyl) ) -4,4'-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used singly or in combination of two or more kinds.

As the tetravalent organic group represented by Y in the formula (1), a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. Formula (5) [Chemical Formula 12] In formula (5), R ¹¹² is a single bond or selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO _2- , -NHCO- The groups in these and combinations thereof are preferable, and are single bonds or selected from the group consisting of alkylene having 1 to 3 carbon atoms, -O-, -CO-, -S-, and -SO ₂ -which may be substituted by fluorine atoms. The group is more preferably selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S-, and -SO _2- The divalent group in this group is further preferred.

Formula (6) [Chemical Formula 13]

Specific examples of the tetravalent organic group represented by Y in the formula (1) include a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used alone, or two or more of them may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical Formula 14] In the formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same definition as the tetravalent organic group represented by Y in formula (1), and the preferred range is also the same.

Specific examples of the tetracarboxylic dianhydride may be selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetra Carboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ', 4'-Biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic 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-fluorene tetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene Tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, their alkyl derivatives with 1 to 6 carbon atoms, and alkoxy groups with 1 to 6 carbon atoms Base derivative.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are mentioned. [Chemical Formula 15]

It is also preferable that at least one of X and Y in formula (1) has a hydroxyl group.

R ¹ in Formula (1) represents a polymerizable group. The polymerizable group is a group capable of performing a cross-linking reaction by the action of heat, a radical, or the like. The polymerizable group is preferably a photoradical polymerizable group. Specific examples of the polymerizable group include a group containing a carbon-carbon unsaturated double bond, an alkoxymethyl group, a methylol group, a fluorenylmethyl group, an epoxy group, an oxetanyl group, and a benzoxane. An azole group, a block isocyanate group, a methylol group, and an amine group. The polymerizable group is preferably a group containing a carbon-carbon unsaturated double bond. Examples of the group containing a carbon-carbon unsaturated double bond include a vinyl group, an allyl group, a (meth) acrylfluorenyl group, a group represented by the formula (R-1), and a group represented by the formula (R-2). A group represented by the formula (R-3), and the like. Among them, because the residual film rate of the exposed portion can be increased and the residual film rate of the unexposed portion can be further reduced, the group represented by the formula (R-1) and the group represented by the formula (R-2) are relatively good. [Chemical Formula 16] In the above formula, * represents a bonding site. R ²⁰⁰ represents a hydrogen atom or a methyl group. Z represents an oxygen atom or NH. R ²⁰¹ represents a single bond, an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- , or a polyoxyalkylene group having 4 to 30 carbon atoms. R ²⁰⁰ is preferably methyl. Specific examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. methylene, octamethylene, _{dodecamethylene, -CH 2 CH (OH) CH} 2 - , ethyl stretching, stretch propylene, _{trimethylene, -CH 2 CH (OH) CH} 2 - is more Ethyl is more preferred.

R ² in formula (1) represents a monovalent organic group. Examples of the monovalent organic group include a linear or branched alkyl group, a cyclic alkyl group, a group containing an aromatic group, and a polymerizable group. Examples of the monovalent organic group include an aromatic group having one, two, or three (preferably one) acidic groups bonded to a carbon bond constituting an aryl group, and a carbon bond having a carbon bond constituting an aryl group. Aralkyl groups having 1, 2 or 3 (preferably 1) acidic groups, etc. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group, and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably a hydroxyl group.

The linear or branched alkyl group preferably has 1 to 30 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, and octadecane Base, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, norbornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and fluorene. Fluorenyl, dicyclohexyl and pinenyl. Among them, cyclohexyl is preferred from the viewpoint of taking into account the high sensitivity. Examples of the aromatic group include a substituted or unsubstituted benzene ring group, a naphthalene ring group, a pentalene ring group, an indenyl ring group, a fluorene ring group, a heptene ring group, a lead ring group, and a fluorene ring. Group, fused pentaphenyl ring group, ethanenaphthalene ring group, phenanthrene ring group, anthracene ring group, fused tetraphenyl ring group, fluorene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring Group, furan ring group, thienyl ring group, imidazole ring group, oxazole ring group, thiazole ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, pyridazine ring group, indazine ring group, indole ring Group, benzofuran ring group, benzothiophene ring group, isobenzofuran ring group, quinazine ring group, quinoline ring group, phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxazole Phenyl ring group, isoquinoline ring group, carbazole ring group, morphine ring group, acridine ring group, morpholine ring group, thiathracene ring group, chromene ring group, dibenzopiperanyl ring group, phenoxaline Thiyl, phenothiazine, or phenazine. A phenyl ring group is preferred. Examples of the polymerizable group include a polymerizable group described with R ¹ .

It is preferable that R ² in the formula (1) is a polymerizable group. That is, it is preferable that R ¹ and R ² in the formula (1) are polymerizable groups. According to this aspect, the solubility in the developing solution is improved, and the residual film rate of the unexposed portion can be further reduced.

The polyfluorene imide precursor of the present invention has a structure represented by Formula (2) at at least one terminal. (A) _l -L ^1- * (2) In formula (2), A represents a polymerizable group, L ¹ represents a single bond or an l + 1 valence organic group, l represents an integer of 2 to 10, and * represents an integer from other parts. The bonding site.

As the polymerizable group represented by A of the formula (2), a group containing a carbon-carbon unsaturated double bond is preferred. Specifically, a vinyl group, an allyl group, a (meth) acrylfluorenyl group, a group represented by the following formula (A-1), and a group represented by the formula (A-2), (methyl ) Acrylofluorenyl is more preferred, and acrylfluorenyl is further preferred. In particular, in the present invention, it is preferred that all polymerizable groups contained in the polyfluorene imide precursor are (meth) acrylfluorenyl groups, and acrylfluorenyl groups are further preferred. [Chemical Formula 17] In the above formula, * represents a bonding site with L ¹ in formula (2). R ³ represents a hydrogen atom or a methyl group, and Z represents an oxygen atom or NH.

In the formula (2), L ¹ represents a single bond or a l + 1-valent organic group, and a l + 1-valent organic group is more preferred. Examples of the l + 1-valent organic group include groups containing 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Specific examples of the l + 1-valent organic group include the following structural units or groups formed by combining two or more of the following structural units (which may form a ring structure).

[Chemical Formula 18]

In the formula (2), l represents an integer of 2 to 10, an integer of 2 to 8 is preferable, and an integer of 2 to 5 is more preferable. According to this aspect, the residual film rate after development in the exposure section can be increased.

The structure represented by the formula (2) is preferably the structure represented by the formula (3) or (4), and the structure represented by the formula (3) is more preferable. According to this aspect, the residual film rate after development in the exposure section can be increased. [Chemical Formula 19] In formula (3), R ³ represents a hydrogen atom or a methyl group, Z represents an oxygen atom or NH, L ² represents a single bond or an m + 1-valent organic group, m represents an integer of 2 to 10, and * represents a bond with another site Knot site. In the formula (4), L ³ represents a single bond or an n + 1-valent organic group, n represents an integer of 2 to 10, and * represents a bonding site with another site.

Regarding the m + 1-valent organic group represented by L ^{2 in} formula (3) and the n + 1-valent organic group represented by L ^{3 in} formula (4), examples include l + represented by L ^{1 in} formula (2). The preferred range of the monovalent organic group is the same.

In the formula (3), m is preferably an integer of 2 to 8, and an integer of 2 to 5 is more preferred. According to this aspect, the residual film rate in the exposure portion can be increased. In formula (4), n is preferably an integer of 2 to 8, and an integer of 2 to 5 is more preferred. According to this aspect, the residual film rate in the exposure portion can be increased.

It is also preferred that the polyfluorene imide precursor of the present invention has a fluorine atom in the repeating unit. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

In order to improve the adhesion to the substrate, the polyfluorene imide precursor of the present invention may further include an aliphatic group having a siloxane structure. Examples of the diamine component for introducing an aliphatic group having a siloxane structure include bis (3-aminopropyl) tetramethyldisilaxane and bis (p-aminophenyl) octamethylpentasilyl. Oxane and so on.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one type, or may be two or more types. The polyfluorene imide precursor may include a structural isomer of a repeating unit represented by formula (1). The polyfluorene imide precursor may include not only the repeating unit represented by the formula (1), but also other types of repeating units.

