TWI728137B - Negative photosensitive resin composition, cured film, cured film manufacturing method, semiconductor device, laminated body manufacturing method, semiconductor device manufacturing method, and polyimide precursor - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition comprising a polyimide precursor, a photopolymerization initiator, and a solvent. The polyimine precursor has a repeating unit represented by formula (1), and has at least one The end of has a structure represented by "(A) _l -L ¹ -*", and the weight average molecular weight is below 50,000. In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R ¹ and R ² are each independently a non-polymerizable organic group. In addition, in the above structure, A represents a polymerizable group, L ¹ represents a single bond or a l+1 valent organic group, l represents an integer of 1 to 10, and * represents a bonding site to another site.

Description

Negative photosensitive resin composition, cured film, curing film manufacturing method, Semiconductor device, method of manufacturing laminate, method of manufacturing semiconductor device, and polyimide precursor

The present invention relates to a negative photosensitive resin composition, a cured film, a method of manufacturing a cured film, a method of manufacturing a semiconductor device, a laminate, a method of manufacturing a semiconductor device, and a polyimide precursor.

Thermosetting resins that are cured by cyclization, such as polyimide resins, are used in insulating layers of semiconductor devices because they are excellent in heat resistance and insulating properties. In addition, polyimide resins have low solubility in solvents, so they are used in the state of precursors (polyimide precursors) before the cyclization reaction, and after they are applied to substrates, etc., they are heated The polyimide precursor is cyclized to form a hardened film.

式中，R¹ 係4價有機基，R² 係2價有機基。 [先前技術文獻] [專利文獻]For example, Patent Document 1 describes a photosensitive resin composition containing: (A) having a repeating unit represented by the general formula (1) in the main chain, and having photopolymerizable carbon-carbon at both ends of the molecule A polyimide precursor of a double bond substituent and an actinic ray functional group whose end is modified by aminobenzenes or trimellitic acid derivatives, (B) has a photopolymerizable functional group The photosensitive assistant and (C) a photopolymerization initiator containing N-aryl-α-amino acids and thioxanthones, wherein the content of the photopolymerization initiator is relative to 100 masses of the polyimide precursor The parts are 7-15 parts by mass. [Chemical formula 1]

In the formula, R ¹ is a tetravalent organic group, and R ² is a divalent organic group. [Prior Technical Documents] [Patent Documents]

[Patent Document 1]: JP 2013-76845 A

In Patent Document 1, since it has a polyamide structure, it is susceptible to hydrolysis by water. Therefore, the stability over time is low, and it is impossible to purify the synthesized resin with water series. Therefore, it is difficult to apply to semiconductor applications that require high quality.

Therefore, the object of the present invention is to provide a negative photosensitive resin composition with excellent resolution. In addition, there is provided a cured film using the negative photosensitive resin composition, a cured film manufacturing method, a semiconductor device, a laminate manufacturing method, a semiconductor device manufacturing method, and a polyimide precursor.

式（1）中，X表示2價有機基，Y表示4價有機基，R¹ 及R² 分別獨立地係非聚合性有機基， （A）_l -L¹ -* （2） 式（2）中，A表示聚合性基，L¹ 表示單鍵或l+1價有機基，l表示1～10的整數，*表示與其他部位的鍵結部位。 ＜2＞如＜1＞所述之負型感光性樹脂組成物，其中式（2）中的l係2～5的整數。 ＜3＞如＜1＞或＜2＞所述之負型感光性樹脂組成物，其中R¹ 及R² 分別獨立地係碳數1～4的非聚合性有機基。 ＜4＞如＜1＞～＜3＞中任一項所述之負型感光性樹脂組成物，其中式（2）中的A係包含碳-碳不飽和雙鍵之基團。 ＜5＞如＜1＞～＜4＞中任一項所述之負型感光性樹脂組成物，其中由式（2）表示之結構係由式（3）或式（4）表示之結構， [化學式3]

式（3）中，R³ 表示氫原子或甲基，Z表示氧原子或NH，L² 表示單鍵或m+1價有機基，m表示1～10的整數，*表示與其他部位的鍵結部位; 式（4）中，L³ 表示單鍵或n+1價有機基，n表示1～10的整數，*表示與其他部位的鍵結部位。 ＜6＞＜1＞～＜5＞中任一項所述之負型感光性樹脂組成物，其中聚醯亞胺前驅物的重量平均分子量係5000以上。 ＜7＞如＜1＞～＜6＞中任一項所述之負型感光性樹脂組成物，其還包含多官能自由基聚合性單體。 ＜8＞如＜1＞～＜7＞中任一項所述之負型感光性樹脂組成物，其還包含熱鹼產生劑。 ＜9＞如＜1＞～＜8＞中任一項所述之負型感光性樹脂組成物，光聚合起始劑係選自肟化合物及茂金屬化合物中之至少一種。 ＜10＞如＜1＞～＜9＞中任一項所述之負型感光性樹脂組成物，其為再配線層用層間絕緣膜形成用負型感光性樹脂組成物。 ＜11＞一種硬化膜，其藉由對＜1＞～＜10＞中任一項所述之負型感光性樹脂組成物進行硬化而成。 ＜12＞如＜11＞所述之硬化膜，其膜厚係1～30μm。 ＜13＞一種硬化膜的製造方法，其具有： 感光性樹脂組成物層形成製程，將＜1＞～＜10＞中任一項所述之負型感光性樹脂組成物應用於基板而形成為層狀； 曝光製程，對負型感光性樹脂組成物層進行曝光；及 顯影處理製程，對所曝光之感光性樹脂組成物層進行顯影處理。 ＜14＞如＜13＞所述之硬化膜的製造方法，其包括於顯影處理製程後，以50～500℃的溫度對已顯影之負型感光性樹脂組成物層進行加熱之加熱製程。 ＜15＞一種半導體裝置，其具有＜11＞或＜12＞所述之硬化膜。 ＜16＞一種積層體的製造方法，其包括＜13＞或＜14＞所述之硬化膜的製造方法。 ＜17＞一種半導體裝置的製造方法，其包括＜13＞或＜14＞所述之硬化膜的製造方法。 ＜18＞一種聚醯亞胺前驅物，其具有由式（1）表示之重複單元，並於至少一方的末端具有由式（2）表示之結構，且重量平均分子量係50000以下， [化學式4]

式（1）中，X表示2價有機基，Y表示4價有機基，R¹ 及R² 分別獨立地係非聚合性有機基， （A）_l -L¹ -* （2） 式（2）中，A表示聚合性基，L¹ 表示單鍵或l+1價有機基，l表示1～10的整數，*表示與其他部位的鍵結部位。 ＜19＞如＜18＞所述之聚醯亞胺前驅物，其中R¹ 及R² 分別獨立地係碳數1～4的非聚合性有機基。 ＜20＞如＜18＞或＜19＞所述之聚醯亞胺前驅物，其中式（2）中的A係包含碳-碳不飽和雙鍵之基團。 ＜21＞如＜18＞～＜20＞中任一項所述之聚醯亞胺前驅物，其中式（2）中的l係2～5的整數。 [發明效果]As a result of intensive research, the inventors found that by providing a polymerizable group at the end of the polyimide precursor and setting the weight average molecular weight of the polyimine precursor to less than 50,000, the resolution can be improved and completed The present invention. Thus, the present invention provides the following. <1> A negative photosensitive resin composition comprising a polyimide precursor, a photopolymerization initiator, and a solvent, wherein the polyimine precursor has a repeating unit represented by formula (1), and at least One end has a structure represented by formula (2), and the weight average molecular weight is below 50,000, [Chemical formula 2]

In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ and R ² are each independently a non-polymerizable organic group, (A) _l -L ¹ -* (2) formula (2) In ), A represents a polymerizable group, L ¹ represents a single bond or a l+1 valent organic group, l represents an integer from 1 to 10, and * represents a bonding site with other sites. <2> The negative photosensitive resin composition as described in <1>, wherein l in formula (2) is an integer of 2 to 5. <3> The negative photosensitive resin composition as described in <1> or <2>, wherein R ¹ and R ² are each independently a non-polymerizable organic group having 1 to 4 carbon atoms. <4> The negative photosensitive resin composition according to any one of <1> to <3>, wherein A in formula (2) is a group containing a carbon-carbon unsaturated double bond. <5> The negative photosensitive resin composition according to any one of <1> to <4>, wherein the structure represented by formula (2) is a structure represented by formula (3) or formula (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 from 1 to 10, and * represents a bond with other parts Junction site; In formula (4), L ³ represents a single bond or an n+1 valent organic group, n represents an integer from 1 to 10, and * represents a bonding site with other sites. <6> The negative photosensitive resin composition according to any one of <1> to <5>, wherein the weight average molecular weight of the polyimide precursor is 5000 or more. <7> The negative photosensitive resin composition according to any one of <1> to <6>, which further contains a polyfunctional radical polymerizable monomer. <8> The negative photosensitive resin composition according to any one of <1> to <7>, which further contains a thermal base 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 rewiring layer. <11> A cured film formed by curing the negative photosensitive resin composition described in any one of <1> to <10>. <12> The cured film as described in <11>, which has a thickness of 1 to 30 μm. <13> A method for producing a cured film, comprising: a photosensitive resin composition layer forming process, and the negative photosensitive resin composition according to any one of <1> to <10> is applied to a substrate to form Laminar; an exposure process to expose the negative photosensitive resin composition layer; and a development process to develop the exposed photosensitive resin composition layer. <14> The method for producing a cured film as described in <13>, 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. <15> A semiconductor device having the cured film described in <11> or <12>. <16> A method of manufacturing a laminate, including the method of manufacturing a cured film described in <13> or <14>. <17> A method of manufacturing a semiconductor device, including the method of manufacturing a cured film described in <13> or <14>. <18> A polyimide precursor, which has a repeating unit represented by formula (1), has a structure represented by formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less, [Chemical formula 4 ]

In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, R ¹ and R ² are each independently a non-polymerizable organic group, (A) _l -L ¹ -* (2) formula (2) In ), A represents a polymerizable group, L ¹ represents a single bond or a l+1 valent organic group, l represents an integer from 1 to 10, and * represents a bonding site with other sites. <19> The polyimide precursor according to <18>, wherein R ¹ and R ² are each independently a non-polymerizable organic group having 1 to 4 carbon atoms. <20> The polyimide precursor as described in <18> or <19>, wherein A in formula (2) is a group containing a carbon-carbon unsaturated double bond. <21> The polyimide precursor according to any one of <18> to <20>, wherein l in formula (2) is an integer of 2 to 5. [Effects of the invention]

According to the present invention, a negative photosensitive resin composition with excellent resolution can be provided. Furthermore, it is possible to provide a cured film using the negative photosensitive resin composition, a cured film manufacturing method, a semiconductor device, a laminate manufacturing method, a semiconductor device manufacturing method, and a polyimide precursor. [Illustration brief description]

FIG. 1 is a schematic diagram showing the structure of an embodiment of a semiconductor device.

