Photosensitive resin composition, cured product, patterned cured product production method, and electronic component

Abstract

Provided is a photosensitive resin composition containing: a polyimide precursor having a polymerizable unsaturated bond; a first crosslinking agent having a polymerizable group and a boiling point at 5 mmHg of 130°C or higher; a second crosslinking agent having a polymerizable group and a boiling point at 760 mmHg of 200°C or lower; a photopolymerization initiator; and a solvent. Also provided are a cured product using said photosensitive resin composition, a patterned cured product production method, and an electronic component.

Description

Method for producing photosensitive resin compositions, cured products, and patterned cured products, and electronic components

[0001] This disclosure relates to a photosensitive resin composition, a cured product, a method for producing a patterned cured product, and an electronic component.

[0002] Conventionally, polyimides, polybenzoxazoles, and the like, which possess excellent heat resistance, electrical properties, and mechanical properties, have been used for surface protective films and interlayer insulating films of semiconductor devices. In recent years, photosensitive resin compositions, in which these resins themselves are given photosensitive properties, have been used. Using these compositions simplifies the manufacturing process of patterned cured products and shortens the complex manufacturing process (see, for example, Patent Document 1).

[0003] Japanese Patent Publication No. 2009-265520

[0004] Photosensitive resin compositions containing polyimide precursors that impart photosensitive properties are sometimes required to yield cured products with excellent photosensitivity and high elastic modulus. However, until now, adopting compositions with excellent photosensitivity has resulted in insufficient elastic modulus, leaving room for improvement in achieving both excellent photosensitivity and high elastic modulus of cured products. In view of these circumstances, this disclosure aims to provide a photosensitive resin composition that can achieve both excellent photosensitivity and high elastic modulus of cured products, as well as a method for manufacturing cured products and patterned cured products using the photosensitive resin composition, and electronic components.

[0005] Means for solving the above problems include the following embodiments: <1> A photosensitive resin composition comprising: a polyimide precursor having polymerizable unsaturated bonds; a first crosslinking agent having polymerizable groups with a boiling point of 130°C or higher at 5 mmHg; a second crosslinking agent having polymerizable groups with a boiling point of 200°C or lower at 760 mmHg; a photopolymerization initiator; and a solvent. <2> The photosensitive resin composition according to <1>, wherein the polymerizable groups in the first crosslinking agent and the second crosslinking agent are each independently vinyl groups bonded to (meth)acryloyl groups or hydrocarbon groups. <3> The photosensitive resin composition according to <1> or <2>, wherein the main chain of the first crosslinking agent has 8 or more atoms. <4> The first crosslinking agent is an alkylene group having 2 to 16 carbon atoms, or (R ａ O) ｎ１It has a group represented by the formula, where R ａ The photosensitive resin composition according to any one of <1> to <3>, wherein each is independently an alkylene group having 1 to 8 carbon atoms, and n1 is an integer from 2 to 10. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the first crosslinking agent is selected from the group consisting of tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and diethylene glycol dimethacrylate. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the number of atoms in the main chain of the second crosslinking agent is 5 to 12. <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the second crosslinking agent has a vinyl group bonded to a hydrocarbon group. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the second crosslinking agent is selected from the group consisting of allyl methacrylate, allyl acrylate, vinyl methacrylate, and isoprenyl methacrylate. <9> The photosensitive resin composition according to any one of <1> to <8>, wherein the ratio of the first crosslinking agent to the total amount of the first crosslinking agent and the second crosslinking agent is 33% to 66% by mass. <10> The photosensitive resin composition according to any one of <1> to <9>, wherein the polyimide precursor has a structural unit represented by the following general formula (1). In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, R ６ and R ７At least one of the members has a polymerizable unsaturated bond. <11> A photosensitive resin composition according to any one of <1> to <10>, further comprising at least one selected from the group consisting of a sensitizer, an ultraviolet absorber, and a stabilizer. <12> A method for producing a patterned cured product, comprising: coating the photosensitive resin composition according to any one of <1> to <11> onto a substrate and drying it to form a photosensitive resin film; pattern exposing the photosensitive resin film to obtain a resin film; developing the resin film after pattern exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film. <13> A cured product of the photosensitive resin composition according to any one of <1> to <11>. <14> The cured product according to <13> used as an interlayer insulating film, a cover coat layer, a surface protective film, a passivation film, or a buffer coat film. <15> An electronic component comprising the cured product according to <13> or <14>.

[0006] This disclosure provides a photosensitive resin composition that can achieve both excellent photosensitivity and a high modulus of elasticity in the cured product, as well as a method for manufacturing cured products and patterned cured products using the photosensitive resin composition, and electronic components.

[0007] This is a manufacturing process diagram of an electronic component according to one embodiment of the present disclosure.

[0008] The embodiments for carrying out the embodiments of this disclosure will be described in detail below. However, the embodiments of this disclosure are not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the embodiments of this disclosure.

[0009] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that are not clearly distinguishable from other processes, provided that the purpose of the process is achieved. In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced by the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the terms "layer" or "film" include cases where, when observing the region in which the layer or film exists, it is formed not only over the entire region, but also on only a part of the region. The thickness of a layer or film can be measured using a micrometer, a scanning stylus, an optical interferometry film thickness analyzer, etc. In this disclosure, if the thickness of a layer or film can be measured directly, it is measured using an optical interferometry film thickness analyzer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing the cross-section of the object to be measured using an electron microscope. In this disclosure, "(meth)acryloyl group" means at least one of an acryloyl group and a methacryloyl group. In this disclosure, a structural unit based on a tetracarboxylic dianhydride may be any structural unit having a structure formed by ring-opening of a tetracarboxylic dianhydride or any structural unit in which a part of said structure is substituted with an organic group, and the raw material for the polyimide precursor is not limited to a tetracarboxylic dianhydride, but may be a tetracarboxylic acid or a tetracarboxylic acid derivative. In this disclosure, a structural unit based on a diamine compound may be any structural unit having a structure in which one hydrogen atom is removed from each of two amino groups, and the raw material for the polyimide precursor is not limited to a diamine compound, but may be a derivative of a diamine compound.Even if an element is expressed in the singular form in this disclosure, unless otherwise explicitly stated, this does not preclude the existence of multiple elements unless it would result in a technical inconsistency.