The polyfluorene imide precursor of the present invention contains 30 mol% or more of repeating units represented by formula (1) of the total repeating unit, more preferably 50 mol% or more, and more preferably 70 mol% or more. It is particularly preferable to contain more than 90 mol%.

Among polyimide precursors, the ratio of the structure represented by -COOR (R is a substituent) contained in the repeating unit constituting the polyimide precursor is: More than 30% is better, more than 45% is better, more than 55% is further better, more than 60% is particularly good, more than 65% is further better, more than 72% is further better, and more than 75% is better It is even more preferred, with 80% or more being particularly preferred, and 90% or more being most preferred. The upper limit of the value is not particularly limited, and may be 100%. Here, the structure represented by -COOR (R is a substituent) contained in the repeating unit constituting the polyfluorene imide precursor means that the structure is bonded to the side chain portion of the repeating unit constituting the polyfluorene imide precursor. -COOR, for example, a tetracarboxylic dianhydride or a group having a repeating unit derived from a derivative thereof. Specific examples of -COOR include -COOR ¹ and -COOR ² in the repeating unit represented by formula (1). In addition, when the polyfluorene imide precursor of the present invention includes a repeating unit other than the repeating unit represented by the formula (1), a structure represented by -COOR among the other repeating units is also included.

The weight average molecular weight (Mw) of the polyimide precursor is preferably less than 100,000, more preferably less than 70,000, further preferably less than 50,000, and even more preferably less than 35,000. The lower limit is preferably 5,000 or more, more preferably 6,000 or more, and more preferably 7,000 or more. As long as the weight average molecular weight of the polyimide precursor is 100,000 or less, the resolution is excellent. Moreover, as long as the weight average molecular weight of a polyimide precursor is 5000 or more, the mechanical strength of the obtained cured film will become more favorable. In particular, in the present invention, even if Mw is set to a value greater than 50,000, excellent resolution can be maintained.

The dispersion degree (Mw / Mn) of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the dispersion of the polyimide precursor is not particularly limited, for example, 4.5 or lower is preferred, 4.0 or lower is more preferred, 3.8 or lower is further preferred, 3.2 or lower is further preferred, and 3.1 or lower is further preferred. Preferably, 3.0 or lower is further preferred, and 2.95 or lower is particularly preferred.

The content of the polyimide precursor in the composition of the present invention is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and 70 to 96% by mass of the total solid content of the composition of the present invention. Further preferred. In the composition of the present invention, the content of the polyimide precursor having a repeating unit represented by the formula (1) and having a structure represented by "(A) _l -L ^1- *" at at least one end 10 to 99% by mass of the total solid content of the composition of the present invention is preferred, 50 to 98% by mass is more preferred, and 70 to 96% by mass is even more preferred.

The polyfluorene imide precursor of the present invention is preferably produced by reacting a compound having a polymerizable group (hereinafter, sometimes referred to as compound A) with tetracarboxylic dianhydride or a derivative thereof, and then The amine reacts therewith, and further reacts a compound having a polymerizable group (hereinafter, sometimes referred to as a compound B) with the reactant. In the present invention, the molar ratio of the raw material of the tetracarboxylic dianhydride or its derivative to the compound A (tetracarboxylic dianhydride or its derivative: the compound A) is preferably 0.9 to 1.1: 2.1 to 1.9. In the present invention, the molar ratio of the raw material of the tetracarboxylic dianhydride or its derivative to the diamine (tetracarboxylic dianhydride or its derivative: diamine) is preferably 0.8 to 1.2: 1.2 to 0.8, and 1.001 ~ 1.2: 0.999 ~ 0.8 is more preferable. In this manner, by making the tetracarboxylic dianhydride or its derivative slightly thicker, the terminal before the addition of the compound B has an acid anhydride structure, and the compound B having a hydroxyl group or an amine group can reliably introduce a polymerizable group. The reaction temperature of the above reaction is preferably -20 to 60 ° C. The reaction time is preferably 30 minutes to 10 hours.

Examples of the compound A having a polymerizable group that reacts with a tetracarboxylic dianhydride include compounds having a group in which a polymerizable group reacts with a carboxyl group or an acid anhydride group of a tetracarboxylic dianhydride to form an ester bond or an amidine bond. . The number of polymerizable groups in the compound A having a polymerizable group is preferably from 1 to 10, more preferably from 1 to 5, more preferably from 1 to 3, and particularly preferably from 1 to 3. The polymerizable group is preferably a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group, an allyl group, a (meth) acrylfluorenyl group, the group represented by the formula (R-1), the group represented by the formula (R-2), and the group described above. Among the groups represented by formula (R-3), a (meth) acrylfluorenyl group is preferred. Examples of the group which reacts with a carboxyl group or an acid anhydride group of the tetracarboxylic dianhydride to form an ester include a group having an active hydrogen. For example, a hydroxyl group, an amino group, etc. are mentioned, A hydroxyl group is preferable.

Regarding the compound A having a polymerizable group, the number of atoms between the group which forms the ester and the polymerizable group by reacting with a carboxyl group or an acid anhydride group is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. . The number of atoms between the group that forms the ester and the polymerizable group by reacting with the carboxyl group or the acid anhydride group, for example, when it is hydroxyethyl methacrylate, it is the main constituent of the alkylene chain connecting the acrylyl group and the hydroxyl group The number of atoms in the chain is three. The other compounds are considered the same. The molecular weight of Compound A having a polymerizable group is preferably 100 to 1,000, more preferably 110 to 500, and even more preferably 120 to 300. If the molecular weight of the compound A having a polymerizable group is within the above range, a polyimide precursor having excellent resolution can be easily obtained. Specific examples of the compound A include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-aminostyrene, allyl alcohol, N- (2-hydroxyethyl) maleimide.

As the compound B having a polymerizable group, a compound having 2 to 10 polymerizable groups is more preferable, a compound having 2 to 8 polymerizable groups is more preferable, and a compound having 2 to 5 polymerizable groups is Further preferred. The polymerizable group is preferably a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group, a (meth) allyl group, a (meth) acrylfluorenyl group, a group represented by the formula (A-1), and a group represented by the formula (A-2). Groups, etc. Moreover, the molecular weight of the compound B having a polymerizable group is preferably 100 to 2000, more preferably 100 to 1500, and even more preferably 100 to 1,000. As long as the molecular weight of the compound B having a polymerizable group is within the above range, a polyimide precursor having excellent resolution can be easily obtained. As a specific example of the compound B, when acid dianhydride is excessively used, neopentyl tetraol tri (meth) acrylate, glycerol di (meth) acrylate, and isocyanuric acid ethylene oxide (EO) can be exemplified. Di (meth) acrylate, and when diamine is used excessively, 1,1- (bispropenyloxymethyl) isocyanate can be exemplified.

When producing a polyfluorene imide precursor, an organic solvent is preferably used. The organic solvent may be one kind, or two or more kinds. The organic solvent can be appropriately set depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

In the production of a polyfluorene imide precursor, in order to further improve storage stability, one end of the main chain end of the precursor may be blocked with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monofluorinated chlorine compound, or a single active ester compound. Among these, a monoamine is more preferable, and as a preferable compound of a monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxy group are mentioned. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amine Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-amine Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amine Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenol and the like. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

When manufacturing a polyimide precursor, a process for precipitating solids may be included. Specifically, a polyimide precursor in the reaction solution can be precipitated in a poor solvent such as water or alcohol, thereby enabling solid precipitation. Then, the polyfluorene imide precursor is dried to obtain a powdery polyfluorene imide precursor.

<< Photopolymerization initiator >> The composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator, a photoradical polymerization initiator, and the like, and a photoradical polymerization initiator is preferred. Since the composition of the present invention contains a photo-radical polymerization initiator, the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a negative photosensitive resin composition layer, and then the light is irradiated to thereby cause a radical-induced It hardens and can reduce the solubility in the light-irradiated part. Therefore, there is an advantage that, for example, by exposing the negative photosensitive resin composition layer through a mask having a pattern that only shields the electrode portion, it is possible to easily create regions having different solubility according to the electrode pattern.