The description of the constituent elements of the present invention described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. Regarding the labeling of the group (atomic group) in this specification, it is not recorded that the substituted and unsubstituted labels include both a group having no substituent and a group having a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). As long as "exposure" in this specification is not particularly limited, in addition to exposure with light, drawing with particle beams such as electron beams and ion beams is also included in exposure. In addition, as the light used for exposure, active rays or radiations such as extreme ultraviolet, extreme ultraviolet (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers are usually cited. In this specification, the numerical range indicated by "-" refers to the range that includes the numerical values described before and after the "-" as the lower limit and the upper limit. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". 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 intended effect of the process can be achieved, it is also included in this term. In this specification, the solid content concentration refers to the mass percentage of components other than the solvent relative 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, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured based on gel permeation chromatography (GPC), and are defined as styrene conversion values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard column TSKguardcolumn SuperAW-H or TSK SuperAWM-H (TOSOH CORPORATION) can be used as the column. System) and find out. As long as there is no special description, the eluent shall be measured with N-methyl-2-pyrrolidone (NMP). In addition, as long as there is no special description, the detection is made as 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) is characterized by containing a polyimide precursor, a photopolymerization initiator and a solvent, and The imine precursor has a repeating unit represented by the formula (1) described later, has a structure represented by the formula (2) described later at at least one end, and has a weight average molecular weight of 50,000 or less.

According to the composition of the present invention, it can be a negative photosensitive resin composition with excellent resolution. It is estimated that the mechanism by which this effect can be obtained is based on the following. According to research conducted by the inventors of the present invention, it has been found that the glass transition temperature (Tg) can be increased by providing a polymerizable group at the end of the polyimide precursor. So far, because the polymerizable group can be introduced at a high density, the polyimide precursor usually has a polymerizable group in the side chain. However, it is known that when a polymerizable group is introduced into the side chain of the polyimide precursor, when the polyimide precursor is cyclized, the polymerizable group of the side chain may be detached. In contrast, if a polymerizable group is introduced to the end of the polyimide precursor, even if cyclization is performed, the polymerizable group will not be detached. However, it is known that if only a polymerizable group is provided at the end, the resolution during development deteriorates. It is considered that this is because the amount of polymerizable groups relative to the polyimide precursor is relatively small. Therefore, by setting the weight average molecular weight of the polyimide precursor to 50,000 or less, the amount of polymerizable groups relative to the polyimide precursor can be relatively increased, and as a result, the resolution has been successfully improved. Furthermore, according to the present invention, the resolution can be improved while maintaining the high Tg of the cured film of the negative photosensitive resin composition.

Furthermore, in the present invention, by setting R ¹ and R ^{2 of the} formula (1) as a non-polymerizable group having 1 to 4 carbon atoms, the residual film rate after thermal curing can be increased. That is, when the polyimide is cyclized, ^{part of R 1} and R ² of the formula (1) is easily detached, and if detached, film loss will be caused. In the present invention, by setting ^{a part of R 1} and R ² of formula (1) as a non-polymerizable group having 1 to 4 carbon atoms, even if these groups are detached due to cyclization, the film can be more effectively suppressed. loss. That is, it is also possible to maintain a high residual film rate after thermal curing.

In the composition of the present invention, the lower limit of the glass transition temperature measured by the method described in the following Examples 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 higher than the above-mentioned value, it can be expected that the reliability in high-temperature processes such as the vapor deposition process for forming metal wiring or the bonding process between electrodes can be improved. The upper limit of the glass transition temperature is not particularly limited. For example, the desired performance can be sufficiently exhibited even at 350°C or lower.

In the composition of the present invention, it is preferable that the residual film rate in the exposed area is 50% or more, more preferably 70% or more, and more preferably 90% or more. In addition, the residual film rate of the exposure part means the value defined by the following. For the details of the measurement method, reference can be made to the description of Examples described later. Residual film rate in exposed area (%)=[film thickness of exposed area after development/film thickness of unexposed area before development]×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. In addition, the residual film rate after thermal curing means a value defined as follows. For the details of the measurement method, reference can be made to the description of Examples described later. Residual film rate after thermal curing (%)=[film thickness after thermal curing/film thickness before thermal curing]×100

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

式（1）中，X表示2價有機基，Y表示4價有機基，R¹ 及R² 分別獨立地係非聚合性有機基; （A）_l -L¹ -* （2） 式（2）中，A表示聚合性基，L¹ 表示單鍵或l+1價有機基，l表示1～10的整數，*表示與其他部位的鍵結部位。＜＜Polyimine precursor＞＞ The composition of the present invention contains a repeating unit represented by formula (1), and has a structure represented by formula (2) at at least one end, and has a weight average molecular weight of 50,000 or less The polyimide precursor. The polyimide precursor is also the polyimide precursor of the present invention. [Chemical formula 5]

In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and R ¹ and R ² are each independently a non-polymerizable organic group; (A) _l -L ¹ -* (2) formula (2) In ), A represents a polymerizable group, L ¹ represents a single bond or a l+1 valent organic group, l represents an integer from 1 to 10, and * represents a bonding site with other sites.

As the divalent organic group represented by X in the formula (1), a group including a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms can be exemplified A group, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination thereof is preferred. The group containing an aromatic group with 6 to 20 carbons is Better. As a particularly preferred embodiment, a group represented by "-Ar-L-Ar-" can be cited. Among them, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and Including the above-mentioned two or more groups in combination. Ar-based phenylene is preferred. L is an aliphatic hydrocarbon group with 1 or 2 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO ₂ -is preferred. Among them, aliphatic hydrocarbon-based alkylene groups are preferred.

The divalent organic group represented by X in the formula (1) is preferably a group derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, the divalent organic group represented by X includes a linear or branched aliphatic group having 2 to 20 carbons, a cyclic aliphatic group having 6 to 20 carbons, an aromatic group having 6 to 20 carbons, or Diamines including a combination of these groups are preferred, and diamines including an aromatic group having 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.

上述芳香族基中，A係單鍵或選自可以由氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHCO-及它們的組合之基團為較佳，係單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-、-SO₂ -之基團為更佳，選自包括-CH₂ -、-O-、-S-、-SO₂ -、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之組中之2價基團為進一步較佳。[Chemical formula 6]

Among the above aromatic groups, A is a single bond or is selected from aliphatic hydrocarbon groups having 1 to 10 carbons which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, -S(=O ) ₂ -, -NHCO- and their combination groups are preferred, which are single bonds or selected from alkylene groups with 1 to 3 carbons that can be substituted by fluorine atoms, -O-, -C (=O) -, -S-, -SO ₂ -groups are more preferably selected from the group including -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -and -C( The divalent group in the group of _{CH 3} ) _{2-is further preferred.}

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1 ,6-Diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane 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'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 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-aminophenyl) -Hydroxyphenyl) propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfide, bis(4-amino- 3-Hydroxyphenyl) sulfide, 4,4'-diaminopterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) )Phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(2-aminophenoxy)phenyl] ash, 1,4-bis(4- Aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 1,3-bis (4-aminophenoxy)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-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis (4-Aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4 -Diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)pyridium , 4,4'-dimethyl-3,3'-bis Aminodiphenyl sulfide, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diamine Base cumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m Phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminobenzene Base) ethane, diaminobenzylaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl) Hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-amino) Phenyl) Tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy) Phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4- Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'- Bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'- Bis(4-amino-2-trifluoromethylphenoxy) diphenyl sulfide, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl sulfide, 2 ,2-Bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-bis Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, At least one diamine of 2,2',5,5',6,6'-hexafluorotolidine and 4,4'''-diaminotetrabiphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[Chemical formula 7]

[Chemical formula 8]

In addition, as a preferred example, diamines having at least two alkylene glycol units in the main chain can also be cited. Preferably, it is a diamine that contains two or more of ethylene glycol chains and propylene glycol chains or both in total in one molecule, and more preferably does not contain an aromatic ring. 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 product names, made by HUNTSMAN), 1-(2-(2-(2-aminopropoxy) Ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., but It is not limited to these. The following shows 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) The structure of EDR-176.

[Chemical formula 9]

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

式（51）中，R¹⁰ ～R¹⁷ 分別獨立地係氫原子、氟原子或1價有機基，R¹⁰ ～R¹⁷ 中的至少一個係氟原子、甲基或三氟甲基。 作為R¹⁰ ～R¹⁷ 的1價有機基，可列舉碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 式（61） [化學式11]

式（61）中，R¹⁸ 及R¹⁹ 分別獨立地係氟原子或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可列舉2,2’-二甲基-4,4’-二胺基聯苯、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該些可以使用一種或可以組合使用兩種以上。From the viewpoint of 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, from the viewpoint of i-ray transmittance and availability, the divalent organic group represented by formula (61) is more preferable. 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 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably 1 to 6 carbons). 6) The fluorinated alkyl group and so on. Formula (61) [Chemical Formula 11]

In the formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group. As the diamine compound imparting the structure of formula (51) or (61), 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl) ) -4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.