[0010] ≪Photosensitive Resin Composition≫ The photosensitive resin composition of this disclosure comprises a polyimide precursor having polymerizable unsaturated bonds, a first crosslinking agent having polymerizable groups with a boiling point of 130°C or higher at 5 mmHg, a second crosslinking agent having polymerizable groups with a boiling point of 200°C or lower at 760 mmHg, a photopolymerization initiator, and a solvent. Hereinafter, "polyimide precursor having polymerizable unsaturated bonds" will also be referred to as "unsaturated polyimide precursor." Furthermore, "first crosslinking agent having polymerizable groups with a boiling point of 130°C or higher at 5 mmHg" will simply be referred to as "first crosslinking agent," and "second crosslinking agent having polymerizable groups with a boiling point of 200°C or lower at 760 mmHg" will simply be referred to as "second crosslinking agent." The photosensitive resin composition of this disclosure can achieve both excellent photosensitivity and a high modulus of elasticity in the cured product. The reason for this is not entirely clear, but it is presumed to be as follows. Generally, in photosensitive resin compositions containing unsaturated polyimide precursors, compounds with relatively high boiling points that exhibit excellent photosensitivity have been used as crosslinking agents. However, relatively high boiling point crosslinking agents tend to leave some unreacted residues in the cured product, reducing the elastic modulus of the cured product. Therefore, conventional photosensitive resin compositions containing polyimide precursors sometimes failed to produce cured products with sufficiently high elastic modulus. On the other hand, the photosensitive resin composition of this disclosure uses a first crosslinking agent with a relatively high boiling point in combination with a second crosslinking agent with a relatively low boiling point. The second crosslinking agent is thought to be less likely to leave unreacted residues in the system when the photosensitive resin composition is cured, thereby suppressing the reduction in the elastic modulus of the cured product. This is thought to enable both excellent photosensitivity and a high elastic modulus of the cured product. The components of the photosensitive resin composition will be described below. It is preferable that the photosensitive resin composition of this disclosure is a negative-type photosensitive resin composition.

[0011] <Unsaturated Polyimide Precursor> The photosensitive resin composition contains an unsaturated polyimide precursor. Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

[0012] The unsaturated polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. The unsaturated polyimide precursor may also be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0013] The unsaturated polyimide precursor preferably has a structural unit represented by the following general formula (1).

[0014]

[0015] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and at least one of R ６ and R ７ has a polymerizable unsaturated bond.

[0016] The unsaturated polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, R ６ and R ７ in the plurality of structural units may be the same or different from each other. Incidentally, R ６ and R ７ are each independently a hydrogen atom or a monovalent organic group, and the combination thereof is not particularly limited. For example, one of R ６ and R ７ may be a hydrogen atom and the other may be a monovalent organic group described later, or both may be the same or different monovalent organic groups. As described above, when the unsaturated polyimide precursor has a plurality of structural units represented by the above general formula (1), the combination of R ６ and R ７ in each structural unit may be the same or different from each other.

[0017] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (for example, aromatic rings with 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, heterocyclic rings with 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings. When the tetravalent organic group represented by X includes an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of substituents on aromatic rings include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, and amino groups.

[0018] When the tetravalent organic group represented by X contains a benzene ring, it is preferable that the tetravalent organic group represented by X contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), or a silylene bond (-Si(R)). Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. The rings may be linked by linking groups such as ( ), or by a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be linked at two locations by a single bond and at least one of a linking group, forming a five-membered or six-membered ring containing a linking group between the two benzene rings.

[0019] In general formula (1), -COOR ６ The group and the -CONH- group are preferably in the ortho position relative to each other, and -COOR ７ It is preferable that the group and the -CO- group are in the ortho position relative to each other.

[0020] Specific examples of the tetravalent organic group represented by X include the groups represented by formulas (A) to (F) below. From the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, the group represented by formula (E) below is preferred, the group represented by formula (E) below, in which Z contains an ether bond is more preferred, and the group represented by formula (E) below, in which Z is an ether bond, is even more preferred. Formula (F) below is a structure in which Z in formula (E) below is a single bond. However, this disclosure is not limited to the following specific examples.

[0021]

[0022] In formula (D), A and B are independently single bonds or divalent groups not conjugated to a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups not conjugated to a benzene ring include methylene groups, halide methylene groups, halide methylmethylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), sulfide bonds (-S-), and silylene bonds (-Si(R)). Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group.) are some examples. Among these, A and B are preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, etc., and an ether bond is more preferred.

[0023] In formula (E), Z is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-O-C(=O)-), silylene bond (-Si(R) Ａ ) ２ -; Two R's ＡEach of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. Z preferably contains an ether bond, and more preferably is an ether bond. Furthermore, Z may include a structure represented by the following formula (C1).

[0024]

[0025] The alkylene group represented by Z in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by Z in formula (E) include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; methylmethylene group, methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, and 1,1-dimethylmethylene group. Examples of branched alkylene groups include tiltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group. Among these, methylene groups are preferred.

[0026] The halogenated alkylene group represented by Z in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by Z in formula (E) include alkylene groups in which at least one hydrogen atom in the alkylene group represented by Z in formula (E) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene groups, difluoromethylene groups, and hexafluorodimethylmethylene groups are preferred.

[0027] R included in the above silylene bond or siloxane bond Ａ or R Ｂ The alkyl group represented by is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Ａ or R Ｂ Specific examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0028] The tetravalent organic group represented by X may also be a group represented by the following formulas (J) to (O).

[0029]

[0030] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bond positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (for example, groups with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0031] Examples of divalent aromatic groups represented by Y include the group represented by the following formula (G) and the group represented by the following formula (H). Among these, the group represented by the following formula (H) is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, the group represented by the following formula (H) in which D is a single bond or an ether bond is more preferred, the group represented by the following formula (H) in which D is an ether bond is particularly preferred, and the group represented by the following formula (H) in which D is an ether bond is extremely preferred.

[0032]

[0033] In formulas (G) to (H), R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. In formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), or a silylene bond (-Si(R) Ａ ) ２ -; Two R's ＡEach of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of the following independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents 1 or an integer of 2 or more. ) or a divalent group formed by combining at least two of these. Furthermore, D may be the structure represented by formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of Z in formula (E). In formula (H), D is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group.

[0034] The alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulas (G) to (H) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0035] The alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (H) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups.

[0036] The halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups are preferred.

[0037] In equations (G) to (H), n is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0.

[0038] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups having a polyalkylene oxide structure.

[0039] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonameethylene, and 2-methyldecamethylene.

[0040] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include cyclopropylene and cyclohexylene.

[0041] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among these, polyethylene oxide structure or polypropylene oxide structure is preferred as the polyalkylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0042] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of divalent groups having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, a C1-C20 alkyl group, or a C6-C18 aryl group. Specific examples of C1-C20 alkyl groups bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, and n-dodecyl group. Among these, the methyl group is preferred. The C6-C18 aryl group bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents when the aryl group has a substituent include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, phenyl groups are preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via methylene groups, alkylene groups such as ethylene groups, or arylene groups such as phenylene groups.

[0043] The group represented by formula (G) is preferably the group represented by formula (G') below. The group represented by formula (H) is preferably the group represented by formula (H'), formula (H''), or formula (H''') below, and is more preferably the group represented by formula (H') or formula (H'') below from the viewpoint of having a flexible skeleton and excellent bonding properties.

[0044]

[0045] In formula (H'''), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0046] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited. Examples of combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include: A combination where X is the group represented by formula (E) and Y is the group represented by formula (H) A combination where X is the group represented by formula (F) and Y is the group represented by formula (H) A combination where X is the group represented by formula (E) and Y is the groups represented by formulas (G) and (H) A combination where X is the group represented by formulas (A) and (E) and Y is the group represented by formula (H) A combination where X is the group represented by formula (A) and Y is the group represented by formula (H)

[0047] R ６ and R ７ Each independently represents a hydrogen atom or a monovalent organic group, wherein at least one has a polymerizable unsaturated bond. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably one of the groups represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably includes an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). In this case, R ６ and R ７At least one of the groups is represented by general formula (2). When the monovalent organic group includes an organic group having an unsaturated double bond, preferably the group represented by general formula (2) below, the transmittance of i-line is high, and good cured products tend to be formed even when curing at low temperatures of 400°C or below. Furthermore, when the monovalent organic group includes an organic group having an unsaturated double bond, preferably the group represented by general formula (2) below, at least a portion of the unsaturated double bond portion is eliminated by imidization.