The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it may be an active agent that generates some action with a photo-excited sensitizer and generates an active radical. The photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a well-known method. For example, it is preferable to perform measurement at a concentration of 0.01 g / L by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Corporation) and using an ethyl acetate solvent.

As the photopolymerization initiator, any known compound can be used arbitrarily, and examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group), fluorene Phosphonium phosphine compounds such as phosphonium oxide, oxime compounds such as hexaarylbiimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyl groups Acetophenone, azo-based compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic compounds, and the like. Regarding these details, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357 and incorporate the contents into this specification.

As the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 with a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm can also be used. Examples of the fluorenylphosphine-based initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF) can be used as commercially available products. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using an oxime compound, exposure latitude can be further effectively improved. Among the oxime compounds, exposure latitude (exposure margin) is wide, and it also functions as a hot alkali generator, so it is particularly preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. . Preferred examples of the oxime compound include compounds having the following structure, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3 -Propanyloxyiminobutane-2-one, 2-Ethyloxyiminopentane-3-one, 2-Ethyloxyimino-1-phenylpropane-1-one , 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Imino-1-phenylpropane-1-one and the like. [Chemical Formula 20] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF), ADEKA OPTOMERN-1919 (made by ADEKA CORPORATION, Japanese Patent Application Laid-Open No. 2012-14052) Photopolymerization initiator 2) described in the publication. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. It is also possible to use DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.). Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds described in Japanese Patent Application No. 2014-500852, paragraph 0345, and Japanese Patent Laid-Open No. 24-36. Compound (C-3) and the like described in paragraph 0101 of 2013-164471. Examples of the preferred oxime compound include an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, and an oxime compound having a sulfur aryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. Wait.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenylphosphine compounds. , Phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene- Iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferred photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds. , Benzophenone compound, acetophenone compound, at least selected from the group consisting of trihalomethyltriazine compound, α-aminoketone compound, oxime compound, triarylimidazole dimer, and benzophenone compound One compound is further preferred, and the use of a metallocene compound or an oxime compound is further preferred, and an oxime compound is particularly preferred. As the photopolymerization initiator, N, N 'such as benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) can be used. -Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2- Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-acetone-1, alkyl anthraquinones, and other quinones and benzoin which are condensed with aromatic rings Benzoyl ether compounds such as phenyl ether, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. A compound represented by the following formula (I) can also be used. [Chemical Formula 21] In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; It is interrupted by an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, cyclopentyl, cyclohexyl, and an alkenyl group having 2 to 12 carbon atoms, interrupted by one or more oxygen atoms. A phenyl or biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbons and an alkyl group having 1 to 4 carbons, and R ⁵¹ is a group represented by formula (II) or is the same as R ⁵⁰ The groups, R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen. [Chemical Formula 22] In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

As the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content of the composition of the present invention, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 10% by mass. The photopolymerization initiator may contain only one kind, or may contain two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total thereof is preferably in the above range.

<< Solvent> The composition of the present invention contains a solvent. The solvent can be any known one. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, fluorenes, and amidines. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl acetate. Butyl ester, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) , Alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., 2-alkoxy Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy Methyl-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, 2-oxo Ethyl butyrate, etc. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Esters, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene. As a fluorene, a dimethyl sulfene is mentioned suitably. Examples of the amidines include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and the like. .

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the properties of the coating surface. Among them, selected from the group consisting of 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, dimethylsulfinium, ethylcarbitol acetate, butylcarbitol ethyl A mixed solution composed of two or more of an acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use both dimethyl sulfene and γ-butyrolactone.

From the viewpoint of coatability, it is preferable to set the content of the solvent to a total solid content concentration of 5 to 80% by mass, more preferably 5 to 70% by mass, and 10 to 60% by mass. % Is particularly good. The content of the solvent may be adjusted according to the desired thickness and coating method. For example, as long as the coating method is a spin coating method or a slit coating method, the content of the solvent having the solid content concentration in the above range is preferred. As long as it is a spray coating method, it is more preferable to set it as the amount of 0.1-50 mass%, and it is more preferable to set it as the amount of 1.0-25 mass%. By adjusting the content of the solvent according to the coating method, a photosensitive resin composition layer having a desired thickness can be uniformly formed. The solvent may contain only one kind or two or more kinds. When two or more solvents are contained, the total is preferably in the above range.

<<< Polyfunctional radical polymerizable monomer> It is preferable that the composition of this invention contains a polyfunctional radical polymerizable monomer (henceforth a polymerizable monomer). With such a configuration, a cured film having excellent heat resistance can be formed.

As the polymerizable monomer, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acrylfluorenyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acrylfluorenyl group.

The polymerizable monomer preferably has two or more radical polymerizable groups, and more preferably has three or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the composition of the present invention preferably contains at least one bifunctional or more polymerizable monomer containing two or more polymerizable groups, and more preferably contains at least one trifunctional or more polymerizable monomer. . Moreover, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or more polymerizable monomer. The number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.

Specific examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), or esters and amines thereof. It is an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amine of an unsaturated carboxylic acid and a polyamine compound. In addition, an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group, and an addition reaction product of a monofunctional or polyfunctional isocyanate or epoxy, and Dehydration condensation reactants of monofunctional or polyfunctional carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or amidoamines having an electrophilic substituent such as an isocyanate group or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group or toluene Substituted reactants of unsaturated carboxylic acid esters or amidoamines having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

A polymerizable monomer having a boiling point of 100 ° C. or higher under normal pressure is also preferred. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and neopentaerythritol tri ( (Meth) acrylates, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, hexanediol (methyl ) Acrylates, trimethylolpropane tris (propylene ethoxypropyl) ether, tris (propylene ethoxyethyl) isotricyanate, glycerol or trimethylolethane, etc. in polyfunctional alcohols (Meth) acrylate compound after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 The (meth) acrylic acid urethanes described therein, the polyester acrylates described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490 Multifunctional, such as epoxy acrylates, which is the reaction product of epoxy resin and (meth) acrylic acid Acrylate or methacrylate, and a mixture of these. The compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred. Furthermore, polyfunctional (meth) acrylate etc. obtained by making a polyfunctional carboxylic acid react with the compound which has a cyclic ether group and an ethylenically unsaturated group, such as glycidyl (meth) acrylate, etc. are mentioned. In addition, as other preferable polymerizable monomers, fluorene rings described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like can also be used. Compounds or cardo resins containing more than one ethylenically unsaturated bond-containing group. Furthermore, as another example, Japanese Unexamined Patent Publication No. 46-43946, Japanese Unexamined Patent Publication No. 1-40337, Japanese Unexamined Patent Publication No. 1-40336, and specific unsaturated compounds described in Japanese Unexamined Patent Publication No. Hei 2-200 can be cited. A vinylphosphonic acid-based compound described in Japanese Patent No. 25493 and the like. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-22048 can also be used. Furthermore, the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used as the introducer of the photopolymerizable monomer and oligomer.

In addition to the above, a polymerizable monomer represented by the following formulae (MO-1) to (MO-5) can be preferably used. In the formula, when T is an oxyalkylene group, a carbon atom-side end is bonded to R.

[Chemical Formula 23]

[Chemical Formula 24]

In each of the above formulas, n is an integer of 0 to 14 and m is an integer of 0 to 8. A plurality of R and T may be the same or different in the molecule. In each of the polymerizable compounds represented by the above formulae (MO-1) to (MO-5), at least one of the plurality of R is represented by -OC (= O) CH = CH ₂ or -OC (= O) C (CH ₃ ) = A group represented by CH ₂ . As specific examples of the polymerizable monomer represented by the formulae (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779 can be preferably used.

In addition, the following compounds, which are described in Japanese Patent Application Laid-Open No. 10-62986 as formulas (1) and (2) together with specific examples thereof, can also be used as polymerizable monomers. The compounds are added to a polyfunctional alcohol. A compound obtained by (meth) acrylated with ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as polymerizable monomers, and these contents can be incorporated into this specification.

As the polymerizable monomer, dipivalyltriol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (commercially available product is KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD D- 310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and these (meth) acrylfluorenyl groups are preferably bonded via ethylene glycol residues and propylene glycol residues. It is also possible to use their oligo type. In addition, as a preferable example, a neopentaerythritol derivative and / or a dipentaerythritol derivative of the above formula (MO-1) and (MO-2) can be mentioned.