式（5）中，R¹¹² 係單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO₂ -、-NHCO-及它們的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO₂ -中之基團為更佳，選自包括-CH₂ -、-C（CF₃ ）₂ -、-C（CH₃ ）₂ -、-O-、-CO-、-S-及-SO₂ -之組中之2價基團為進一步較佳。As the tetravalent organic group represented by Y of the formula (1), a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. Formula (5) [Chemical Formula 12]

In formula (5), R ¹¹² is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which may be substituted by fluorine atoms, -O- _{, -CO-, -S-, -SO 2} -, -NHCO- Groups in their combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons, -O-, -CO-, -S- and -SO ₂ -which may be substituted by fluorine atoms The group is more preferably selected from among -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO _2- The divalent group in the group is further preferred.

Formula (6) [Chemical Formula 13]

式（O）中，R¹¹⁵ 表示4價有機基。R¹¹⁵ 與由式（1）的Y表示之4價有機基的定義相同，較佳範圍亦相同。Regarding the tetravalent organic group represented by Y of the formula (1), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be cited. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical formula 14]

In 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.

As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetra Carboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3 ',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'oxydiphthalic 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-perylenetetracarboxylic 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, At least one of 3,4-benzenetetracarboxylic dianhydride and their C1-C6 alkyl derivatives and C1-C6 alkoxy derivatives.

In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples. [Chemical formula 15]

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

^{As the non-polymerizable organic group represented by R 1} and R ^{2 of the} formula (1), a group that does not contain a carbon-carbon unsaturated double bond is preferred. For example, linear or branched alkyl groups, cyclic alkyl groups, and aromatic groups are preferred. As an aromatic group, an aryl group, an aralkyl group, etc. are mentioned. The non-polymerizable organic group represented by R ¹ and R ² is more preferably a non-polymerizable organic group having 1 to 4 carbons, and more preferably a linear or branched alkyl group having 1 to 4 carbons. Preferred specific examples of non-polymerizable organic groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, decyl Tetraalkyl, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl, methyl, ethyl, propyl, iso Propyl, butyl, isobutyl, second butyl, and tertiary butyl are preferred, methyl and ethyl are more preferred, and methyl is further preferred.

The polyimide 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 a l+1 valent organic group, l represents an integer from 1 to 10, and * represents other parts The bonding site.

上述式中，*表示與式（2）的L¹ 的鍵結部位。R³ 表示氫原子或甲基，Z表示氧原子或NH。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, a (meth)allyl group, a (meth)acryloyl group, a group represented by the following formula (A-1), and a group represented by the formula (A-2) can be cited . [Chemical formula 16]

In the above formula, * represents the bonding site ^{with L 1 of 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 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. As specific examples of the l+1 valent organic group, the following structural units or a group constituted by combining two or more of the following structural units (which may form a ring structure) can be cited.

[Chemical formula 17]

In formula (2), l represents an integer from 1 to 10, preferably an integer from 2 to 10, more preferably an integer from 2 to 8, and even more preferably an integer from 2 to 5. According to this aspect, the residual film rate after development in the exposure part can be increased.

式（3）中，R³ 表示氫原子或甲基，Z表示氧原子或NH，L² 表示單鍵或m+1價有機基，m表示1～10的整數，*表示與其他部位的鍵結部位。 式（4）中，L³ 表示單鍵或n+1價有機基，n表示1～10的整數，*表示與其他部位的鍵結部位。The structure represented by formula (2) is preferably the structure represented by formula (3) or formula (4), and the structure represented by formula (3) is more preferable. According to this aspect, the residual film rate after development in the exposure part can be increased. [Chemical formula 18]

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 from 1 to 10, and * represents a bond with other parts Knot site. In the formula (4), L ³ represents a single bond or an n+1 valent organic group, n represents an integer of 1 to 10, and * represents a bonding site with other sites.

Regarding the m+1 valent organic group represented ^{by L 2 of} formula (3) and the n+1 valent organic group represented ^{by L 3 of} formula (4), there can be mentioned l+ represented ^{by L 1 of formula (2)} The preferred range of the group described with the monovalent organic group is also the same.

In formula (3), m represents an integer of 1-10, preferably an integer of 2-10, more preferably an integer of 2-8, and even more preferably an integer of 2-5. According to this aspect, the residual film rate in the exposure part can be increased. In formula (4), n represents an integer of 1-10, preferably an integer of 2-10, more preferably an integer of 2-8, and even more preferably an integer of 2-5. According to this aspect, the residual film rate in the exposure part can be increased.

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

For the purpose of improving the adhesion to the substrate, the polyimide precursor of the present invention may also include an aliphatic group having a siloxane structure. Specifically, as the diamine component used to introduce the aliphatic group of the silicone structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethyl Base pentasiloxane and so on.

In the polyimide precursor, the repeating unit represented by formula (1) may be one type or two or more types. In addition, the polyimide precursor may include structural isomers of the repeating unit represented by formula (1). In addition, the polyimide precursor includes not only the repeating unit represented by formula (1), but also other types of repeating units.

The polyimide precursor of the present invention preferably contains 50 mol% or more of the total repeating units of the repeating unit represented by formula (1), more preferably 70 mol% or more, and more than 90 mol% Further better.

The weight average molecular weight (Mw) of the polyimide precursor is 50,000 or less, preferably 40,000 or less, and more preferably 35,000 or less. The lower limit is preferably more than 2000, more preferably 5000 or more, more preferably 6000 or more, and more preferably 7000 or more. As long as the weight average molecular weight of the polyimide precursor is 50,000 or less, the developability is excellent. Moreover, if the weight average molecular weight of the polyimide precursor is 5000 or more, the mechanical strength of the cured film obtained will be good.

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 less is preferred, 4.0 or less is more preferred, 3.8 or less is more preferred, 3.2 or less is more preferred, and 3.1 or less is further Preferably, 3.0 or less is more preferable, and 2.95 or less is especially more preferable.

The content of the polyimide precursor in the composition of the present invention is preferably 10 to 99% by mass of the total solid content of the composition of the present invention, more preferably 50 to 98% by mass, and 70 to 96% by mass Further better. In addition, it has a repeating unit represented by formula (1) in the composition of the present invention, and has a structure represented by "(A) _l -L ¹ -*" at at least one end, and has a weight average molecular weight of 50,000 or less The content of the polyimide precursor is preferably 10 to 99% by mass of the total solid content of the composition of the present invention, more preferably 50 to 98% by mass, and more preferably 70 to 96% by mass.

The polyimide precursor of the present invention can be produced by reacting a diamine with tetracarboxylic dianhydride or its derivative, and then further reacting a compound having a polymerizable group with the reactant, and then carboxyl ester化. In addition, as another method, after reacting diamine, tetracarboxylic dianhydride, etc., with an alcohol ester, it can be produced by further reacting a compound having a polymerizable group with the reactant. In the present invention, the molar ratio of the raw material of the tetracarboxylic dianhydride or its derivative to the aforementioned alcohol (tetracarboxylic dianhydride or its derivative: alcohol) is preferably 0.9 to 1.1: 2.1 to 1.9. In the present invention, the molar ratio of the raw materials of tetracarboxylic dianhydride or its derivative and diamine (tetracarboxylic dianhydride or its derivative: diamine) is preferably 0.8-1.2: 1.2-0.8, 1.001- 1.2: 0.999 to 0.8 is more preferable. In this way, by making the tetracarboxylic dianhydride or its derivative slightly concentrated, the end before the addition of the polymerizable compound becomes an acid anhydride structure, and the compound having a hydroxyl group or an amino group and a polymerizable group can be reliably introduced Polymeric base. The reaction temperature of the above reaction is preferably -20 to 60°C. In addition, the reaction time is preferably 30 minutes to 10 hours.

In addition, the molecular weight of the alcohol reacted with tetracarboxylic dianhydride is preferably 30-150, more preferably 30-80, and still more preferably 30-65. As long as the molecular weight of the alcohol reacted with tetracarboxylic dianhydride is within the above range, a polyimide precursor with excellent resolution can be easily obtained. The alcohol that reacts with tetracarboxylic dianhydride is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, and even more preferably an alcohol having 1 to 3 carbon atoms, and an alcohol having 1 or 2 carbon atoms. Alcohol is more preferable, and alcohol (methanol) having a carbon number of 1 is still more preferable. Specific examples of the above alcohol include methanol, ethanol, propanol, and n-butanol, and methanol is particularly preferred.

The compound having a polymerizable group is preferably a compound having 1 to 10 polymerizable groups, a compound having 2 to 8 polymerizable groups is more preferred, and a compound having 2 to 5 polymerizable groups is even more preferred. As the polymerizable group, a group containing a carbon-carbon unsaturated double bond is preferred. Specifically, vinyl groups, (meth)allyl groups, (meth)acryloyl groups, styryl groups, groups represented by the above-mentioned formula (A-1), and groups represented by the above-mentioned formula (A- 2) The group represented. In addition, the molecular weight of the compound having a polymerizable group is preferably from 100 to 2000, more preferably from 100 to 1500, and even more preferably from 100 to 1000. As long as the molecular weight of the compound having a polymerizable group is within the above range, it is a specific example of a compound that can easily obtain a polyimide precursor with excellent resolution. When an excessive amount of acid dianhydride is used, neopentylerythritol can be exemplified Tri(meth)acrylate, glycerol di(meth)acrylate, isocyanuric acid ethylene oxide (EO) modified di(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-aminostyrene, and when an excessive amount of diamine is used, 2-isocyanatoethyl ( Meth) acrylate, 1,1-bisacryloxymethyl) ethyl isocyanate.

In the production method of the polyimide precursor, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.

When producing the polyimide precursor, in order to further improve the storage stability, one of the main chain ends of the precursor may be blocked with a blocking agent such as acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound. Among these, it is more preferable to use monoamines. Preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyl 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 -Aminothiophenols, etc. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of capping agents.

When the polyimide precursor is manufactured, a process of precipitation of solids may be included. Specifically, by precipitating the polyimide precursor in the reaction liquid in a poor solvent such as water or alcohol, the solid can be precipitated. Then, by drying the polyimide precursor, a powdery polyimine precursor can be obtained.