[0048] Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups, with ethyl, isobutyl, and t-butyl groups being preferred.

[0049]

[0050] In general formula (2), R ８ ~R １０ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R ｘ This represents a divalent linking group.

[0051] R in general formula (2) ８ ~R １０ The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. ８ ~R １０ Specific examples of the aliphatic hydrocarbon group represented by include methyl group, ethyl group, n-propyl group, isopropyl group, etc., with methyl group being preferred.

[0052] R in general formula (2) ８ ~R １０ As for combinations, R ８ and R ９ is a hydrogen atom, R １０ A combination in which the group is a hydrogen atom or a methyl group is preferred.

[0053] R in general formula (2) ｘ R is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups. ｘThe number of carbon atoms in this compound is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0054] In general formula (1), R ６ and R ７ Preferably, at least one of them is a group represented by the general formula (2), R ６ and R ７ It is more preferable that both are groups represented by the general formula (2).

[0055] If the unsaturated polyimide precursor contains a compound having a structural unit represented by the general formula (1) above, the R of all structural units contained in the compound ６ and R ７ The group R, represented by general formula (2), for the sum of the units. ６ and R ７ The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. The upper limit of the proportion is not particularly limited and may be 100 mol%. The proportion may also be 0 mol% or more and less than 60 mol%.

[0056] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0057]

[0058] In general formula (2'), R ８ ~R １０ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer from 1 to 10. In general formula (2'), R ８ ~R １０ For further details, see R in general formula (2). ８ ~R １０ The details are the same as above.

[0059] In general formula (2'), q is an integer from 1 to 10, preferably from 2 to 5, and more preferably 2 or 3.

[0060] The content of the structural unit represented by general formula (1) in a compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to the total structural units. The upper limit of the above content is not particularly limited and may be 100 mol%.

[0061] The unsaturated polyimide precursor may be synthesized using tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The unsaturated polyimide precursor may also be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0062] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. Dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 1,1,4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl Examples include 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornanetetracarboxylic acid dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propanetetracarboxylic acid dianhydride.Among these, from the viewpoint of mechanical properties and patternability, at least one selected from the group consisting of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride is preferred, and at least one selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride is more preferred. Tetracarboxylic dianhydrides may be used individually or in combination of two or more.

[0063] Specific examples of diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2 ,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6- Diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-A Minophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,Examples include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc. Among these, from the viewpoints of mechanical properties and light transmittance of the pre-baked film, at least one selected from the group consisting of 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, m-phenylenediamine, and 1,3-bis(3-aminophenoxy)benzene is more preferable, and 2,2'-dimethylbiphenyl-4,4'-diamine is even more preferable. The diamine compound may be used alone or in combination of two or more kinds.,

[0064] A compound having a structural unit represented by the general formula (1) and at least one of R ６ and R ７ in the general formula (1) being a monovalent organic group (hereinafter also referred to as "Compound A") can be obtained, for example, by the following method (a) or (b). (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) and a compound represented by R-OH are reacted in an organic solvent to form a diester derivative, and then the diester derivative and a diamine compound represented by H ２ N-Y-NH ２ are subjected to a condensation reaction. (b) A tetracarboxylic dianhydride and a diamine compound represented by H ２ N-Y-NH ２ are reacted in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted in an organic solvent to introduce an ester group.,

[0065] Since at least one of R ６ [[ID=2X]] and R ７ selected from the group consisting of in the general formula (1) has a polymerizable unsaturated bond, at least one of R-OH having a polymerizable unsaturated bond is used for R.,

[0066] Here, H ２ N-Y-NH ２Y in the diamine compound represented by [Formula 0] is the same as Y in General Formula (1), and specific examples and preferred examples are also the same. Further, R in the compound represented by R-OH represents a monovalent organic group, and specific examples and preferred examples are the same as R in General Formula (1). ６ and R ７ are the same as in the case of. The tetracarboxylic dianhydride represented by General Formula (8), H ２ N-Y-NH ２ The diamine compound represented by and the compound represented by R-OH may each be used alone or in combination of two or more.

[0067] Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N,N-dimethylpropionamide, etc. Among them, 3-methoxy-N,N-dimethylpropanamide and N,N-dimethylpropionamide are preferred. A dehydrating condensing agent may be allowed to act on the polyamic acid solution together with the compound represented by R-OH to synthesize an unsaturated polyimide precursor. The dehydrating condensing agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0068] The aforementioned compound A contained in the unsaturated polyimide precursor is obtained by allowing the compound represented by R-OH to act on the tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, then allowing a chlorinating agent such as thionyl chloride to act thereon to convert it into an acid chloride, and then reacting the diamine compound represented by H ２ N-Y-NH ２ with the acid chloride. The aforementioned compound A contained in the unsaturated polyimide precursor is obtained by allowing the compound represented by R-OH to act on the tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, and then reacting the diamine compound represented by H ２ N-Y-NH ２ with the diester derivative in the presence of a carbodiimide compound.

[0069] The aforementioned compound A contained in the unsaturated polyimide precursor consists of a tetracarboxylic dianhydride represented by the following general formula (8) and H ２ N-Y-NH ２ It can be obtained by reacting a diamine compound represented by with a polyamic acid, isoimidizing the polyamic acid in the presence of a dehydrating condensation agent such as trifluoroacetic anhydride, and then reacting it with a compound represented by R-OH. Alternatively, a portion of a tetracarboxylic dianhydride can be reacted with a compound represented by R-OH beforehand to partially esterify the tetracarboxylic dianhydride and H ２ N-Y-NH ２ It may also be reacted with a diamine compound represented by .

[0070]

[0071] In general formula (8), X is the same as X in general formula (1), and the specific examples and preferred examples are also the same.

[0072] The compound represented by R-OH used in the synthesis of the aforementioned compound A contained in the unsaturated polyimide precursor is the R group represented by general formula (2). ｘ The compound may be one in which a hydroxyl group is bonded to the group, or one in which a hydroxyl group is bonded to the terminal methylene group of the group represented by general formula (2'). Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0073] There are no particular restrictions on the molecular weight of the unsaturated polyimide precursor; for example, the weight-average molecular weight is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight-average molecular weight can be measured by gel permeation chromatography (GPC) and determined by conversion using a standard polystyrene calibration curve.

[0074] The photosensitive resin composition may further contain a dicarboxylic acid, and the unsaturated polyimide precursor contained in the photosensitive resin composition may have a structure in which some of the amino groups in the unsaturated polyimide precursor react with the carboxyl groups in the dicarboxylic acid. For example, when synthesizing the unsaturated polyimide precursor, some of the amino groups of the diamine compound may be reacted with the carboxyl groups of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acryloyl group, and may be, for example, a dicarboxylic acid represented by the following formula. In this case, when synthesizing the unsaturated polyimide precursor, a methacrylic group derived from the dicarboxylic acid can be introduced into the unsaturated polyimide precursor by reacting some of the amino groups of the diamine compound with the carboxyl groups of the dicarboxylic acid.