Examples of commercially available polymerizable monomers include SR-494, which is a four-functional acrylate having four ethoxy groups, and bifunctional acrylic, which has four ethoxy groups, manufactured by Sartomer Company, Inc. SR-209 manufactured by Sartomer Company, Inc. of the methyl ester, DPCA-60 as a 6-functional acrylate having 6 pentyloxy chains, and 3 isobutoxy groups by the Nippon Kayaku Co., Ltd. Trifunctional acrylate TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M -9300, NK ester A-9300, UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I , AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), and the like.

Examples of the polymerizable monomer include amines described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Carbamate acrylates, as disclosed in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Urethane compounds having an ethane-based skeleton are also preferable. Furthermore, as the polymerizable monomer, it is also possible to use an amine structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. Or compounds with sulfide structure.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphate group. Among the polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to polymerize the acid group. Sexual monomers are more preferred. Particularly preferred is a polymerizable monomer having an acid group for reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The aliphatic polyhydroxy compound is used as neopentyl tetraol and / or dipentaerythritol. Of compounds. As a commercial item, M-510, M-520, etc. are mentioned as a polyacid modified acrylic oligomer by TOAGOSEI CO., LTD., For example. The polymerizable monomer having an acid group may be used singly or in combination of two or more kinds. If necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used simultaneously. The preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. As long as the acid value of the polymerizable monomer is within the above range, it is excellent in manufacturing or handling properties, and further, it is excellent in developability. The polymerizability was also good.

From the viewpoint of good polymerizability and heat resistance, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 30% by mass or less. The polymerizable monomers may be used singly or in combination of two or more kinds. The mass ratio of the polyimide precursor to the polymerizable monomer (polyimide precursor / polymerizable monomer) is preferably 98/2 to 10/90, and more preferably 95/5 to 30/70. Good, 90/10 ～ 50/50 is the best. If the mass ratio of a polyimide precursor and a polymerizable monomer is the said range, a hardened film which is more excellent in polymerizability and heat resistance can be formed.

From the viewpoint of suppressing warpage due to the control of the elastic modulus of the cured film, the composition of the present invention can preferably use a monofunctional polymerizable monomer. As the monofunctional polymerizable monomer, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxy can be preferably used. Ethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N -Derivatives of (meth) acrylic acid, such as methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. Compounds, N-vinyl compounds such as N-vinylpyrrolidone, N-vinyl caprolactam, alkenyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Propyl compounds and so on. As the monofunctional polymerizable monomer, in order to suppress volatilization before exposure, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.

<< Other Polymerizable Compounds >> The composition of the present invention can further contain other polymerizable compounds other than the aforementioned polyfluorene imide precursors and polymerizable monomers. Examples of other polymerizable compounds include compounds having a methylol group, an alkoxymethyl group, or an oxomethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

(Compound having methylol, alkoxymethyl, or oxomethyl) As the compound having methylol, alkoxymethyl, or oxomethyl, a compound represented by the following formula (AM1) is preferable.

[Chemical Formula 25] (In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or An organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass based on 100 parts by mass of the polyimide precursor. It is more preferably 10 to 35 parts by mass. Moreover, it is also preferable that the total amount of other polymerizable compounds contains 10 to 90% by mass of a compound represented by the following formula (AM4), and 10 to 90% by mass of a compound represented by the following formula (AM5).

[Chemical Formula 26] (In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. , R ⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical Formula 27] (In the formula, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom. Or an organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

By using a compound having the above-mentioned methylol group or the like, when the composition of the present invention is applied to an uneven substrate, the occurrence of cracks can be more effectively suppressed. In addition, it is possible to form a cured film which has excellent pattern processability and has a high heat resistance of 350 ° C. or higher at a temperature of 5% in mass reduction, more preferably 380 ° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-2-diethoxymethyl- P-cresol) and so on.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, and HML-TPPHBA. , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compound (compound having an epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy undergoes a crosslinking reaction based on a temperature of 200 ° C or lower, and it is difficult to cause film shrinkage because it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing an epoxy compound, low-temperature hardening and warping of a composition can be suppressed effectively.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. In addition, the flexibility of the film is increased, and a cured film excellent in elongation and the like can be obtained. The polyethylene oxide group is one in which the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of the epoxy compound include polyalkylene glycol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Epoxy group-containing silicones such as alkyl diol-type epoxy resins and polymethyl (glycidyloxypropyl) siloxanes are not limited thereto. Specific examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, and EPICLON (registered trademark) HP-4700. , EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) ) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) ) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), and the like. Among these, a polyethylene oxide-based epoxy resin is preferable from the viewpoint of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

The content of the epoxy compound is preferably 5 to 50 parts by mass relative to 100 parts by mass of the polyfluorene imide precursor, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass. As long as the content of the epoxy compound is 5 parts by mass or more, warpage of the obtained cured film can be suppressed, and as long as it is 50 parts by mass or less, pattern embedding caused by reflow during hardening can be further suppressed.

(Oxetane compound (compound having oxetanyl group)) Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, and 3-ethyl group -3-hydroxymethoxybutane, 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, and the like. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. Can be preferably used, and these can be used alone or in combination. More than two.

The content of the oxetane compound is preferably 5 to 50 parts by mass relative to 100 parts by mass of the polyimide precursor, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass.

(Benzoxazine compounds (compounds having a benzoxazolyl group)) The benzoxazine compounds do not generate outgassing during hardening due to the crosslinking reaction originating from the ring-opening addition reaction, thereby reducing thermal contraction and inhibiting generation Warping is therefore preferred.

Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (the above are trade names, manufactured by Shikoku Chemicals Corporation), and benzoxazine of polyhydroxystyrene resin. Product, novolak dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyfluorene imide precursor.

<<< Metal discoloration inhibitor> It is preferable that the composition of the present invention further contains a metal discoloration inhibitor. The composition of the present invention contains a metal discoloration inhibitor, whereby the transfer of metal ions originating from the metal layer (metal wiring) into the negative photosensitive resin composition layer can be effectively suppressed. The metal discoloration inhibitor is not particularly limited, and examples thereof include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, Azole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having sulfur Urea and mercapto compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.

Moreover, an ion trapping agent that captures anions such as halogen ions can also be used.

As other metal discoloration inhibitors, the rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-15701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and Japanese Patent Laid-Open Compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-59656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Publication No. 2012-194520.

Specific examples of the metal discoloration inhibitor include the following compounds. [Chemical Formula 28]

When the composition of the present invention has a metal discoloration inhibitor, the content of the metal discoloration inhibitor relative to the total solid content of the composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 It is more preferably -1.0% by mass. The metal discoloration inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of metal discoloration inhibitors, it is preferable that the total is within the above range.

<<< polymerization inhibitor> The composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, p-third-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6 -Third butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-third-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N-nitroso -N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-third butyl) phenylmethane and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. WO2015 / 125469 can also be used. The following compounds (Me is methyl) can also be used. [Chemical Formula 29] When the composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the composition of the present invention. The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total is preferably in the above range.

<< Thermal alkali generator >> The composition of the present invention preferably contains a thermal alkali generator. There is no particular limitation on the type of the hot alkali generator, and it is preferable to include a hot alkali generator. The hot alkali generator contains an acidic compound selected from the group consisting of an acidic compound that generates an alkali when heated to 40 ° C or higher and a pKa1 of 0 to 4. At least one of an anion and an ammonium salt of an ammonium cation. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the inverse of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later.

The acidic compound (A1) and the ammonium salt (A2) generate a base when heated. Therefore, the base generated from these compounds can promote the cyclization reaction of polyimide precursors and the like at low temperatures. Cyclization of a polyfluorene imide precursor and the like is performed next. In addition, these compounds can be prepared even if they exist together with a polyimide precursor that is cyclized and hardened by a base, and the polyimide precursor and the like are hardly circulated unless heated. Composition with excellent storage stability. In addition, in the present specification, an acidic compound refers to a compound having a value less than 7 obtained by measuring a solution at 20 ° C using a pH (power of hydrogen, pH value) meter, and the solution is obtained by extracting 1 g of a compound into a container. 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio: water / tetrahydrofuran = 1/4) was added, and the mixture was stirred at room temperature for 1 hour to obtain it.