<<Photopolymerization initiator>> The composition of the present invention contains a photopolymerization initiator. Regarding the photopolymerization initiator, a photocationic polymerization initiator, a photoradical polymerization initiator, and the like can be cited, 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 light is irradiated to generate radicals caused by free radicals. It hardens and can reduce the solubility in the light-irradiated part. Therefore, for example, there is an advantage that by exposing the photosensitive resin composition layer through a photomask having a pattern for shielding only the electrode portion, it is possible to easily create regions with different solubility in accordance with the electrode pattern.

The photopolymerization initiator is not particularly limited, and it can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that has some effects with light-excited sensitizers and generates active free radicals. It is preferable that the photopolymerization initiator contains at least one compound having at least about 50 molar absorption coefficient in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.) can be used. , Phosphine oxides and other phosphine compounds, hexaarylbisimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds , Hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Regarding these details, reference can be made to the description in paragraphs 0165 to 0182 of JP 2016-027357 A, and the contents are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and the content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the phosphine 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 (brand names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, it is also possible to use the compound described in Japanese Patent Application Laid-Open No. 2009-191179 that has a maximum absorption wavelength that matches a light source of wavelengths such as 365 nm or 405 nm. Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (brand name: both manufactured by BASF Corporation), which are commercially available products, can be used. As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like are exemplified.

市售品中，還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMERN-1919（ADEKA CORPORATION製、日本特開2012-14052號公報中所記載之光聚合起始劑2）。又，能夠使用TR-PBG-304（常州強力電子新材料有限公司製）、ADEKAARKLS NCI-831及ADEKAARKLS NCI-930（ADEKA CORPORATION製）。又，還能能使用DFI-091（DAITO CHEMIX Co.,Ltd.製）。 進而，還能夠使用具有氟原子之肟化合物。作為該種肟化合物的具體例，可列舉日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等。 作為最佳的肟化合物，可列舉日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物、日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。As the photopolymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a thermal base generator, so it is particularly preferred. As specific examples of the oxime compound, the compounds described in JP 2001-233842, the compounds described in JP 2000-80068, and the compounds described in JP 2006-342166 can be used. . As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxy Group imino-1-phenylpropan-1-one and so on. [Chemical formula 19]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMERN-1919 (made by ADEKA CORPORATION, Japanese Patent Publication No. 2012-14052 The photopolymerization initiator described in the gazette 2). In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36-40, and the compounds described in paragraph 0345 of JP 2014-500852 A. The compound (C-3) and the like described in paragraph 0101 of the 2013-164471 Bulletin. As the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and oxime compounds having sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited. Wait.

式（I）中，R⁵⁰ 係碳數1～20的烷基；因1個以上的氧原子而中斷之碳數2～20的烷基；碳數1～12的烷氧基；苯基；由碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數1～12的烯基、因1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，R⁵¹ 係由式（II）表示之基團，或者係與R⁵⁰ 相同的基團，R⁵² ～R⁵⁴ 各自獨立地係碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式21]

式中，R⁵⁵ ～R⁵⁷ 與上述式（I）的R⁵² ～R⁵⁴ 相同。From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and phosphine compounds. , Phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- Iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferable photopolymerization initiators are trihalomethyl triazine compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds , Benzophenone compounds, acetophenone compounds, at least selected from the group consisting of trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds One kind of compound is more preferable, metallocene compound or oxime compound is more preferable, and oxime compound is particularly preferable. In addition, the photopolymerization initiator can also use N,N', such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. -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, alkylanthraquinones, etc., quinones formed by the condensation of aromatic rings, and benzoin Benzoin ether compounds such as base ethers, Benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. In addition, a compound represented by the following formula (I) can also be used. [Chemical formula 20]

In formula (I), R ⁵⁰ is an alkyl group with 1 to 20 carbons; an alkyl group with 2 to 20 carbons interrupted by more than one oxygen atom; an alkoxy group with 1 to 12 carbons; a phenyl group; Alkyl with 1 to 20 carbons, alkoxy with 1 to 12 carbons, halogen atoms, cyclopentyl, cyclohexyl, alkenyl with 1 to 12 carbons, carbon interrupted by more than one oxygen atom A phenyl group or biphenyl group substituted with at least one of an alkyl group having 2 to 18 and an alkyl group having 1 to 4 carbons, R ⁵¹ is a group represented by formula (II), or the same group as ^{R 50} In the group, R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen. [Chemical formula 21]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as ^{R 52} to R ^{54 in the} above formula (I).

In addition, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication 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 type, or two or more types. When two or more types of photopolymerization initiators are contained, the total amount is preferably in the above-mentioned range.

<<Solvent>> The composition of the present invention contains a solvent. As the solvent, a known solvent can be used arbitrarily. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl Butyl acid, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example, alkoxy methyl acetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) , 3-alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy propionic acid ethyl ester, etc. (for example, 3-methoxy propionic acid methyl ester, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 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)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy Ethyl-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, acetone Ethyl acrylate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate are preferably mentioned. , 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 acetic acid Ester etc. As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are preferably mentioned. As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably mentioned. As the sulfenites, dimethyl sulfenite can preferably be cited. As the amides, preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, etc. .

Regarding the solvent, from the viewpoint of improvement of coating surface properties, etc., a form in which two or more of them are mixed is also preferable. Among them, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol ethyl A mixed solution composed of two or more of the acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone at the same time.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the composition of the present invention is 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 can 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-mentioned range is preferable. As long as it is a spraying method, it is preferable to set it as the amount of 0.1 mass%-50 mass %, and it is more preferable to set it as the amount of 1.0 mass%-25 mass %. By adjusting the content of the solvent according to the coating method, a photosensitive resin composition layer of a desired thickness can be uniformly formed. The solvent may be only one type or two or more types. When two or more kinds of solvents are used, it is preferable that the total of them is in the above-mentioned range.

<<Multifunctional radical polymerizable monomer>> The composition of the present invention preferably contains a polyfunctional radical polymerizable monomer (hereinafter, also referred to as a polymerizable monomer). With this configuration, a cured film with 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 groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth)acryloyl group, and a (meth)allyl group. The radical polymerizable group is preferably a (meth)acryloyl group.

The polymerizable monomer preferably has two or more radical polymerizable groups, and more preferably has three or more. 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 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. . In addition, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or higher polymerizable monomer. In addition, the number of functional groups of a polymerizable monomer refers to the number of radical polymerizable groups in one molecule.

Specific examples of polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof. They are esters of unsaturated carboxylic acids and polyhydric alcohols, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl, amine, and mercapto groups and monofunctional or polyfunctional isocyanates or epoxy groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. Dehydration condensation reaction product of functional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or toluene Substitution reactants of unsaturated carboxylic acid esters or amides having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, reference can be made to the description in paragraphs 0113 to 0122 of JP 2016-027357 A, and the content can be incorporated into this specification.

Moreover, the compound which has a boiling point of 100 degreeC or more of a polymerizable monomer under normal pressure is also preferable. As an example, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentyl erythritol tri(meth)acrylate can be cited. Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohols Compounds that are (meth)acrylated after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Application Publication No. 51-37193 (Meth) acrylate urethanes, polyester acrylates described in Japanese Patent Application Publication No. 48-64183, Japanese Patent Application Publication No. 49-43191, Japanese Patent Application Publication No. 52-30490 , Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. Moreover, the polyfunctional (meth)acrylate etc. which are obtained by making the compound which has a cyclic ether group and ethylenically unsaturated group, such as a polyfunctional carboxylic acid and glycidyl (meth)acrylate react, are mentioned. In addition, as other preferable polymerizable monomers, those described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, Japanese Patent No. 4364216, etc. can also be used. More than one compound or cardo resin containing ethylenically unsaturated bond groups. Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, or Japanese Patent Application Publication No. 2- Vinyl phosphonic acid compounds and the like described in the Gazette No. 25493. In addition, the perfluoroalkyl group-containing compound described in JP 61-22048 A can also be used. Furthermore, it is also possible to use those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

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

[Chemical formula 22]

[Chemical formula 23]

In each of the above formulas, n is an integer of 0-14, and m is an integer of 0-8. A plurality of R and T in the molecule may be the same or different. In each of the polymerizable compounds represented by the above formulas (MO-1) to (MO-5), at least one of the plural Rs is represented by -OC (=O) CH=CH ₂ or -OC (=O) C(CH ₃ )=CH ₂ represents a group. As specific examples of polymerizable monomers represented by the above formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP 2007-269779 A can be preferably used.

In addition, the following compounds described as formula (1) and formula (2) in Japanese Unexamined Patent Publication No. 10-62986 and their specific examples can also be used as polymerizable monomers. The compound is added to a polyfunctional alcohol. It is a compound formed by (meth)acrylic acid esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as a polymerizable monomer, and these contents are incorporated in this specification.

As polymerizable monomers, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dineopentaerythritol penta(meth)acrylate (as a commercial product is KAYARAD D- 310; manufactured by Nippon Kayaku Co., Ltd.), dineopentyl erythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues and propylene glycol residues are preferred. It is also possible to use their oligomer types. Moreover, as a preferable example, the neopentyl erythritol derivative and/or dineo erythritol derivative of the above-mentioned formula (MO-1) and formula (MO-2) can also be cited.