[0075]

[0076] The photosensitive resin composition may contain a polyimide resin in addition to the unsaturated polyimide precursor. By combining the unsaturated polyimide precursor and the polyimide resin, it is possible to suppress the generation of volatile substances due to dehydration cyclization during imide ring formation, and thus tend to suppress the generation of voids. The polyimide resin referred to here is a resin in which all or part of the resin skeleton has an imide skeleton. It is preferable that the polyimide resin is soluble in the solvent in the photosensitive resin composition using the unsaturated polyimide precursor.

[0077] The polyimide resin is not particularly limited as long as it is a polymer compound having multiple structural units containing imide bonds. For example, it is preferable to include a compound having a structural unit represented by the following general formula (X). This tends to result in a semiconductor device with an insulating film that exhibits high reliability.

[0078]

[0079] In general formula (X), X represents a tetravalent organic group and Y represents a divalent organic group. Preferred examples of substituents X and Y in general formula (X) are the same as preferred examples of substituents X and Y in general formula (1) described above.

[0080] When the photosensitive resin composition contains polyimide resin, the proportion of polyimide resin to the total of the unsaturated polyimide precursor and polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass.

[0081] The photosensitive resin composition may or may not contain other resins besides the unsaturated polyimide precursor and polyimide resin. Examples of other resins, from the viewpoint of heat resistance, include novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. One of these other resins may be used alone, or two or more may be used in combination.

[0082] In the photosensitive resin composition of this disclosure, the content of the unsaturated polyimide precursor relative to the total amount of solids is preferably 50% to 99% by mass, more preferably 70% to 99% by mass, and may be 90% to 99% by mass. The solids refer to the residue when the photosensitive resin composition is dried at 230°C.

[0083] <Crosslinking Agent> The photosensitive resin composition comprises a first crosslinking agent having polymerizable groups with a boiling point of 130°C or higher at 5 mmHg, and a second crosslinking agent having polymerizable groups with a boiling point of 200°C or lower at 760 mmHg.

[0084] The first crosslinking agent and the second crosslinking agent each independently have one or more polymerizable groups, preferably two or more, more preferably two to six, even more preferably two to four, and particularly preferably two. In particular, the first crosslinking agent and the second crosslinking agent each independently are compounds in which two polymerizable groups in the molecule are linked by a linear divalent organic group.

[0085] The polymerizable groups in the first and second crosslinking agents are preferably radical polymerizable groups, and more preferably polymerizable groups containing a carbon-carbon double bond. Specifically, the polymerizable groups are preferably groups containing vinyl groups, and from the viewpoint of availability, photoreactivity, etc., they are preferably (meth)acryloyl groups or vinyl groups bonded to hydrocarbon groups, respectively. From the viewpoint of high crosslinking reactivity and ease of suppressing cracks in the cured product, (meth)acryloyl groups are preferred. From the viewpoint of not having excessively high crosslinking reactivity, suppressing crosslinking due to unintended exposure light leakage, and suppressing the generation of residues, vinyl groups bonded to hydrocarbon groups are preferred. Compared to (meth)acryloyl groups, vinyl groups bonded to hydrocarbon groups tend to react more slowly. Therefore, if the first and / or second crosslinking agents have vinyl groups bonded to hydrocarbon groups, unintended reactions tend to be suppressed. The first crosslinking agent and the second crosslinking agent may each independently contain one type of polymerizable group, two types of polymerizable groups, or three or more types.

[0086] A "vinyl group bonded to a hydrocarbon group" is a vinyl group in which one carbon atom is bonded to a hydrocarbon group. A partial structure of the hydrocarbon group bonded to a vinyl group is *-CH ２ Examples include -, *-CH<, and *-C≡. * represents the bond position with the vinyl group. Note that -CH=CH is included in the acryloyl group. ２ -C (CH) contained in the group and methacryloyl group ３ ) = CH ２ Since each group is bonded to a carbonyl group (or ester group), it is not referred to as a "vinyl group bonded to a hydrocarbon group" in this disclosure.

[0087] -First Crosslinking Agent- The first crosslinking agent has a boiling point of 130°C or higher at 5 mmHg. From the viewpoint of process stability for pattern formation by development, the boiling point of the first crosslinking agent at 5 mmHg is preferably 150°C or higher, and more preferably 200°C or higher. The boiling point of the first crosslinking agent at 5 mmHg may be 300°C or lower. From this viewpoint, the boiling point of the first crosslinking agent at 5 mmHg is preferably 130°C to 300°C, more preferably 150°C to 300°C, and even more preferably 200°C to 300°C.

[0088] The first crosslinking agent preferably has a (meth)acryloyl group or a vinyl group bonded to a hydrocarbon group as a polymerizable group, and it is more preferable to have a (meth)acryloyl group from the viewpoint of high crosslinking reactivity and ease of suppressing cracks in the cured product. If the first crosslinking agent has two or more polymerizable groups, it is preferable that all of the polymerizable groups are (meth)acryloyl groups.

[0089] In one embodiment, the number of atoms in the main chain of the first crosslinking agent is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more, from the viewpoint of high molecular flexibility and ease of suppressing cracking of the cured product. In this disclosure, the main chain of the first crosslinking agent means the longest chain among the chains containing polymerizable groups, and if there is one polymerizable group, it is the longest chain containing that one polymerizable group, and if there are two or more polymerizable groups, it is the longest chain among the chains containing two or more polymerizable groups. Furthermore, the number of atoms in the main chain means the number of atoms on the main chain and does not include hydrogen atoms, substituents, or atoms on branched chains. From the viewpoint of thermal reliability of the device on which the cured film is mounted, the number of atoms in the main chain of the first crosslinking agent is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. From this viewpoint, the number of atoms in the main chain of the first crosslinking agent is preferably 8 to 40, more preferably 10 to 35, and even more preferably 12 to 30.

[0090] The first crosslinking agent is preferably a compound having a divalent organic group with two or more atoms in the main chain, and vinyl groups bonded to a (meth)acryloyl group or a hydrocarbon group at both ends. Examples of divalent organic groups with two or more atoms in the main chain include alkylene groups and groups having an oxygen atom at the end of the alkylene group or between carbon atoms. The divalent organic group with two or more atoms may be linear or branched, but a linear configuration is preferred from the viewpoint of high molecular flexibility and ease of suppressing cracking of the cured product. As for the alkylene group, an alkylene group having 2 to 20 carbon atoms is preferred, an alkylene group having 4 to 16 carbon atoms is more preferred, and an alkylene group having 6 to 14 carbon atoms is even more preferred. As for the alkylene group, a linear alkylene group with the above number of carbon atoms is preferred. Examples of groups having an oxygen atom at the end of the alkylene group or between carbon atoms include the groups having one or more oxygen atoms at the end of the alkylene group or between carbon atoms as exemplified above, and (poly)alkylene oxy groups. Here, (poly)alkyleneoxy group refers to either an alkyleneoxy group or a polyalkyleneoxy group. The number of carbon atoms in the alkyleneoxy unit of the (poly)alkyleneoxy group is preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The number of alkyleneoxy units in the polyalkyleneoxy group is preferably 2 to 10. As a group having an oxygen atom at the end of the alkylene group or between carbon atoms, it may be a group having an oxygen atom at the alkylene side end of the (poly)alkyleneoxy group, or a group having an alkylene group at the oxygen atom side end of the (poly)alkyleneoxy group. Among these, from the viewpoint of high molecular flexibility and easier suppression of cracks in the cured product, the (poly)alkyleneoxy group is preferred as a divalent organic group with 6 or more atoms, and the polyalkyleneoxy group is particularly preferred.