In this embodiment, the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, and more preferably 120 to 200 ° C. The upper limit of the alkali generation temperature is preferably 190 ° C or lower, more preferably 180 ° C or lower, and even more preferably 165 ° C or lower. The lower limit of the alkali generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. As long as the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or higher, alkali is not easily generated during storage, so a composition having excellent stability can be prepared. As long as the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or lower, the cyclization temperature of the polyfluorene imide precursor and the like can be reduced. Regarding the alkali generation temperature, for example, differential scanning calorimetry can be used to heat the compound in a pressure-resistant capsule to 250 ° C at 5 ° C / min, read the peak temperature of the lowest exothermic peak, and use the peak temperature as the alkali. The temperature was measured.

In this embodiment, the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, and a tertiary amine is more preferred. Tertiary amines are more basic, so they can further reduce the cyclization temperature of polyfluorene imide precursors and polybenzoxazole precursors. The boiling point of the alkali generated by the hot alkali generator is preferably 80 ° C or higher, more preferably 100 ° C or higher, and even more preferably 140 ° C or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. In addition, the molecular weight value is a theoretical value calculated | required based on a structural formula.

In this embodiment, it is preferable that the acidic compound (A1) contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.

In this embodiment, it is preferable that the said ammonium salt (A2) is an acidic compound. In addition, the above-mentioned ammonium salt (A2) may be a compound containing an acidic compound that generates a base upon heating to 40 ° C or higher (preferably 120 to 200 ° C), or it may be other than heating to 40 ° C or higher (preferably 120 to 200) ℃) to produce compounds other than the acidic compounds of the base.

In this embodiment, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation through a covalent bond, and may also be present outside the molecule of the ammonium cation, but it is preferably present outside the molecule of the ammonium cation. In addition, the presence of the anion outside the molecule of the ammonium cation means that the ammonium cation is not bonded to the anion via a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as a counter anion. Formula (101) Formula (102) [Chemical Formula 30] In formulae (101) and (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ^{7 in the} formula (101) and the formula (102) may be bonded to form a ring, respectively.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-5). [Chemical Formula 31]

In the formulae (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are the same as defined in the formula (101) or the formula (102). In the formulae (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In this embodiment, the ammonium salt preferably has an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. As long as the pKa1 of the anion is within the above range, the polyfluorene imide precursor and the like can be cyclized at a low temperature, and the stability of the composition can be further improved. As long as pKa1 is 4 or less, the stability of the hot alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the composition is good. As long as pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyfluorene imide precursor is good. The type of the anion is preferably one selected from the group consisting of a carboxylic acid anion, a phenol anion, a phosphate anion, and a sulfuric acid anion, and a carboxylic acid anion is more preferable from the reason that the stability of a salt and the thermal decomposition property can be taken into consideration. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion. The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be set as the hot alkali generator which can further improve the stability, hardenability, and developability of a composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the composition can be further improved. In this embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. It is more preferable that pKa1 is 3.5 or less, and it is more preferable that 3.2 or less. According to this aspect, the stability of the composition can be further improved. Thereto, and pKa1 of the solution represents a first proton acid dissociation constant of the reciprocal, and can see the Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; codification: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (OF: Dawson, RMCet al; Oxford, Clarendon Press, 1959 values) described in the. For compounds not described in these documents, software using ACD / pKa (manufactured by ACD / Labs) and values calculated from the structural formulas were used.

The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical Formula 32] In the formula (X1), EWG represents an electron withdrawing group.

In this embodiment, the electron-withdrawing group means a value where the Hammett substituent constant σm represents a positive value. Among them, σm was explained in detail by Yu Takao, Journal of Synthetic Organic Chemistry, Japan Vol. 23 No. 8 (1965) pages 631-642. The electron-withdrawing group in this embodiment is not limited to the substituents described in the aforementioned documents. Examples of substituents in which σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and CH ₂ = CH group ( σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), etc. . In addition, Me represents a methyl group, Ac represents an ethenyl group, and Ph represents a phenyl group.

EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6). [Chemical Formula 33] In the formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

In this embodiment, the carboxylic acid anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 34] In the formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenyl group, an aromatic group, -NR ^X- , and a combination thereof, and R ^X represents a hydrogen atom and an alkyl group. , Alkenyl or aryl.

Specific examples of the carboxylic acid anion include a maleic acid anion, a phthalic acid anion, an N-phenyliminodiacetic acid anion, and an oxalic acid anion. These can be preferably used.

Specific examples of the hot alkali generator include the following compounds. [Chemical Formula 35] [Chemical Formula 36]

[Chemical Formula 37]

When the composition of the present invention contains a hot alkali generator, the content of the hot alkali generator is preferably 0.1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. As the hot alkali generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<<< Metal Adhesion Improver> The composition of the present invention preferably contains a metal adhesion improver for improving adhesion with a metal material used for electrodes, wiring, and the like. Examples of the metal adhesion improving agent include a silane coupling agent.

Examples of the silane coupling agent include compounds described in paragraphs 0061 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and Japanese Patent Laid-Open No. 2014 The compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. -191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group. [Chemical Formula 38]

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and sulfides described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can be used.

The content of the metal adhesion improver is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, based on 100 parts by mass of the polyfluorene imide precursor. When it is 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the hardening process becomes good, and when it is 30 parts by mass or less, the heat resistance and mechanical properties of the hardened film after the hardening process become good. The metal adhesion improver may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.

<< Other additives >> The composition of the present invention can be added to various additives, for example, a photobase generator, a thermal polymerization initiator, a thermal acid generator, and a sensitizer as needed, as long as the effects of the present invention are not impaired. Pigments, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase Generator) The composition of the present invention may contain a photobase generator. A photobase generator is a compound that generates a base by exposure, as long as it does not show activity under normal conditions of room temperature and pressure, but compounds that generate a base (alkaline substance) when irradiated with electromagnetic waves and heated as an external stimulus are combined. There is no particular limitation. The alkali generated by exposure functions as a catalyst when the polyimide precursor and the like are hardened by heating, and thus can be preferably used in a negative type.

The content of the photobase generator is not particularly limited as long as it is an amount capable of forming a pattern of a desired resin, and can be set to a normal content. The photobase generator is preferably in a range of 0.01 parts by mass or more and less than 30 parts by mass with respect to 100 parts by mass of the polyimide precursor, more preferably in a range of 0.05 parts by mass to 25 parts by mass, and is 0.1 part by mass. The range of from 20 to 20 parts by mass is more preferable. The photobase generator may be only one type, or two or more types. When there are two or more types of photobase generators, the total range is preferably the above range.

In the present invention, a known compound can be used as the photobase generator. For example, such as M. Shirai, and M. Tsusunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. ., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol 13,153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol ., 9,13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), examples of migration metal compound complexes, Structures such as ammonium salts, such as those in which the fluorenyl moiety is potentialized by the formation of carboxylic acids and salts, the alkali components are derived from the ionic compounds, carbamate derivatives, and oxime esters that are neutralized by the formation of salts. Non-ionic compounds such as compounds, fluorenyl compounds, and the like whose base components are potentially converted by a urethane bond or an oxime bond.

In addition, as the photobase generator, a urethane derivative, an amidine derivative, an amidine derivative, an α-cobalt complex, an imidazole derivative, an ammonium cinnamate derivative, an oxime derivative, or the like may be used. In addition, a photobase generator having an ammonium cinnamate structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO2009 / 123122, Japanese Patent Application Laid-Open No. 2006-189591, and Japanese Patent Laid-Open No. 2008- A photobase generator having a carbamate structure described in JP 247747, a photobase generator having an oxime structure and a carbamate oxime structure described in JP 2007-249013 and JP 2008-003581 Photo-alkali generator. Examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Application Laid-Open No. 2012-93746, and 0022 of Japanese Patent Laid-Open No. 2013-194205. Compounds described in paragraphs 0 to 0069, compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and compounds described in paragraph 0052 of International Publication WO2010 / 064631.