Commercially available polymerizable monomers include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having 4 vinyloxy chains, and SR-494 as a 2-functional acrylate having 4 vinyloxy chains. SR-209 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxy chains, and DPCA-60 as a 6-functional acrylate with 3 isobutoxy chains. 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 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH- 600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As polymerizable monomers, amines such as those 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 It has epoxy resins as described 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 with an ethane-based skeleton are also preferred. Furthermore, as the polymerizable monomer, the structure having an amino group in the molecule as described in JP 63-277653 A, JP 63-260909 A, and JP 1-105238 A can also be used. Or compounds of sulfide structure.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Among the polymerizable monomers with acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The unreacted hydroxyl groups of the aliphatic polyhydroxy compounds are reacted with non-aromatic carboxylic anhydrides to polymerize with acid groups. Sexual monomer is better. Particularly preferred is that among polymerizable monomers having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides, aliphatic polyhydroxy compounds are used as neopentyl erythritol and/or dineopentaerythritol The compound. As a commercially available product, for example, M-510, M-520, etc. can be cited as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. The polymerizable monomer having an acid group may be used singly or in combination of two or more. In addition, if necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group can be used at the same time. The preferable acid value of the polymerizable monomer having an acid group is 0.1-40 mgKOH/g, and particularly preferably 5-30 mgKOH/g. As long as the acid value of the polymerizable monomer is within the above-mentioned range, the manufacturing or handling properties are excellent, and the developability is further excellent. In addition, the polymerizability is also good.

From the viewpoint of good polymerizability and heat resistance, the content of the polymerizable monomer is preferably 1 to 50% by mass relative to the total solid content of the composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 30% by mass or less. A polymerizable monomer may be used individually by 1 type, and may mix and use 2 or more types. In addition, the mass ratio of polyimide precursor to 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. As long as the mass ratio of the polyimide precursor to the polymerizable monomer is in the above range, a cured film with more excellent polymerizability and heat resistance can be formed.

From the viewpoint of suppressing warpage due to the control of the modulus of elasticity of the cured film, the composition of the present invention can preferably use a monofunctional polymerizable monomer. As a 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 -Methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylic acid derivatives Compounds, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Propyl compounds and so on. As a 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 also contain other polymerizable compounds other than the aforementioned polyimide precursor and polymerizable monomers. Examples of other polymerizable compounds include compounds having methylol, alkoxymethyl, or oxymethyl; epoxy compounds; oxetane compounds; and benzoxazine compounds.

(The compound having a hydroxymethyl group, an alkoxymethyl group, or an oxymethyl group) As a compound having a hydroxymethyl group, an alkoxymethyl group or an oxymethyl group, a compound represented by the following formula (AM1) is preferred.

（式中，t表示1～20的整數，R⁴ 表示碳數1～200的t價有機基，R⁵ 表示由-OR⁶ 或-OCO-R⁷ 表示之基團，R⁶ 表示氫原子或碳數1～10的有機基，R⁷ 表示碳數1～10的有機基。）[Chemical formula 24]

(In the formula, t represents an integer from 1 to 20, R ⁴ represents a t-valent organic group with a carbon number of 1 to 200, 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 carbons, and R 7} represents an organic group having 1 to 10 carbons.)

The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass relative to 100 parts by mass of the polyimide precursor. More preferably, it is 10 to 35 parts by mass. In addition, the total amount of other polymerizable compounds contains 10 to 90% by mass of the compound represented by the following formula (AM4), and preferably 10 to 90% by mass of the compound represented by the following formula (AM5).

（式中，R⁴ 表示碳數1～200的2價有機基，R⁵ 表示由-OR⁶ 或-OCO-R⁷ 表示之基團，R⁶ 表示氫原子或碳數1～10的有機基，R⁷ 表示碳數1～10的有機基。）[Chemical formula 25]

(In the formula, R ⁴ represents a divalent organic group with 1 to 200 carbons, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ and R ⁶ represents a hydrogen atom or an organic group with 1 to 10 carbons. , R ⁷ represents an organic group having 1 to 10 carbons.)

（式中，u表示3～8的整數，R⁴ 表示碳數1～200的u價有機基，R⁵ 表示由-OR⁶ 或、-OCO-R⁷ 表示之基團，R⁶ 表示氫原子或碳數1～10的有機基，R⁷ 表示碳數1～10的有機基。）[Chemical formula 26]

(In the formula, u represents an integer from 3 to 8, R ⁴ represents a U-valent organic group with 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 carbons, and R 7} represents an organic group having 1 to 10 carbons.)

By using a compound having the above-mentioned hydroxymethyl group or the like, when the composition of the present invention is applied to an uneven substrate, the generation of cracks can be more effectively suppressed. In addition, it is possible to form a cured film having excellent pattern processability and a 5% mass reduction temperature of 350°C or higher, more preferably 380°C or higher, and high heat resistance. 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 the trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-t-buthylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6 acetoxymethyl-p-cresol) Wait.

Also, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, 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 epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy is based on cross-linking reaction below 200°C, and it is difficult to cause film shrinkage because it does not cause dehydration reaction from cross-linking. Therefore, by containing the epoxy compound, the low-temperature hardening and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. With this, the modulus of elasticity is further reduced, and warping can be suppressed. In addition, the flexibility of the film is increased, and a cured film having excellent elongation and the like can be obtained. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, propylene glycol diglycidyl ether and other alkylene glycol type epoxy resins, and polypropylene glycol diglycidyl ethers and the like. Epoxy group-containing silicones such as alkyl glycol type epoxy resins and polymethyl (glycidoxypropyl) silicones, etc., but are not limited to these. Specifically, you can include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, 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, EPICLONEXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E ( Trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), etc. Among these, from the viewpoints of suppressing warpage and excellent heat resistance, epoxy resins containing polyethylene oxide groups are preferred. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups, so they are preferred.

The content of the epoxy compound is preferably 5-50 parts by mass relative to 100 parts by mass of the polyimide precursor, more preferably 10-50 parts by mass, and still more preferably 10-40 parts by mass. If the content of the epoxy compound is 5 parts by mass or more, it is possible to suppress the warpage of the cured film obtained, and if it is 50 parts by mass or less, it is possible to further suppress pattern embedding due to reflow during curing.

(Oxetane compound (compound with oxetanyl group)) As the oxetane compound, a compound having two or more oxetane rings in one molecule, 3-ethyl -3-hydroxymethoxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2 -Ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, Aron Oxetane series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or in combination. Two or more.

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

(Benzoxazine compounds (compounds with benzoxazole groups)) Benzoxazine compounds do not produce outgassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing heat shrinkage and inhibiting production Warpage is therefore preferable.

Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine (the above are trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), and benzoxazine addition of polyhydroxystyrene resin Materials, novolac-type dihydrobenzoxazine compounds. These can be used alone, or two or more of them can be mixed and used.

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

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

In addition, an ion scavenger that traps anions such as halogen ions can also be used.

As other metal discoloration inhibitors, rust inhibitors described in paragraph 0094 of JP 2013-15701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP The compound described in paragraph 0052 of 2011-59656, the compound described in paragraphs 0114, 0116, and 0118 of JP 2012-194520, etc.

As a specific example of a metal discoloration inhibitor, the following compounds can be mentioned, for example. [Chemical formula 27]

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 -1.0% by mass is more preferable. The metal discoloration inhibitor may be one type or two or more types. When there are two or more types of metal discoloration inhibitors, it is preferable that the total of them is in the above-mentioned range.

當本發明的組成物具有聚合抑制劑時，聚合抑制劑的含量相對於本發明的組成物的總固體成分係0.01～5質量%為較佳。 聚合抑制劑可以僅為一種，亦可以為兩種以上。當聚合抑制劑為兩種以上時，其合計為上述範圍為較佳。<<Polymerization inhibitor>> The composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6 -Tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-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-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used. In addition, the following compounds (Me is a methyl group) can also be used. [Chemical formula 28]

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 relative to the total solid content of the composition of the present invention. There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the sum total is the above-mentioned range.

<<Thermal base generator>> The composition of the present invention preferably contains a thermal base generator. The type of the thermal base generator is not particularly limited, and it is preferable to include a thermal base generator. The thermal base generator includes an acidic compound selected from bases generated when heated to 40°C or higher and has a pKa1 of 0-4 At least one of the anion and the ammonium salt of the ammonium cation. _{Here, pKa1 represents the logarithm (-Log 10} Ka) of the reciprocal of the dissociation constant (Ka) of the first proton of the acid, and the details will be described later.

Regarding the acidic compound (A1) and the ammonium salt (A2), when heated, a base is generated. Therefore, the base generated from these compounds can promote the cyclization reaction of polyimide precursors and the like, and can be used at low temperatures. Next, cyclization of polyimide precursors, etc. is performed. In addition, even if these compounds coexist with polyimide precursors etc. which are cyclized and hardened by a base, as long as they are not heated, the cyclization of the polyimide precursors etc. will hardly proceed, so they can be prepared. Composition with excellent storage stability. In addition, in this specification, an acidic compound refers to a compound whose value is less than 7 obtained by measuring the following solution at 20°C using a pH (power of hydrogen) meter. The solution is to extract 1g of the compound into a container , Add 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water/tetrahydrofuran = 1/4), and stir at room temperature for 1 hour to obtain.

In this embodiment, the base 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, the alkali is unlikely to be generated during storage, so a composition with excellent stability can be prepared. As long as the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor and the like can be lowered. Regarding the alkali generation temperature, for example, differential scanning calorimetry can be used to heat the compound in a pressure-resistant capsule at 5°C/min to 250°C, read the peak temperature of the heating peak with the lowest temperature, and use the peak temperature as the alkali Generate temperature for measurement.

In this embodiment, alkali-based secondary amines or tertiary amines produced by a thermal alkali generator are preferred, and tertiary amines are more preferred. The tertiary amine has high basicity, so it can further reduce the cyclization temperature of polyimine precursors and polybenzoxazole precursors. In addition, the boiling point of the alkali produced by the thermal alkali generator is preferably 80°C or higher, more preferably 100°C or higher, and more preferably 140°C or higher. In addition, the molecular weight of the base produced is preferably from 80 to 2,000. It is more preferable that the lower limit is 100 or more. The upper limit is more preferably 500 or less. In addition, the value of the molecular weight is a theoretical value obtained based on the structural formula.

In this embodiment, the acidic compound (A1) preferably contains one or more selected from the group consisting of an ammonium salt and a compound represented by the formula (101) or (102) described later.