[0091] In one embodiment, the first crosslinking agent is an alkylene group having 2 to 20 carbon atoms, or (R ａ O) ｎ１ It is preferable to have a group represented by the formula. In the formula, R ａ Each of these is an alkylene group having 1 to 8 carbon atoms, and n1 is an integer from 2 to 10.

[0092] The alkylene group having 2 to 20 carbon atoms may be linear or branched, but a linear configuration is preferable from the viewpoint of high molecular flexibility and ease of suppressing cracking in the cured product. The number of carbon atoms in the alkylene group is preferably 4 to 16, and more preferably 6 to 14.

[0093] Formula (R ａ O) ｎ１ Medium, R ａ is an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Examples of alkylene groups include linear or branched alkylene groups, specifically methylene group, ethylene group, trimethylene group, methylethylene group, dimethylmethylene group, tetramethylene group, hexamethylene group, octamethylene group, etc., with ethylene group being preferred. n1 is an integer from 2 to 20, preferably an integer from 2 to 10, and particularly preferably an integer from 2 to 4.

[0094] In one embodiment, the first crosslinking agent preferably has a structure represented by the following formula (1A) or formula (1B). ａ -R １ -Y ａ ... (1A) Y ａ - (O) ｍ１ - (R ａ O) ｎ１ - (R ａ ) ｑ１ -Y ａ ... (1B)

[0095] In formula (1A), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, R １ This is an alkylene group having 2 to 20 carbon atoms.

[0096] In formula (1B), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, m1 is 0 or 1, and R ａ Each of these is an alkylene group having 1 to 8 carbon atoms, n1 is an integer from 2 to 20, and q1 is 0 or 1.

[0097] In formula (1A), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, and from the viewpoint of high crosslinking reactivity and ease of suppressing cracks in the cured product, Y ａ Preferably, each of these is independently a (meth)acryloyl group. In particular, two Y ａ Preferably, all of them are (meth)acryloyl groups.

[0098] In formula (1A), R １ This is an alkylene group having 2 to 20 carbon atoms, preferably an alkylene group having 4 to 16 carbon atoms, and more preferably an alkylene group having 6 to 14 carbon atoms.

[0099] In formula (1B), R ａ Details of n1 and n1 are given by equation (R ａ O) ｎ１ R inside ａ And it is the same as the definition of n1.

[0100] In formula (1B), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, and from the viewpoint of high crosslinking reactivity and ease of suppressing cracks in the cured product, Y ａ Preferably, each of these is independently a (meth)acryloyl group. In particular, two Y ａ Preferably, all of them are (meth)acryloyl groups.

[0101] From the viewpoint of easily suppressing cracks in the cured product, the molecular weight of the first crosslinking agent is preferably 150 or more, more preferably 175 or more, and even more preferably 200 or more. From the viewpoint of suppressing the coefficient of linear expansion when it becomes a cured film, the molecular weight of the first crosslinking agent is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. From this viewpoint, the molecular weight of the first crosslinking agent is preferably 150 to 1000, more preferably 175 to 800, and even more preferably 200 to 500.

[0102] Examples of the first crosslinking agent include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, triallyl isocyanurate, ethoxylated pentaerythritol tetraacrylate, and compounds represented by the following general formula (3). Among these, at least one selected from tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and diethylene glycol dimethacrylate is preferred from the viewpoint of easily improving photosensitivity. The first crosslinking agent may be used alone or two or more may be used in combination.

[0103]

[0104] In general formula (3), R １ and R ２ Each of these is independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following general formula (3-1). p1 represents 0 or 1, p2 represents an integer from 0 to 2, and p1 + p2 is 2 or 3. p1 R １ and p2 R ２ At least two of these are groups represented by the following general formula (3-1).

[0105]

[0106] In general formula (3-1), R １Ａ represents a hydrogen atom or a methyl group, and m represents an integer from 1 to 10.

[0107] R １ and R ２ Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and the like.

[0108] The compound represented by general formula (3) may also be the compound represented by the following formula (3A) or formula (3B).

[0109]

[0110] The compound represented by formula (3A) is available, for example, as A-DCP (tricyclodecanedimethanol diacrylate) from Shin-Nakamura Chemical Industry Co., Ltd., and the compound represented by formula (3B) is available, for example, as DCP (tricyclodecanedimethanol dimethacrylate) from Shin-Nakamura Chemical Industry Co., Ltd.

[0111] -Second Crosslinking Agent- The second crosslinking agent has a boiling point of 200°C or less at 760 mmHg. From the viewpoint of minimizing the presence of unreacted crosslinking agent in the cured product, the boiling point of the second crosslinking agent at 760 mmHg is preferably 190°C or less, more preferably 185°C or less, even more preferably 180°C or less, particularly preferably 170°C or less, extremely preferably 160°C or less, and even more preferably 150°C or less. The boiling point of the second crosslinking agent at 760 mmHg is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. From this viewpoint, the boiling point of the second crosslinking agent at 760 mmHg is preferably 80°C to 200°C, more preferably 80°C to 190°C, even more preferably 80°C to 185°C, particularly preferably 80°C to 180°C, extremely preferably 80°C to 170°C, and even more preferably 80°C to 160°C.

[0112] The second crosslinking agent preferably has a polymerizable group, which is either a (meth)acryloyl group or a vinyl group bonded to a hydrocarbon group. If the second crosslinking agent has two or more polymerizable groups, all of the polymerizable groups may be (meth)acryloyl groups, all of the polymerizable groups may be vinyl groups bonded to a hydrocarbon group, or both (meth)acryloyl groups and vinyl groups bonded to hydrocarbon groups may be included.

[0113] In one embodiment, from the viewpoint of preventing excessive crosslinking reactivity, suppressing crosslinking due to unintended exposure light leakage, and inhibiting the generation of residues, it is preferable that the second crosslinking agent has vinyl groups that bond to hydrocarbon groups.

[0114] In one embodiment, the number of atoms in the main chain of the second crosslinking agent is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less, from the viewpoint of preventing a decrease in the elastic modulus of the cured product. In this disclosure, the main chain of the second crosslinking agent means the longest chain among the chains containing polymerizable groups, and if there is one polymerizable group, it is the longest chain containing that one polymerizable group, and if there are two or more polymerizable groups, it is the longest chain among the chains containing two or more polymerizable groups. From this viewpoint, the number of atoms in the main chain of the second crosslinking agent is preferably 5 to 14, more preferably 5 to 12, and even more preferably 5 to 10.