(Thermal polymerization initiator) The composition of the present invention may include a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, cyclization of the polyfluorene imide precursor can be performed, and polymerization reaction of the polyfluorene imide precursor can be performed, so that higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-63554.

When the composition of the present invention has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator relative to the total solid content of the composition of the present invention is preferably from 0.1 to 50% by mass, and from 0.1 to 30% by mass % Is more preferred, and 0.1 to 20% by mass is particularly preferred. Moreover, it is more preferable to contain 0.1-50 mass parts of thermal radical polymerization initiators with respect to 100 mass parts of polyimide precursors, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, a cured film having more excellent heat resistance can be easily formed. The thermal radical polymerization initiator may be only one type, or may be two or more types. When there are two or more types of thermal radical polymerization initiators, it is preferable that the total is within the above range.

(Thermal Acid Generator) The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the polyimide precursor to further improve the mechanical properties of the cured film. Examples of the thermal acid generator include the compounds described in paragraph 0059 of Japanese Patent Application Laid-Open No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 part by mass or more with respect to 100 parts by mass of the polyfluorene imide precursor, and more preferably 0.1 part by mass or more. By containing a thermal acid generator in an amount of 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. From the viewpoint of the electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass or less is a particularly preferred thermal acid generator. One type, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

(Sensitizing dye) The composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with an alkali generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, thereby causing electron transfer, energy transfer, and heat generation. As a result, the base generator, thermal radical polymerization initiator, and photopolymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification.

When the composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.5 to 10 The mass% is more preferable. The sensitizing dye may be used singly or in combination of two or more kinds.

(Chain Transfer Agent) The composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These radicals are generated by supplying hydrogen to low-active radicals, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Class, etc.).

When the composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably from 0.01 to 20 parts by mass, more preferably from 1 to 10 parts by mass, relative to 100 parts by mass of the total solid content of the composition of the present invention. Particularly preferred is 1 to 5 parts by mass. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, the total range is preferably the above range.

(Surfactant) Various surfactants can be added to the composition of the present invention from the viewpoint of improving coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. The following surfactants are also preferred. [Chemical Formula 39]

When the composition of the present invention has a surfactant, the content of the surfactant relative to the total solid content of the composition of the present invention is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind, or two or more kinds. When there are two or more surfactants, the total range is preferably the above range.

(Higher Fatty Acid Derivatives) In order to prevent polymerization inhibition by oxygen, the composition of the present invention may add a higher fatty acid derivative such as behenic acid or ammonium behenate to the drying process after coating. It is localized on the surface of the composition. When the composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the composition of the present invention. The higher fatty acid derivative may be only one, or may be two or more. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

<<< Restrictions on Other Contained Substances> From the viewpoint of coating surface properties, the moisture content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass. .

From the viewpoint of insulation, the metal content of the composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably in the above range. In addition, as a method for reducing the metal impurities inadvertently contained in the composition of the present invention, it is possible to select a raw material having a small metal content as a raw material constituting the composition of the present invention, and filter the raw material constituting the composition of the present invention. Filtering, lining the inside of the element with polytetrafluoroethylene, and performing distillation under conditions that minimize contamination.

From the viewpoint of wiring corrosiveness, in the composition of the present invention, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, the presence of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion are in the above-mentioned ranges, respectively.

<Preparation of a composition> The composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. In addition, for the purpose of removing foreign matters such as garbage and particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, 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. The filter may be previously cleaned with an organic solvent. In the filtration process of the filter, a plurality of filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be circular filtering. In addition, filtration may be performed after pressurization. When the filtration is performed after the pressurization, the pressure for pressurizing is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine a filter and an impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

<Curable film, semiconductor element, method for producing cured film, semiconductor element, method for producing laminated body, and method for producing semiconductor element> Next, the cured film, semiconductor element, method for producing a cured film, semiconductor element, and laminated body of the present invention A method of manufacturing a semiconductor device and a method of manufacturing a semiconductor device will be described. The cured film of the present invention is obtained by curing the composition of the present invention. The thickness of the cured film of the present invention can be, for example, 1 μm or more, and can be 5 μm or more. The upper limit value can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers of the cured film of the present invention can be used as a laminate. It is preferable that the laminated body has a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

Examples of a field to which the cured film of the present invention can be applied include an insulating film for a semiconductor element, and an interlayer insulating film for a redistribution layer. In particular, since the resolution is good, the interlayer insulating film for a redistribution layer in a three-dimensional mounting element can also be preferably used. The cured film in the present invention can also be used for photoresists for electronics, galvanic resists, etching resists, solder top resists, and the like. In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen printing plates, the use of molded parts, the production of protective lacquers and dielectric layers in electronics, especially microelectronics, and the like.

The manufacturing method of the cured film of this invention includes the case where the composition of this invention is used. Preferably, the negative photosensitive resin composition of the present invention is applied to a substrate to form a layer of a negative photosensitive resin composition layer forming process and an exposure process of exposing the negative photosensitive resin composition layer. And a process of developing the exposed negative photosensitive resin composition layer. In the manufacturing method of the present invention, the manufacturing process may include a manufacturing process of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the developing process. Since the cured film of the present invention is excellent in heat resistance, it can maintain good performance even when heated at 150 to 500 ° C.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the method for manufacturing a laminated body of the present invention, according to the method for manufacturing a cured film of the present invention, after the cured film is formed, the negative photosensitive resin composition layer forming process, the exposure process, and the development processing process are sequentially performed again in order. . In particular, it is preferable to further perform the negative photosensitive resin composition layer forming process, the exposure process, and the development process process in order 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this manner, a laminated body can be obtained. In the present invention, it is preferable to provide a metal layer on a portion removed after development, especially after the hardened film is provided and after development.

The present invention also discloses a semiconductor device including the cured film of the present invention. Hereinafter, an embodiment of a semiconductor element using the composition of the present invention for an interlayer insulating film for a redistribution layer will be described.

The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting element, and a multilayer body 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are laminated is arranged on a wiring substrate 120. In addition, in this embodiment, a case where the number of stacked layers of a semiconductor element (semiconductor wafer) is mainly described will be described, but the number of stacked layers of a semiconductor element (semiconductor wafer) is not particularly limited, and may be, for example, two layers, eight layers, 16 floors, 32 floors, etc. It may be one floor.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101a not having a through electrode and semiconductor elements 101b to 101d having a through electrode 102b to 102d are flip-chip bonded. That is, the electrode pad of the semiconductor element 101a without a through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b with a through electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump. The connection pad on the other side of the semiconductor element 101b having the through electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent to the connection pad are formed by a metal bump 103b such as a solder bump. connection. Similarly, the connection pads on the other side of the semiconductor element 101c having the through electrode 102c and the connection pads on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto are connected by metal bumps such as solder bumps. 103c and connected.

An underfill layer 110 is formed in a gap between each of the semiconductor elements 101 a to 101 d, and each of the semiconductor elements 101 a to 101 d is laminated via the underfill layer 110.

The laminated body 101 is disposed on the wiring substrate 120. As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring substrate 120 using a resin substrate include a multilayer copper-clad laminate (multilayer printed wiring board) and the like.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which the redistribution layer 105 is formed is arranged between the wiring substrate 120 and the multilayer body 101, and the wiring substrate 120 and the multilayer body 101 are electrically connected via the redistribution layer 105. The insulating layer 115 is formed using the composition of the present invention. That is, one end of the redistribution layer 105 is connected to an electrode pad formed on a surface of the redistribution layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Further, an underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. An underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120.

In addition to the above, the cured film of the present invention can be widely used in various applications using polyimide. In addition, because polyimide has high heat resistance, the cured film and the like in the present invention can also be suitably used as a plastic substrate or an interlayer insulating film for display elements such as liquid crystal displays, organic EL displays, and electronic paper, automotive parts, Heat-resistant paint, coating agent, film application. Furthermore, the polyimide precursor of the present invention can also be used for a positive-type photosensitive resin composition. [Example]

Hereinafter, the present invention will be described in more detail with examples. The materials, usage amounts, proportions, processing contents, and processing steps shown in the following examples are within the scope not departing from the spirit of the present invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Part" and "%" are quality standards as long as there is no special restriction.