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

式（101）及式（102）中，R¹ ～R⁶ 分別獨立地表示氫原子或烴基，R⁷ 表示烴基。式（101）及式（102）中的R¹ 與R² 、R³ 與R⁴ 、R⁵ 與R⁶ 、R⁵ 與R⁷ 可以分別鍵結而形成環。In this embodiment, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bonded to any part of the ammonium cation via a covalent bond, or it may be present outside the molecule of the ammonium cation, but it is preferred to have it 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 and the anion are not bonded by 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 29]

In formula (101) and formula (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 , and R ⁵ and R ^{7 in} formula (101) and formula (102) may be respectively bonded to form a ring.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5). [Chemical formula 30]

In formulas (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 formula (101) or formula (102). In formulas (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 0-5.

In this embodiment, it is preferable that the ammonium salt has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and 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 in the above range, the polyimide precursor or the like can be cyclized at a low temperature, and furthermore, the stability of the composition can be improved. As long as pKa1 is 4 or less, the stability of the thermal base generator will be good, the generation of base will be suppressed without heating, and the stability of the composition will be good. As long as pKa1 is 0 or more, the generated alkali is not easily neutralized, and the cyclization efficiency of polyimide precursors and the like is good. The type of anion is preferably one selected from the group consisting of carboxylic acid anion, phenol anion, phosphoric acid anion, and sulfuric acid anion, and carboxylic acid anion is more preferable from the viewpoint of compatibility of salt stability and thermal decomposition. That is, a salt of an ammonium salt-based ammonium cation and a carboxylic anion is more preferable. The carboxylic acid anion is preferably an anion of a divalent or more 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 used as a thermal alkali generator that can further improve the stability, curability, and developability of the 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 anion of the carboxylic acid whose pKa1 of the carboxylic acid anion system is 4 or less is preferable. It is more preferable that the pKa1 is 3.5 or less, and it is still more preferable that it is 3.2 or less. According to this aspect, the stability of the composition can be further improved. Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software using ACD/pKa (manufactured by ACD/Labs) was used.

式（X1）中，EWG表示吸電子基。The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical formula 31]

In formula (X1), EWG represents an electron withdrawing group.

In this embodiment, the electron withdrawing group refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail by Yu Tono Yu, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents whose σm represents a positive value include CF ₃ groups (σm=0.43), CF ₃ CO groups (σm=0.63), HC≡C groups (σm=0.21), and CH ₂ =CH groups ( 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 acetyl group, and Ph represents a phenyl group.

式（EWG-1）～（EWG-6）中，R^x1 ～R^x3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 32]

In the formulas (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.

式（XA）中，L¹⁰ 表示單鍵或選自伸烷基、伸烯基、芳香族基團、-NR^X -及它們的組合中之2價連接基，R^X 表示氫原子、烷基、烯基或芳基。In this embodiment, the carboxylic acid anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 33]

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, -NR ^X -and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group , Alkenyl or aryl.

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

[化學式35]

As specific examples of the thermal base generator, the following compounds can be cited. [Chemical formula 34]

[Chemical formula 35]

[Chemical formula 36]

When the composition of the present invention contains a thermal base generator, the content of the thermal base generator is preferably 0.1-50% by mass relative to 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. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above-mentioned range.

<<Metal adhesion improver>> The composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, and the like. As an example of a metal adhesion improving agent, a silane coupling agent etc. are mentioned.

Examples of silane coupling agents include the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication WO2011/080992A1, and JP 2014 -191252, the compound described in paragraphs 0060 to 0061, the compound described in JP 2014-41264, paragraphs 0045 to 0052, and the compound described in international publication WO2014/097594, paragraph 0055. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group. [Chemical formula 37]

In addition, as the metal adhesion modifier, the compound described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the sulfides described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used.

The content of the metal adhesion modifier is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass relative to 100 parts by mass of the polyimide precursor. By setting it as 0.1 parts by mass or more, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it as 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing process become better. There may be only one type of metal adhesion modifier, or two or more types. When two or more are used, it is preferable that the sum total is the above-mentioned range.

＜＜Other additives＞＞ The composition of the present invention can add various additives, such as photobase generators, thermal polymerization initiators, thermal acid generators, and sensitizers, as needed, within the range that does not impair the effects of the present invention. 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, and does not show activity under normal temperature and pressure conditions. However, if it is irradiated and heated by electromagnetic waves as an external stimulus, it is not a compound that generates a base (alkaline substance). There is no particular limitation. The alkali generated by exposure functions as a catalyst when the polyimide precursor or the like is hardened by heating, and therefore can be preferably used in a negative type.

The content of the photobase generator is not particularly limited as long as it can form a pattern of the desired resin, and can be set to a normal content. The photobase generator is preferably within the range of 0.01 parts by mass or more and less than 30 parts by mass relative to 100 parts by mass of the polyimide precursor, more preferably within the range of 0.05 parts by mass to 25 parts by mass, which is 0.1 parts by mass It is more preferable to be in the range of 20 parts by mass. The photobase generator may be only one type or two or more types. When there are two or more photobase generators, the total range is preferably the above-mentioned range.

In the present invention, compounds known as photobase generators can be used. For example, such as M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Kadooka Masahiro, 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). Structures such as ammonium salts, such as those where the amidino moiety is latentized by the formation of carboxylic acids and salts, ionic compounds in which alkali components are neutralized by the formation of salts, by carbamate derivatives, oximes A nonionic compound in which urethane bonds such as ester derivatives and acyl compounds or alkali components such as oxime bonds are latentized.

In addition, as the photobase generator, urethane derivatives, amide derivatives, amide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, etc. can also be used. In addition, the photobase generator having a cinnamic acid amide structure described in Japanese Patent Application Publication No. 2009-80452 and International Publication No. WO2009/123122, Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008- The photobase generator having a carbamate structure described in 247747, and those having an oxime structure and a carbamate structure described in JP 2007-249013 and 2008-003581 Photo base generator. In addition, examples of photobase generators include compounds described in paragraphs 0185 to 0188, paragraphs 0199 to 0200, and paragraph 0202 of JP 2012-93746 A, and 0022 of JP 2013-194205 A The compound described in paragraph-0069, the compound described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compound described in paragraph 0052 of International Publication WO2010/064631.

(Thermal polymerization initiator) The composition of the present invention may contain 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. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the cyclization of the polyimine precursor can be performed, and the polymerization reaction of the polyimine precursor can be performed, so that a higher degree of heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A.

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 0.1-50% by mass, 0.1-30% by mass % Is more preferable, and 0.1-20% by mass is particularly preferable. Moreover, it is 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 with more excellent heat resistance can be easily formed. The thermal radical polymerization initiator may be only one type or two or more types. When two or more types of thermal radical polymerization initiators are used, the total amount is preferably in the above-mentioned range.

(Thermal acid generator) The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates acid by heating and promotes the cyclization of the polyimide precursor to further improve the mechanical properties of the cured film. As for the thermal acid generator, the compounds described in paragraph 0059 of JP 2013-167742 A, etc. can be cited.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polyimide precursor, and more preferably 0.1 parts by mass or more. Containing 0.01 parts by mass or more of the thermal acid generator promotes the crosslinking reaction and the cyclization of the polyimide precursor, and therefore can further improve the mechanical properties and chemical resistance of the cured film. In addition, 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 particularly preferably 10 parts by mass or less. Only one type of thermal acid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above-mentioned range.

(Sensitizing dye) The composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a base generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, etc. Thereby, the alkali generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo chemical changes and decompose to generate radicals, acids, or alkalis. For the details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A, and the contents are incorporated into this specification.

When the composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01-20% by mass relative to the total solid content of the composition of the present invention, more preferably 0.1-15% by mass, and 0.5-10 The mass% is more preferable. The sensitizing dye may be used singly, or two or more of them may be used at the same time.

(Chain transfer agent) The composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or after oxidation, they can generate free radicals by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole Class etc.).

When the composition of the present invention has a chain transfer agent, the content of the chain transfer agent relative to 100 parts by mass of the total solid content of the composition of the present invention is preferably 0.01-20 parts by mass, more preferably 1-10 parts by mass, It is particularly preferably 1 to 5 parts by mass. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total range is preferably the above-mentioned range.

(Surfactant) From the viewpoint of improving coatability, various surfactants can be added to the composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants can be used. [Chemical formula 38]

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

(Higher fatty acid derivatives) In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide can be added to the composition of the present invention during the drying process after coating Locally exists 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 relative to the total solid content of the composition of the present invention. The higher fatty acid derivative may be one type or two or more types. When there are two or more higher fatty acid derivatives, it is preferable that the total range is the above-mentioned range.

＜＜Restrictions on other substances contained＞＞ 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 metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably in the above-mentioned range. In addition, as a method of reducing metal impurities inadvertently included in the composition of the present invention, it is possible to select a raw material with a lower 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. Filter by filter, lining the device with polytetrafluoroethylene, and carry out distillation under the condition of suppressing pollution as much as possible.

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

<Preparation of composition> The composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. In addition, for the purpose of removing foreign substances such as garbage or particulates in the composition, filtration using only a filter is preferable. 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 can be cleaned in advance with an organic solvent. In the filtration process of the filter, the 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 cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbents. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

<Cured film, semiconductor device, cured film manufacturing method, semiconductor device, laminated body manufacturing method, and semiconductor device manufacturing method> Next, the cured film, semiconductor device, cured film manufacturing method, semiconductor device, and laminated body of the present invention The manufacturing method of the semiconductor device and the manufacturing method of the semiconductor device will be described. The cured film of the present invention is formed 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. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

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

As a field to which the cured film of this invention can be applied, the insulating film of a semiconductor device, the interlayer insulating film for rewiring layers, etc. are mentioned. In particular, since the resolution is good, it can also be suitably used for interlayer insulating films for rewiring layers in three-dimensional mounting devices, and the like. In addition, 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 plates, the use of molded parts, the production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

The production method of the cured film of the present invention may include the use of the composition of the present invention. Preferably, it has a process for forming a negative photosensitive resin composition layer in which the negative photosensitive resin composition of the present invention is applied to a substrate to form a layer, and an exposure process for exposing the negative photosensitive resin composition layer And the process of developing the exposed negative photosensitive resin composition layer. In the manufacturing method of the present invention, it can also be a state that includes a process of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500° C. after the development process. Since the cured film of this invention is excellent in heat resistance, even if it heats at 150-500 degreeC, it can maintain good performance.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the manufacturing method of the laminated body of the present invention, according to the manufacturing method of the 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 process are preferably performed in sequence again . In particular, it is preferable to further sequentially perform the negative photosensitive resin composition layer forming process, the exposure process, and the development treatment process 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, it can be a laminate. In the present invention, it is particularly preferable to provide a metal layer on the part that has been developed and removed after the hardened film is provided and after the development.