[0115] The second crosslinking agent may be an aromatic compound or an aliphatic compound, with aliphatic compounds being preferred. The second crosslinking agent is preferably a compound having a divalent organic group with 1 to 10 atoms in the main chain, with (meth)acryloyl groups or vinyl groups bonded to a hydrocarbon group at both ends. Examples of the divalent organic group with 1 to 10 atoms in the main chain include alkylene groups and groups having oxygen atoms, etc., at the ends of the alkylene group or between carbon atoms. The divalent organic group with 1 to 10 atoms in the main chain may be linear or branched, with linear being preferred. As for the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As for the alkylene group, a linear alkylene group with the above number of carbon atoms is preferred. Examples of groups having an oxygen atom at the terminal or carbon-carbon axis of an alkylene group include the groups having one or more oxygen atoms at the terminal or carbon-carbon axis of an alkylene group as exemplified above, and alkylene oxy groups. The number of carbon atoms in the alkylene oxy group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0116] In one embodiment, the second crosslinking agent preferably has a structure represented by the following formula (2A) or formula (2B).ａ -R ２ -Y ａ ... (2A) Y ａ - (O) ｍ２ - (R ｃ O) ｎ２ - (R ｃ ) ｑ２ -Y ａ ... (2B)

[0117] In formula (2A), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, R ２ This is an alkylene group having 1 to 4 carbon atoms.

[0118] In formula (2B), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, m2 is 0 or 1, and R ｃ Each of these is an alkylene group having 1 to 4 carbon atoms, n2 is 0 or 1, q2 is 0 or 1, however, m2 + n2 + q2 is 1 or more.

[0119] In formula (2A), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, and from the viewpoint of high crosslinking reactivity and ease of suppressing cracks in the cured product, Y ａ Preferably, each of these is independently a (meth)acryloyl group. From the viewpoint of preventing the reactivity of crosslinking from being too high, suppressing crosslinking due to unintended exposure light leakage, and suppressing the generation of residue, Y ａ Each of these is preferably a vinyl group. ａ Y is a (meth)acryloyl group, and the other Y ａ It is also preferable that the group is a vinyl group.

[0120] In formula (2A), R ２ The alkylene group has 1 to 4 carbon atoms, with a preferred alkylene group having 1 to 3 carbon atoms, and a more preferred alkylene group having 1 or 2 carbon atoms. Examples of hydrocarbon groups include linear or branched alkylene groups, specifically methylene groups, ethylene groups, n-propylene groups, and the like.

[0121] In formula (2B), Y ａ Each is independently a (meth)acryloyl group or a vinyl group, and from the viewpoint of high crosslinking reactivity and ease of suppressing cracks in the cured product, Y ａ Preferably, each of these is independently a (meth)acryloyl group. From the viewpoint of preventing the reactivity of crosslinking from being too high, suppressing crosslinking due to unintended exposure light leakage, and suppressing the generation of residues, Y ａ Each of these is preferably a vinyl group. ａ Y is a (meth)acryloyl group, and the other Y ａ It is also preferable that the group is a vinyl group.

[0122] In formula (2B), R ｃ Each of these is independently an alkylene group having 1 to 4 carbon atoms, with an alkylene group having 1 to 3 carbon atoms being preferred, and an alkylene group having 1 or 2 carbon atoms being more preferred.

[0123] From the viewpoint of easily suppressing cracks in the cured product, the molecular weight of the second crosslinking agent is preferably 70 or more, more preferably 90 or more, and even more preferably 110 or more. From the viewpoint of suppressing a decrease in the elastic modulus of the cured product and suppressing the coefficient of linear expansion of the cured film, the molecular weight of the second crosslinking agent is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less.

[0124] From the viewpoint of suppressing a decrease in the elastic modulus of the cured product, allyl methacrylate, allyl acrylate, vinyl methacrylate, and isoprenyl methacrylate are preferred as the second crosslinking agent. The second crosslinking agent may be used alone or in combination of two or more types.

[0125] The ratio of the first crosslinking agent to the second crosslinking agent is not particularly limited. From the viewpoint of achieving both excellent photosensitivity and a high modulus of elasticity of the cured product in a particularly good manner, the ratio of the first crosslinking agent to the total amount of the first and second crosslinking agents is preferably 33% to 66% by mass, and more preferably 40% to 60% by mass.

[0126] From the viewpoint of achieving both excellent photosensitivity and a high modulus of elasticity of the cured product in a particularly good manner, the total content of the first crosslinking agent and the second crosslinking agent is preferably 1 to 50 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 35 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0127] The crosslinking agent may or may not contain crosslinking agents other than the first and second crosslinking agents. The total content of the first and second crosslinking agents relative to the total amount of crosslinking agents is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0128] From the viewpoint of achieving both excellent photosensitivity and a high modulus of elasticity of the cured product in a particularly good manner, the total content of the crosslinking agent is preferably 1 to 50 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 35 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0129] <Photopolymerization Initiator> The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals upon irradiation with active light. Examples of active light include ultraviolet rays such as i-rays, visible light, and radiation. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0130] Examples of photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, and acyldialkoxymethane compounds.

[0131] Examples of photopolymerization initiators include compounds represented by the following general formula (9A), compounds represented by the following general formula (9B), compounds represented by the following general formula (10A), and compounds represented by the following general formula (10B).

[0132]

[0133] In general formula (9A), R １１ R is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer from 0 to 5. １２ R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. １３ and R １４Each of these independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer of 2 or more, R １１ These may be the same or different.

[0134] R １１ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1. R １２ R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. １３ and R １４ Preferably, each is independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0135] Examples of compounds represented by general formula (9A) include the compound represented by the following formula (9A-1), which is available as "Irgacure® OXE-02" manufactured by BASF Japan Ltd.

[0136]

[0137]

[0138] In general formula (9B), R １５ -OH, -COOH, -OCH ２ OH, -O(CH ２ ) ２ OH, -COOCH ２ OH, or -COO(CH ２ ) ２ OH and R １６ and R １７ Each of these is independently a hydrogen atom, a C1-C12 alkyl group, a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group. b1 is an integer from 0 to 5. If b1 is an integer of 2 or more, R １５ These may be the same or different. １５ Preferably, -O(CH ２ ) ２ It is OH. b1 is preferably 0 or 1. R １６ R is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or a hexyl group. １７The group is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and more preferably a methyl group or a phenyl group.

[0139] Examples of compounds represented by general formula (9B) include the compound represented by the following formula (9B-1), which is available as "Irgacure® OXE-01" manufactured by BASF Japan Ltd. Another example is the compound represented by the following formula (9B-2), which is available as "NCI-930" manufactured by ADEKA Corporation.