Synthesis of Polyimide Precursor <Synthesis of Polyimide Precursor P-1> 20.00 g (64.5 mmol) of 4,4'-oxodiphthalic dianhydride (ODPA, 4 , 4'-oxo diphthalic acid obtained by drying at 140 ° C for 12 hours, difunctional anhydride), 16.79 g (129 mmol) of hydroxyethyl methacrylate (side chain raw material), 0.05 g Hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60 ° C for 18 hours to produce 4,4'-oxo Diester of phthalic acid and hydroxyethyl methacrylate (HEMA). Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. After diluted with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 12.27 g (61.7 mmol) of 4,4'-oxodiphenylamine (ODA, diamine) in 100 mL of N-methylpyrrolidone was dropped at 20 to 23 ° C over 20 minutes. Add to the reaction mixture. Next, 12.96 g (15.5 millimoles) of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd., a terminal raw material) was added to the reaction mixture, and the reaction mixture was stirred at room temperature overnight. . Next, the polyimide precursor was precipitated in a mixed solvent of 3 liters of water and 3 liters of acetone. The polyimide precursor was removed by filtration, and the mixture was again stirred in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure and at room temperature for two days to obtain a polyimide precursor P-1. The structure of the obtained polyfluorene imine precursor P-1 was confirmed by ¹ H-NMR (nuclear magnetic resonance spectroscopy) (DMSO (dimethylsulfinium) -d6 solution). 10.6 to 10.3 ppm (m, 2H), 8.2 to 6.7 ppm (m, 14H), 6.4 to 6.2 ppm (m, 1H), 6.2 to 5.8 ppm (m, 4H), 5.7 to 5.4 ppm (m, 2H), 4.6 to 4.2 ppm (m, 8H), 3.9 to 3.6 ppm (s, 6H), 1.9 to 1.7 ppm (m, 6H). The weight average molecular weight (gel permeation chromatography (eluent: NMP (N-methyl-2-pyrrolidone) polystyrene conversion value) of the obtained P-1) was 70,000. The measurement conditions were as follows. Column: TSKguardcolumn SuperAW-H (4.6mmID. × 35mm) 1 TSK SuperAWM-H (6.0mmID. × 150mm) 2 developing solvents: NMP (10mmol / L lithium bromide, 10mmol / L phosphoric acid solution) Column temperature: 50 ° C Flow rate: 0.35 mL / min sample injection volume: 20 μL sample concentration: 0.1% by mass Element name: HLC-8220GPC (manufactured by TOSOH CORPORATION) Calibration curve base resin: polystyrene

<Synthesis of Polyfluorene Imide Precursor P-2 to P-20> In the synthesis of the polyfluorene imide precursor P-1, the difunctional acid anhydride, diamine, side chain compound, and terminal raw materials were as shown in the following table. Except changing as shown in FIG. 1, polyimide precursors P-2 to P-20 were synthesized in the same manner. In addition, the numerical value described in the raw material column of the side chain raw materials of the polyimide precursors P-13 to P-16 is the mole ratio of the two raw materials.

[Table 1]

ODPA: BPDA manufactured by Tokyo Chemical Industry Co., Ltd .: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, ODA manufactured by Tokyo Chemical Industry Co., Ltd .: Tokyo Chemical Industry Co., Ltd. Production of benzidine (4,4'-diaminobiphenyl): HEA made by Tokyo Chemical Industry Co., Ltd .: hydroxyethyl acrylate 4-aminostyryl: HEMI made by Tokyo Chemical Industry Co., Ltd .: N- (2-hydroxyethyl) maleimide, DPHA manufactured by Tokyo Chemical Industry Co., Ltd .: manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA M-305: neopentaerythritol triacrylate, TOAGOSEI CO., LTD., ARONIX M-305 701: glycerol dimethacrylate, Shin-Nakamura Chemical Co., Ltd. M-215: isocyanurate ethylene oxide (EO) modified diacrylate , Manufactured by TOAGOSEI CO., LTD., ARONIX M-215 G-201P: 2-hydroxy-3-propenyloxypropyl methacrylate manufactured by Kyoeisha chemical Co., Ltd.

<Example 1> << Preparation of negative-type photosensitive resin composition> As shown in Table 2 below, a polyimide precursor, a photopolymerization initiator, a radical polymerizable monomer, a polymerization inhibitor, A metal discoloration inhibitor, a silane coupling agent, and a solvent were mixed, and a negative photosensitive resin composition was prepared as a uniform solution.

<< Resolution >><< Residual film rate of exposed part >> After passing the negative photosensitive resin composition through a filter having a pore width of 0.8 μm and performing pressure filtration under a pressure of 3.0 MPa, A negative photosensitive resin composition layer was formed by applying a negative photosensitive resin composition in a layered manner on a silicon wafer by a spin coating method. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform negative photosensitive resin composition having a thickness of 15 μm on the silicon wafer. Physical layer. A stepper (Nikon NSR 2005 i9C) was used to expose the negative photosensitive resin composition layer on the silicon wafer with an exposure energy of 500 mJ / cm ² . After standing at room temperature for 30 minutes, the film was developed with cyclopentanone for 60 seconds, and the residual film ratio in the exposed portion was determined based on the change in film thickness before and after the development. Residual film rate in the exposed area (%) = [Film thickness after development in the exposed area / Film thickness before development in the unexposed area] × 100 5: 90% or more 4: 70% or more and less than 90% 3: 50% or more And less than 70% 2: 30% or more and less than 50% 1: less than 30% In actual use, it is better to evaluate 3 or more.

<<< Residual film rate of the unexposed part >> The negative photosensitive resin composition was passed through a filter having a pore width of 0.8 μm, and subjected to pressure filtration at a pressure of 3.0 MPa, and then was placed on a silicon wafer. A negative photosensitive resin composition layer was formed by applying the negative photosensitive resin composition in a layer form by a spin coating method. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes, so that a uniform negative photosensitive resin composition having a thickness of 15 μm was formed on the silicon wafer. Physical layer. This was developed with cyclopentanone for 60 seconds, and the residual film rate of the unexposed portion was determined according to the film thickness change before and after the development. Unexposed area residual film rate (%) = [(film thickness after development of unexposed area) / film thickness before development of unexposed area] × 100 5: less than 5% 4: 5% or more and less than 20% 3 : 20% or more and less than 50% 2: 50% or more and less than 90% 1: 90% or more In actual use, an evaluation of 3 or more is preferable.

<< Glass Transition Temperature (Tg) >> The negative photosensitive resin composition is passed through a filter having a pore width of 0.8 μm, and subjected to pressure filtration at a pressure of 3.0 MPa, and then borrowed on a silicon wafer. The negative photosensitive resin composition layer was formed by applying the negative photosensitive resin composition in a layer form by a spin coating method. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform negative photosensitive resin composition having a thickness of 15 μm on the silicon wafer. Physical layer. A stepper (Nikon NSR 2005 i9C) was used to expose the negative photosensitive resin composition layer on the silicon wafer with an exposure energy of 500 mJ / cm ² , and the exposed negative photosensitive was exposed in a nitrogen environment. The temperature of the resin composition layer (resin layer) was increased at a temperature increase rate of 10 ° C / minute, and it was maintained at 230 ° C for 3 hours. The cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin film. The obtained resin film was set on a viscoelasticity measuring element (Rheogel E4000, manufactured by UBM), and the temperature was raised from 0 ° C to 350 ° C by a tensile method at a frequency of 1 Hz and a temperature increase rate of 10 ° C / min. The peak temperature of tan δ was used to determine Tg (° C).

<Other Examples and Comparative Examples> In Example 1, a polyimide precursor, a photopolymerization initiator, a radical polymerizable monomer, a polymerization inhibitor, a metal discoloration inhibitor, a silane coupling agent, and a solvent were added. One or more of them were changed as shown in Table 2 or Table 3, and in some examples, the hot alkali generator was blended as shown in Table 3, and the same procedure was performed.

The obtained results are shown in Tables 2 and 3 below.