The present invention also discloses a semiconductor device including the cured film of the present invention. Hereinafter, an embodiment of a semiconductor device in which the composition of the present invention is used for an interlayer insulating film for a rewiring layer will be described.

The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a laminated body 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are laminated is arranged on a wiring board 120. In addition, in this embodiment, the case where the number of stacked layers of the semiconductor element (semiconductor wafer) is 4 layers is mainly described, but the number of stacked layers of the semiconductor element (semiconductor wafer) is not particularly limited. For example, it can be 2 layers, 8 layers, 16 floors, 32 floors, etc. Also, it can be one layer.

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 having no through electrodes and a semiconductor element 101b to 101d having through electrodes 102b to 102d are flip-chip bonded. That is, the electrode pad of the semiconductor element 101a without the through electrode and the connection pad on the semiconductor element 101a side of the adjacent semiconductor element 101b with the through electrode 102b are connected by metal bumps 103a such as solder bumps. And 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 adjacent semiconductor element 101c having the through electrode 102c are formed by metal bumps 103b such as solder bumps. connection. Similarly, the connection pad on the other side of the semiconductor element 101c with the through electrode 102c and the connection pad on the semiconductor element 101c side of the adjacent semiconductor element 101d with the through electrode 102d are made of metal bumps such as solder bumps. 103c and connected.

An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

The laminated body 101 is arranged on the wiring board 120. As the wiring substrate 120, for example, a multilayer wiring substrate in which an insulating substrate such as a resin substrate, a ceramic substrate, and a glass substrate is used as a base material is used. As the wiring board 120 to which the resin substrate is applied, a multilayer copper-clad laminate (multilayer printed wiring board) or the like can be cited.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. The insulating layer 115 in which the rewiring layer 105 is formed is arranged between the wiring substrate 120 and the laminated body 101, and the wiring substrate 120 and the laminated body 101 are electrically connected via the rewiring layer 105. As the insulating layer 115, the composition of the present invention can be used. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the side of the rewiring layer 105 via a metal bump 103d such as a solder bump. In addition, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Furthermore, an underfill layer 110 a is formed between the insulating layer 115 and the laminated body 101. In addition, 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 strong heat resistance, the cured film in the present invention can also be preferably used as a plastic substrate for display devices such as liquid crystal displays, organic EL displays, electronic paper, or interlayer insulating films, automotive parts, etc. Heat-resistant paint, coating agent, film use. Furthermore, it is also possible to use the polyimide precursor of this invention for a positive photosensitive resin composition. [Example]

Hereinafter, the present invention will be further described in detail with examples. The materials, usage amounts, ratios, 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. "Parts" and "%" are quality standards as long as they are not particularly limited.

Synthesis of polyimide precursor <Synthesis of polyimide precursor P-1> 20.00 g (64.5 millimoles) of 4,4'-oxodiphthalic dianhydride (ODPA, 4 ,4'-oxodiphthalic acid dried at 140°C for 12 hours, difunctional acid anhydride), 4.13g (129 millimoles) of methanol (compound for side chain), 0.05g of terephthalic acid Phenol, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60°C for 18 hours to produce 4,4'-oxodio Diester of phthalic anhydride and methanol. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.88 g (59.3 millimoles) of 4,4'-oxodiphenylamine (ODA, diamine) dissolved in 100 mL of N-methylpyrrolidone was dropped at 20 to 23°C for 20 minutes Add to the reaction mixture. Next, 23.9 g (15.5 millimoles) of dineopentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd. product, terminal compound) 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 it was stirred again for 30 minutes in 4 liters of water to perform filtration 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 polyimide precursor (P-1) was confirmed by ¹ H-NMR (nuclear magnetic resonance spectroscopy) (DMSO (dimethyl sulfide)-d6 solution). 10.6～10.3ppm(m,2H), 8.2～6.7ppm(m,14H), 6.4～6.2ppm(m,1H), 6.2～6.0ppm(m,1H), 6.0～5.8ppm(m,0.9H) , 4.4～4.0ppm (m, 3H), 3.9～3.6ppm (s, 6H). The weight average molecular weight of the obtained P-1 (gel permeation chromatography (eluent: NMP (N-methyl-2-pyrrolidone) in terms of polystyrene)) is 50000. The measurement conditions are as follows. Column: TSKguardcolumn SuperAW -H (4.6mmID.×35mm) 1 TSK SuperAWM-H (6.0mmID.×150mm) 2 Developing solvent: NMP (10mmol/L lithium bromide, 10mmol/L phosphoric acid solution) Column temperature: 50℃ Flow rate: 0.35mL Sample injection volume per minute: 20μL Sample concentration: 0.1% by mass Device name: HLC-8220GPC (manufactured by TOSOH CORPORATION) Calibration curve base resin: Polystyrene

<Synthesis of polyimide precursors P-2 to P-16, P-18> In the synthesis of the polyimine precursor P-1, the difunctional acid anhydride, diamine, side chain compound, and terminal Compounds were changed as shown in Table 1 below, except that the same procedure was used to synthesize polyimide precursors P-2 to P-16, and P-18, respectively.

<Synthesis of P-17> 4,4'-phthalic anhydride (15.51g) and N-methylpyrrolidone (114g) were added to a 3-necked flask equipped with a thermometer, a stirrer, and a calcium chloride tube, and kept at room temperature Stirred. 4,4'-diaminodiphenyl ether (9.21 g) was added to this suspension, and stirred at 30°C. After 1 hour, a mixed liquid of N-methylpyrrolidone (15.27g) and DPHA (18.51g) was added, and stirred at 30°C. After 6 hours, cool to room temperature. Regarding the mixed solution diluted with NMP, the weight average molecular weight measured by GPC is 50,000. 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 it was stirred again for 30 minutes in 4 liters of water to perform filtration again. Next, the obtained polyimide precursor was dried under reduced pressure at room temperature for two days. The obtained solid was dissolved in NMP and measured by GPC. The weight average molecular weight is 20,000. It is believed that it was decomposed during the purification process.

[Table 1]

ODPA: manufactured by Tokyo Chemical Industry Co., Ltd. BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd. ODA: Tokyo Chemical Industry Co., Ltd. Benzidine (4,4'-diaminobiphenyl): Tokyo Chemical Industry Co., Ltd. Ethanol: Wako Pure Chemical Industries, Ltd. n-butanol: Wako Pure Chemical Industries, Ltd. n-octanol : Manufactured by Wako Pure Chemical Industries, Ltd. DPHA: manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA M-305: neopentylerythritol triacrylate, manufactured by TOAGOSEI CO., LTD., ARONIX M-305 701: dimethylglycerol Hydroxyethyl acrylate manufactured by Shin-Nakamura Chemical Co., Ltd: M-215 manufactured by Wako Pure Chemical Industries, Ltd.: Ethylene oxide isocyanurate (EO) modified diacrylate, TOAGOSEI CO. , LTD., ARONIX M-215 Karenz BEI: 1,1-(diacryloxymethyl) ethyl isocyanate, SHOWA DENKO KK, Karenz MOI: 2-isocyanatoethyl methacrylate , 4-Aminostyrene manufactured by SHOWA DENKO KK: manufactured by Tokyo Chemical Industry Co., Ltd.

[表3]

The structure of the obtained polyimide precursor is shown below. In the following, [] refers to a repeating unit. Me represents methyl. [Table 2]

[table 3]

<Example 1> <<Preparation of negative photosensitive resin composition>> As shown in Table 4 below, the polyimide precursor, photopolymerization initiator, radical polymerizable monomer, polymerization inhibitor, The metal discoloration inhibitor, the silane coupling agent, and the solvent were mixed to prepare a negative photosensitive resin composition as a uniform solution.

＜＜Resolution＞＞ ＜＜＜Remaining film rate in exposed area＞＞＞ After passing the negative photosensitive resin composition through a filter with a pore width of 0.8 μm, and performing pressure filtration under a pressure of 3.0 MPa, The negative photosensitive resin composition layer was formed by applying the negative photosensitive resin composition in a layer form by spin coating on the silicon wafer. 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 with a thickness of 15 μm on the silicon wafer物层。 The material 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 ^{500mJ/cm 2.} After being allowed to stand at room temperature for 30 minutes, it was developed with cyclopentanone for 60 seconds, and the residual film rate in the exposed area was determined from the change in film thickness before and after the development. Residual film rate in exposed area (%)=[film thickness of exposed area after development/film thickness of unexposed area before development]×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% is not practical for practical use, evaluation 3 or more is better.

＜＜＜Remaining film rate in unexposed area＞＞＞ The negative photosensitive resin composition is passed through a filter with a pore width of 0.8μm, and filtered under a pressure of 3.0MPa, and then placed 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 at 100°C for 5 minutes on a hot plate to set a uniform negative photosensitive resin composition with a thickness of 15 μm on the silicon wafer物层。 The material layer. This was developed with cyclopentanone for 60 seconds, and the film remaining rate in the unexposed area was determined from the change in film thickness before and after the development. Residual film rate of unexposed area (%)=[(film thickness of unexposed area after development)/film thickness of unexposed area before development]×100 5: less than 5% 4: more than 5% 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, evaluation 3 or more is preferable.