[0140]

[0141]

[0142] In general formula (10A), R ２１ R is an alkyl group having 1 to 12 carbon atoms. ２２ and R ２３ Each of these is independently a hydrogen atom, a C1-C12 alkyl group (preferably C1-C4), a C1-C12 alkoxy group (preferably C1-C4), a C4-C10 cycloalkyl group, a phenyl group, or a tolyl group, and c1 is an integer from 0 to 5. When c1 is an integer of 2 or more, R ２１ These may be the same or different. c1 is preferably 0. R ２２ R is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. ２３ The group is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group or an ethoxy group. Examples of compounds represented by general formula (10A) include the compound represented by the following formula (10A-1), which is available as "G-1820 (PDO)" from Lambson.

[0143]

[0144]

[0145] In general formula (10B), R ２４ and R ２５Each of these is an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each independent integers from 0 to 5, s and t are each independent integers from 0 to 3, and the sum of s and t is 3. When d is an integer of 2 or more, R ２４ These may be the same or different. If e is an integer greater than or equal to 2, R ２５ These may be the same or different. If s is an integer greater than or equal to 2, the bases in the parentheses may be the same or different. If t is an integer greater than or equal to 2, the bases in the parentheses may be the same or different. d is preferably 0. R ２５ Preferably, each is an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. e is preferably an integer from 2 to 4, and more preferably 3. The combination of s and t (s, t) is preferably (1, 2) or (2, 1). Examples of compounds represented by general formula (10B) include the compound represented by the following formula (10B-1), which is available as "Irgacure® TPO" manufactured by BASF Japan Ltd. Also, an example of a compound represented by the following formula (10B-2) is available as "Irgacure® 819" manufactured by BASF Japan Ltd.

[0146]

[0147] The amount of photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 6 parts by mass, per 100 parts by mass of unsaturated polyimide precursor.

[0148] <Solvents> Examples of solvents include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, etc. One solvent may be used alone, or two or more solvents may be used in combination.

[0149] Solvents for esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates such as methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate and ethyl ethoxyacetate), alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate). Examples include alkyl esters of 2-alkoxypropionates such as ethyl toxypropionate, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, and propyl 2-alkoxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

[0150] Examples of solvents for ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of solvents for ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP). Examples of solvents for hydrocarbons include limonene. Examples of solvents for aromatic hydrocarbons include toluene, xylene, and anisole. Examples of solvents for sulfoxides include dimethyl sulfoxide.

[0151] Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred from the viewpoint of excellent solubility of each component and excellent applicability when forming a photosensitive resin film.

[0152] Furthermore, a compound represented by the following general formula (11) may be used as the solvent.

[0153]

[0154] In general formula (11), R ４１ ~R ４３ Each of these is an alkyl group having 1 to 10 carbon atoms.

[0155] R in general formula (11) ４１ ~R ４３ The number of carbon atoms in the alkyl group represented by is preferably 1 to 3, more preferably 1 or 3. ４１ ~R ４３Specific examples of the C1-C10 alkyl group represented by the formula include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl groups. The compound represented by general formula (11) is preferably 3-methoxy-N,N-dimethylpropanamide (for example, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).

[0156] The solvent content can be appropriately adjusted according to the viscosity of the photosensitive resin composition, for example, it may be 50 parts by mass or more, 80 parts by mass or more, or 100 parts by mass or more, per 100 parts by mass of unsaturated polyimide precursor. From the viewpoint of reducing the drying energy when forming a coating film, it is not necessary to include more solvent than necessary, for example, the solvent content per 100 parts by mass of unsaturated polyimide precursor may be 300 parts by mass or less, or 200 parts by mass or less. Therefore, the solvent content may be 50 to 300 parts by mass per 100 parts by mass of unsaturated polyimide precursor.

[0157] <Other Components> The photosensitive resin composition preferably further contains at least one selected from the group consisting of sensitizers, ultraviolet absorbers, and stabilizers. The photosensitive resin composition may also contain antioxidants, imidization accelerators, coupling agents, rust inhibitors, surfactants, leveling agents, thermal polymerization initiators, unavoidable components, etc.

[0158] (Sensitizer) The photosensitive resin composition may contain a sensitizer. By including a sensitizer in the photosensitive resin composition, it is possible to achieve both maintenance of residual film ratio and good resolution over a wide range of exposure levels.

[0159] Sensitizers include Michlar's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, benzyldimethylketone Examples include tar, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrene quinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrene quinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, etc. Sensitizers may be used individually or in combination of two or more.

[0160] When the photosensitive resin composition contains a sensitizer, the amount of sensitizer is not particularly limited, but is preferably 0.1 to 1.0 parts by mass, and more preferably 0.2 to 0.8 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0161] (Ultraviolet Absorber) The photosensitive resin composition may contain an ultraviolet absorber from the viewpoint of suppressing crosslinking of unexposed areas due to diffuse reflection during exposure. The ultraviolet absorber preferably has an absorbance of 0.05 or higher at 365 nm at a concentration of 10 mg / L, and more preferably 0.1 or higher. Examples of ultraviolet absorbers include benzotriazole compounds, salicylate ester compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenylcyanoacrylate compounds, benzothiazole compounds, azobenzene compounds, polyphenol compounds, nickel complex salt compounds, etc. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

[0162] Examples of benzotriazole compounds include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2- Examples include (2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2H-benzotriazole-2-yl)-p-cresol.

[0163] Examples of salicylic acid ester compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0164] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0165] Examples of diphenyl acrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.

[0166] Examples of diphenylcyanoacrylate compounds include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).

[0167] Examples of azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0168] Examples of polyphenol compounds include pyrogallol, phloroglysine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagine, quercetagene, goshipetin, pelargonidine, cyanidin, aurantinidin, luteolinidin, peonidin, rosinidine, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.

[0169] Examples of polyphenol compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).

[0170] Among the above, at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, azobenzene compounds, and polyphenol compounds is preferred as the ultraviolet absorber.

[0171] Furthermore, from the viewpoint of resolution, at least one selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-p-cresol), 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (curcumin), and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione is more preferred as the ultraviolet absorber.

[0172] When the photosensitive resin composition contains an ultraviolet absorber, the amount of ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, per 100 parts by mass of the unsaturated polyimide precursor, from the viewpoint of resolution. Furthermore, from the viewpoint of suppressing insufficient photocuring inside the coating film, the amount of ultraviolet absorber is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the unsaturated polyimide precursor. From this viewpoint, the amount of ultraviolet absorber is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0173] (Stabilizer) The photosensitive resin composition may contain a stabilizer. The inclusion of a stabilizer in the photosensitive resin composition can improve its stability when stored.

[0174] Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenol compounds.

[0175] Stabilizers may be used individually or in combination of two or more. Combining two or more stabilizers tends to make it easier to adjust the photosensitive properties due to differences in reactivity. Hindered phenol compounds may have both the function of a stabilizer and the function of an antioxidant (described later), or they may have only one of the functions.

[0176] Examples of stabilizers include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), and triethylene glycol-bis [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) (Nol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy Roxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxyl Examples include C-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, N,N'-hexane-1,6-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide.

[0177] If the photosensitive resin composition contains a stabilizer, the amount of stabilizer is preferably 0.05 to 1.0 parts by mass, and more preferably 0.1 to 0.8 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0178] (Antioxidant) The photosensitive resin composition may contain an antioxidant to suppress the deterioration of adhesion by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow processing, etc. The inclusion of an antioxidant in the photosensitive resin composition can suppress oxidation of electrodes during insulation reliability testing.