[Table 2]

[table 3]

<Photoradical polymerization initiator> OXE-01: IRGACURE OXE 01 (oxime compound, manufactured by BASF) IRGACURE-784: IRGACURE-784 (metallocene compound, manufactured by BASF) <radical polymerizable monomer> SR209: SR-209 (bifunctional methacrylate with 4 ethoxylated chains, manufactured by Sartomer Company, Inc.) A-9300: NK ester A-9300 (trifunctional acrylate with 3 isobutyranyl chains) (Made by Shin-Nakamura Chemical Co., Ltd.) A-TMMT: made by Shin-Nakamura Chemical Co., Ltd., neo-pentaerythritol tetraacrylate A-DPH: made by Shin-Nakamura Chemical Co., Ltd., two Neopentaerythritol hexaacrylate

<Hot alkali generator> E-1: The following compound E-2: The following compound E-3: The following compound

<Polymerization inhibitor> F-1: The following compound F-2: The following compound F-3: The following compound

<Metal discoloration inhibitor> G-1: The following compound G-2: The following compound G-3: The following compound G-4: The following compound

<Silane coupling agent> H-1: The following compound H-2: The following compound H-3: The following compound

<Solvent> DMSO: Dimethyl sulfene GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone ethyl lactate

[Chemical Formula 40]

From the above results, it is clear that when the negative photosensitive resin composition of the present invention is used, Tg is high and the resolution is excellent. In particular, in the present invention, the Tg is 230 ° C or higher and 5 ° C higher than that of Comparative Example 1. When the Tg rises by 5 ° C, it can be said that it is a very significant effect from the viewpoint of improving the reliability in a high-temperature process such as a vapor deposition process for forming a metal wiring or a bonding process between electrodes.

Example 100 <Production of laminated body 1> After the photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, it was formed on a silicon wafer by a spin coating method. A photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. Next, a stepper (Nikon NSR 2005 i9C) was used to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500 mJ / cm ² , and the exposed photosensitive resin composition was exposed with cyclopentanone. The layer (resin layer) was developed for 60 seconds to form a hole having a diameter of 10 μm. Then, the temperature was raised at a temperature increase rate of 10 ° C / min in a nitrogen environment, and it was maintained at 230 ° C for 3 hours. After cooling to room temperature, the same type of photosensitive resin composition as that of the photosensitive resin composition was used again on the surface of the resin layer, and filtration from the photosensitive resin composition to patterning was performed again in the same manner as described above. The film was heated for 3 hours, thereby forming a laminated body 1 having two resin layers.

<Production of Laminated Body 2> On the surface of the laminated body 1 obtained in the above, the same procedure as in the production of the laminated body 1 was performed by using the photosensitive resin composition of Example 3 to form a resin layer having four layers The laminated body 2.

<Production of Laminate 3> After the photosensitive resin composition of Example 3 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, a photosensitive resin was formed on a silicon wafer by a spin coating method. Composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. A stepper (Nikon NSR 2005 i9C) was used to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500 mJ / cm ² , and the exposed photosensitive resin composition layer ( Resin layer) was developed for 60 seconds to form a hole having a diameter of 10 μm. Next, the temperature was raised at a temperature increase rate of 10 ° C / min in a nitrogen environment, and the temperature was maintained at 230 ° C for 3 hours. After cooling to room temperature, a copper thin film (metal layer) having a thickness of 2 μm was applied to a part of the surface of the photosensitive resin composition layer by a vapor deposition method so as to cover the pores. Furthermore, on the surfaces of the metal layer and the photosensitive resin composition layer, the photosensitive resin composition of Example 3 was used again, and filtration from the photosensitive resin composition to the patterned film was performed again in the same manner as described above. The process of heating for 3 hours was completed to produce a laminated body 3 including a resin layer / metal layer / resin layer.

100‧‧‧Semiconductor element

101a ～ 101d‧‧‧Semiconductor element

101‧‧‧Laminated body

102b ～ 102d‧‧‧through electrode

103a ～ 103e‧‧‧ metal bump

105‧‧‧ redistribution layer

110, 110a, 110b‧‧‧ Underfill

115‧‧‧ Insulation

120‧‧‧ wiring board

120a‧‧‧ surface electrode

FIG. 1 is a schematic diagram showing a configuration of an embodiment of a semiconductor element.

Claims (21)

A negative photosensitive resin composition comprising a polyimide precursor, a photopolymerization initiator, and a solvent, wherein the polyimide precursor has a repeating unit represented by formula (1) and is at least one terminal Has a structure represented by formula (2), In the formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ is a polymerizable group, R ² is a monovalent organic group, (A) _l -L- * (2) Formula (2) Here, A represents a polymerizable group, L represents a single bond or an l + 1-valent organic group, l represents an integer of 2 to 10, and * represents a bonding site with another site. The negative photosensitive resin composition according to item 1 of the scope of the patent application, wherein l in the aforementioned formula (2) is an integer of 2 to 5. The negative-type photosensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein R ² is a polymerizable group. The negative photosensitive resin composition according to item 1 or item 2 of the scope of the patent application, wherein the polymerizable groups possessed by the aforementioned polyfluorene imide precursor are each independently a group containing a carbon-carbon unsaturated double bond group. The negative photosensitive resin composition according to item 1 or 2 of the scope of patent application, wherein the structure represented by the aforementioned formula (2) is a structure represented by the formula (3) or (4), In formula (3), R ³ represents a hydrogen atom or a methyl group, Z represents an oxygen atom or NH, L ² represents a single bond or an m + 1-valent organic group, m represents an integer of 2 to 10, and * represents a bond with another site A junction site. In the formula (4), L ³ represents a single bond or an n + 1-valent organic group, n represents an integer of 2 to 10, and * represents a junction site with another site. The negative photosensitive resin composition according to item 1 or 2 of the scope of the patent application, wherein the polyimide precursor comprises the -COOR contained in the repeating unit constituting the polyimide precursor. In the structure represented, the proportion of the structure of the group containing a polymerizable group in R is 30% or more, and R is a substituent. The negative photosensitive resin composition according to item 1 or item 2 of the scope of patent application, further comprising a polyfunctional radical polymerizable monomer. The negative-type photosensitive resin composition according to item 1 or item 2 of the scope of patent application, further comprising a thermal alkali generator. The negative-type photosensitive resin composition according to claim 1 or claim 2, wherein the photopolymerization initiator is at least one selected from the group consisting of an oxime compound and a metallocene compound. The negative photosensitive resin composition according to item 1 or 2 of the patent application scope, which is a negative photosensitive resin composition for forming an interlayer insulating film for a redistribution layer. A cured film obtained by curing the negative-type photosensitive resin composition according to any one of claims 1 to 10 of the scope of patent application. The hardened film according to item 11 of the scope of patent application, wherein the film thickness of the hardened film is 1 to 30 m. A method for manufacturing a cured film, comprising: a process for forming a photosensitive resin composition layer, and applying the negative photosensitive resin composition according to any one of the first to tenth of the scope of patent application to a substrate to form It is layered; an exposure process, which exposes the negative photosensitive resin composition layer; and a development process, which develops the exposed photosensitive resin composition layer. The method for manufacturing a cured film according to item 13 of the scope of patent application, which includes a heating process of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500 ° C. after the development process. . A semiconductor device having a hardened film as described in claim 11 or 12 of the scope of patent application. A method for manufacturing a laminated body, which includes the method for manufacturing a hardened film as described in item 13 or 14 of the scope of patent application. A method for manufacturing a semiconductor device, which includes the method for manufacturing a cured film according to item 13 or 14 of the scope of patent application. A polyimide precursor having a repeating unit represented by formula (1) and a structure represented by formula (2) at at least one end, In the formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ is a polymerizable group, R ² is a monovalent organic group, (A) _l -L- * (2) Formula (2) Here, A represents a polymerizable group, L represents a single bond or an l + 1-valent organic group, l represents an integer of 2 to 10, and * represents a bonding site with another site. The polyfluorene imide precursor as described in claim 18, wherein R ² is a polymerizable group. The polyimide precursor as described in claim 18 or claim 19, wherein A in the aforementioned formula (2) is a group containing a carbon-carbon unsaturated double bond. The polyimide precursor according to item 18 or item 19 of the scope of patent application, wherein l in the aforementioned formula (2) is an integer of 2 to 5.