＜＜Remaining film rate after thermosetting＞＞ The negative photosensitive resin composition is passed through a filter with a pore width of 0.8μm, and after pressure filtration under a pressure of 3.0MPa, it is borrowed on a silicon wafer The negative photosensitive resin composition was applied in layers by the spin coating method to form a negative photosensitive resin composition layer. The silicon wafer to which the obtained negative photosensitive resin composition layer was applied was dried at 100°C for 5 minutes on a hot plate to set a uniform negative photosensitive resin composition with a thickness of 15 μm on the silicon wafer物层。 The material 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 ^{500mJ/cm 2, and the exposed negative photosensitive resin was exposed in a nitrogen environment} The resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min. After reaching 230°C, the temperature was maintained for 3 hours, and the residual film rate after heating was determined based on the change in film thickness before and after heating. Residual film rate after thermal curing (%)=[film thickness after thermal curing/film thickness before thermal curing]×100 5: 85% or more 4: 80% or more and less than 85% 3: 70% or more and less than 80 % 2: 60% or more and less than 70% 1: less than 60% In actual use, evaluation 2 or more is better.

＜＜Glass transition temperature (Tg)＞＞ The negative photosensitive resin composition is passed through a filter with a pore width of 0.8μm, and is filtered under a pressure of 3.0MPa, and then borrowed on a silicon wafer The negative photosensitive resin composition was applied in layers by the spin coating method to form a negative photosensitive resin composition layer. 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 with a thickness of 15 μm on the silicon wafer物层。 The material 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 ^{500mJ/cm 2, and the exposed negative photosensitive resin was exposed in a nitrogen environment} The resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min, and after reaching 230°C, it was maintained 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 in a viscoelasticity measuring device (manufactured by UBM, Rheogel E4000), and the stretching method was used to raise the temperature from 0°C to 350°C at a frequency of 1 Hz and a heating rate of 10°C/min Tg (°C) was obtained from the peak temperature of tanδ.

<Other Examples and Comparative Examples> In Example 1, the polyimide precursor, photopolymerization initiator, radical polymerizable monomer, polymerization inhibitor, metal discoloration inhibitor, silane coupling agent, and solvent were mixed One or more of them were changed as shown in Table 4 or Table 5, and in some examples, the thermal alkali generator was blended as shown in Table 5, except that it was carried out in the same manner.

The obtained results are shown in Table 4 and Table 5 below.

[Table 4]

[table 5]

The detailed content of each component of the said Table 4 and Table 5 is as follows. <Photo-radical 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 (2-functional methacrylate with 4 vinyloxy chains, manufactured by Sartomer Company, Inc.) A-9300: NK ester A-9300 (3-functional acrylate with 3 isobutyleneoxy chains, (Manufactured by Shin-Nakamura Chemical Co., Ltd.) A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd., neopentylerythritol tetraacrylate A-DPH: manufactured by Shin-Nakamura Chemical Co., Ltd., dinitrogen Alcohol hexaacrylate

<Thermal base 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 sulfide GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone ethyl lactate

[Chemical formula 39]

From the above results, it is clear that when the negative photosensitive resin composition of the present invention is used, the Tg is high and the resolution is excellent. In addition, in the present invention, the glass transition temperature is also 230°C or higher, and is 5°C higher than Comparative Example 1 and Comparative Example 2. With regard to the case of increasing Tg by 5°C, it can be said that the effect is very significant from the viewpoint of reliability improvement in high temperature processes such as the vapor deposition process for forming metal wiring or the bonding process between electrodes. Furthermore, by shortening the side chain of the polyimide precursor (by setting R ¹ and R ^{2 of} formula (1) as an organic group with a carbon number of 1 to 4 as a non-polymerizable group), after thermal curing The residual film rate is significantly improved.

Example 100 <Production of Laminate 1> The photosensitive resin composition of Example 3 was filtered through a filter with a pore width of 0.8 μm, and then formed on a silicon wafer by a spin coating method. 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 with 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 ^{500mJ/cm 2, and the exposed photosensitive resin composition was exposed to cyclopentanone} The layer (resin layer) was developed for 60 seconds to form a hole with a diameter of 10 μm. Next, in a nitrogen environment, the temperature was increased at a temperature increase rate of 10°C/min, and after reaching 230°C, the temperature was maintained for 3 hours. After cooling to room temperature, on the surface of the resin layer, use a photosensitive resin composition of the same type as the photosensitive resin composition again, and perform filtration from the photosensitive resin composition to patterned again in the same manner as above After heating the film for 3 hours, a laminate 1 with two resin layers was formed.

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

<Production of laminated body 3> The photosensitive resin composition of Example 3 was filtered under pressure through a filter with a pore width of 0.8 μm, and then 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 with 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 ^{500mJ/cm 2, and the exposed photosensitive resin composition layer was exposed to cyclopentanone (} The resin layer) was developed for 60 seconds to form a hole with a diameter of 10 μm. Then, in a nitrogen environment, the temperature was increased at a temperature increase rate of 10°C/min, and after reaching 230°C, the temperature was maintained for 3 hours. After cooling to room temperature, a copper thin film (metal layer) with 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 hole portion. Furthermore, on the surface of the metal layer and the photosensitive resin composition layer, the photosensitive resin composition of Example 3 was used again, and the filtration of the photosensitive resin composition to the patterned film was performed again in the same manner as above. After heating for 3 hours, a laminate 3 including a resin layer/metal layer/resin layer was produced.

100‧‧‧Semiconductor device 101a～101d‧‧‧Semiconductor element 101‧‧‧Laminated body 102b～102d‧‧‧Through electrode 103a～103e‧‧‧Metal bump 105‧‧‧Rewiring layer 110, 110a, 110b‧ ‧‧Underfill layer 115‧‧‧Insulation layer 120‧‧‧Wiring board 120a‧‧‧Surface electrode

Claims (21)

A negative photosensitive resin composition comprising a polyimine precursor, a photopolymerization initiator, and a solvent. The polyimine precursor has a repeating unit represented by formula (1) and is at least one terminal It has the structure represented by formula (2), and the weight average molecular weight is below 50,000,

In formula (1), X represents a group represented by -Ar-L-Ar- or a group represented by formula (51), where Ar is each independently an aromatic group, and L is the number of carbons that can be substituted by a fluorine atom 1 to 10 aliphatic hydrocarbon groups, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and groups including a combination of two or more of the above, Y represents a tetravalent organic group, R ¹ And R ² are each independently a non-polymerizable organic group having 1 to 4 carbon atoms, (A) _l -L ¹ -* (2) In formula (2), A represents a polymerizable group, and L ¹ represents a single bond or l +1 valent organic group, l represents an integer from 1 to 10, * represents the bonding site with other sites,

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. The negative photosensitive resin composition as described in item 1 of the scope of patent application, wherein The aforementioned polyimide precursor contains more than 90 mol% of the repeating unit represented by formula (1) of the total repeating unit. The negative photosensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein l in formula (2) is an integer of 2 to 5. The negative photosensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein A in the aforementioned formula (2) is a group containing a carbon-carbon unsaturated double bond. The negative photosensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein the structure represented by the aforementioned formula (2) is the structure represented by formula (3) or formula (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 from 1 to 10, and * represents a bond with other parts Junction site: In formula (4), L ³ represents a single bond or an n+1 valent organic group, n represents an integer from 1 to 10, and * represents a bonding site with other sites. The negative photosensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein the weight average molecular weight of the polyimide precursor is 5000 or more. Composition of negative photosensitive resin as described in item 1 or item 2 of the scope of patent application It also contains a multifunctional radical polymerizable monomer. The negative photosensitive resin composition described in item 1 or item 2 of the scope of the patent application further contains a thermal alkali generator. The negative photosensitive resin composition described in item 1 or item 2 of the scope of the patent application, wherein the photopolymerization initiator is at least one selected from the group consisting of oxime compounds and metallocene compounds. The negative photosensitive resin composition as described in the first or second patent application is used for the formation of an interlayer insulating film for a rewiring layer. A cured film formed by curing the negative photosensitive resin composition described in any one of items 1 to 10 in the scope of the patent application. The thickness of the cured film described in item 11 of the scope of the patent application is 1~30μm. A method for manufacturing a cured film, comprising: a photosensitive resin composition layer forming process, applying the negative photosensitive resin composition described in any one of the scope of the patent application item 1 to item 10 to a substrate to form Laminar; an exposure process to expose the negative photosensitive resin composition layer; and a development process to develop the exposed photosensitive resin composition layer. The method for manufacturing a cured film as described in item 13 of the scope of patent application includes a heating process of heating the developed negative photosensitive resin composition layer at a temperature of 50 to 500° C. after the aforementioned development process. A semiconductor device having the cured film described in item 11 or item 12 of the scope of patent application. A method for manufacturing a laminate, which includes item 13 or 14 of the scope of patent application The manufacturing method of the cured film described in the paragraph. A method of manufacturing a semiconductor device includes the method of manufacturing a cured film described in item 13 or 14 of the scope of the 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, and a weight average molecular weight of 50,000 or less,

In formula (1), X represents a group represented by -Ar-L-Ar- or a group represented by formula (51), where Ar is each independently an aromatic group, and L is the number of carbons that can be substituted by a fluorine atom 1 to 10 aliphatic hydrocarbon groups, -O-, -CO-, -S-, -SO ₂ -or -NHCO- and groups including a combination of two or more of the above, Y represents a tetravalent organic group, R ¹ And R ² are each independently a non-polymerizable organic group having 1 to 4 carbon atoms, (A) _l -L ¹ -* (2) In formula (2), A represents a polymerizable group, and L ¹ represents a single bond or l +1 valent organic group, l represents an integer from 1 to 10, * represents the bonding site with other sites,

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. The polyimine precursor described in item 18 of the scope of patent application, wherein the aforementioned polyimine precursor contains more than 90 mol% of the total repeating units of the repeating unit represented by formula (1). The polyimide precursor described in item 18 or item 19 of the scope of patent application, wherein A in the aforementioned formula (2) is a group containing a carbon-carbon unsaturated double bond. Such as the polyimide precursor described in item 18 or item 19 of the scope of patent application, wherein l in formula (2) is an integer of 2 to 5.

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