[0179] Specific examples of antioxidants include the compounds exemplified above as hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl), propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants may be used individually or in combination of two or more.

[0180] If the photosensitive resin composition contains an antioxidant, the amount of antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0181] (Imidification accelerator) The photosensitive resin composition may contain an imidification accelerator from the viewpoint of promoting the imidification reaction.

[0182] Specific examples of imidation accelerators include N-phenyldiethanolamine, 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc. Among these, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. One type of imidation accelerator may be used alone, or two or more types may be used in combination.

[0183] When the photosensitive resin composition contains an imidation accelerator, the content of the imidation accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0184] (Coupling agent) The photosensitive resin composition may contain a coupling agent. The coupling agent is not particularly limited and may include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidoic acid, benzophenone-3,3'-bis(N-[3-tri Silane coupling agents such as ethoxysilyl)propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane; and aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate. The coupling agents may be used individually or in combination of two or more.

[0185] If the photosensitive resin composition contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0186] (Rust Inhibitor) The photosensitive resin composition may contain a rust inhibitor from the viewpoint of suppressing corrosion and preventing discoloration of copper and copper alloys. The rust inhibitor is not particularly limited and examples include azole compounds and purine derivatives. One rust inhibitor may be used alone, or two or more may be used in combination.

[0187] Specific examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0188] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, and 8-amino Examples include adenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives.

[0189] If the photosensitive resin composition contains a rust inhibitor, the amount of rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0190] (Surfactants and Leveling Agents) The photosensitive resin composition may contain surfactants and / or leveling agents. Examples of surfactants and leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. Commercially available products include the trade names "Megafac® F171", "F173", and "R-08" (all manufactured by DIC Corporation), "Florard FC430" and "FC431" (both manufactured by Sumitomo 3M Limited), and "Organosiloxane Polymer KP341", "KBM303", and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0191] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0192] If the photosensitive resin composition contains a surfactant and / or a leveling agent, the total content of the surfactant and leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0193] (Thermal polymerization initiator) The photosensitive resin composition may further contain a thermal polymerization initiator from the viewpoint of promoting the polymerization reaction. Preferred thermal polymerization initiators are compounds that do not decompose when heated (dried) to remove the solvent during film formation, but decompose when heated during curing to generate radicals, thereby promoting the polymerization reaction between polymerizable monomers or between an unsaturated polyimide precursor and a polymerizable monomer. Preferred thermal polymerization initiators are compounds with a decomposition point of 110°C to 200°C, and from the viewpoint of promoting the polymerization reaction at a lower temperature, compounds with a decomposition point of 110°C to 175°C are more preferred.

[0194] Specific examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, and di- Examples include diacyl peroxides such as uroyl peroxide and dibenzoyl peroxide, peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and bis(1-phenyl-1-methylethyl)peroxide. Commercially available products include those with the trade names "Parkmil D," "Parkmil P," and "Parkmil H" (all manufactured by NOF Corporation).

[0195] When the photosensitive resin composition contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 to 20 parts by mass per 100 parts by mass of the unsaturated polyimide precursor, more preferably 0.2 to 20 parts by mass from the viewpoint of ensuring good flux resistance, and even more preferably 0.3 to 10 parts by mass from the viewpoint of suppressing the decrease in solubility due to decomposition during drying.

[0196] (Content of main components) The total amount of unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, and solvent in the photosensitive resin composition may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. Alternatively, the total amount of unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, solvent, stabilizer, sensitizer, ultraviolet absorber, imidization accelerator, rust inhibitor, antioxidant, and coupling agent in the photosensitive resin composition may be 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or 99% by mass or more.

[0197] ≪Cured Products≫ The cured products of the present disclosure are obtained by curing the photosensitive resin composition of the present disclosure. The cured products of the present disclosure can be suitably used, for example, as patterned cured products.

[0198] The average thickness of the cured product is not particularly limited, but is preferably, for example, 5 μm to 20 μm.

[0199] The cured product of this disclosure can be used as an interlayer insulating film, a cover coat layer, a surface protective film, a passivation film, a buffer coat film, etc. Using one or more selected from the group consisting of the interlayer insulating film, cover coat layer, surface protective film, passivation film, buffer coat film, etc., highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, stacked devices (multi-die fan-out wafer-level packages, etc.), and other electronic components can be manufactured.

[0200] ≪Method for Manufacturing Patterned Cured Products≫ The method for manufacturing patterned cured products according to the present disclosure includes: applying the photosensitive resin composition according to the present disclosure onto a substrate and drying it to form a photosensitive resin film; pattern exposing the photosensitive resin film to light to obtain a resin film; developing the resin film after pattern exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film.

[0201] The substrates include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), and TiO2. ２ Substrate, SiO ２ Examples include metal oxide insulating substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0202] There are no particular restrictions on the method of applying the photosensitive resin composition; it can be done using a spinner or the like.

[0203] Drying can be carried out using a hot plate, oven, or the like. The drying temperature is preferably 90°C to 150°C, and more preferably 90°C to 120°C from the viewpoint of ensuring dissolution contrast. The drying time is preferably 30 seconds to 5 minutes. Drying may be carried out two or more times. This makes it possible to obtain a photosensitive resin film in which the photosensitive resin composition has been formed into a film.

[0204] The average thickness of the photosensitive resin film is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and even more preferably 3 μm to 20 μm.

[0205] Pattern exposure involves exposing a predetermined pattern, for example, through a photomask. The active light used for irradiation can be ultraviolet light such as i-rays, visible light, or radiation, but i-rays are preferred. Exposure devices such as parallel exposure machines, aligners, projection exposure machines, steppers, and scanner exposure machines can be used.

[0206] By developing the film, a patterned resin film (patterned resin film) can be obtained. Generally, when using a negative-type photosensitive resin composition, unexposed areas are removed with a developer. As the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be used in appropriate mixtures. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0207] A surfactant may be added to the developer. The amount added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0208] The development time can be, for example, twice the time it takes for the photosensitive resin film to be immersed and completely dissolved. The development time also varies depending on the unsaturated polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0209] After development, the film may be washed with a rinsing solution. The rinsing solution may be distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., either individually or in appropriate mixtures, or in a stepwise combination.

[0210] A patterned resin film can be heat-treated to obtain a patterned cured product. The unsaturated polyimide precursor undergoes a dehydration and ring-closing reaction during the heat treatment process, becoming the corresponding polyimide resin.

[0211] The heat treatment temperature is preferably 250°C or lower, more preferably 120°C to 250°C, and even more preferably 160°C to 200°C. By keeping the heat treatment temperature within the above range, damage to the substrate or device can be minimized, enabling high-yield device production and energy savings in the process.

[0212] The heat treatment time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heat treatment time within the above range, the crosslinking reaction or dehydration ring-closing reaction can proceed sufficiently. The heat treatment atmosphere may be air or an inert atmosphere such as nitrogen, but from the viewpoint of preventing oxidation of the pattern resin film, a nitrogen atmosphere is preferred.

[0213] Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0214] <<Electronic Components>> The electronic components of this disclosure include the cured products of this disclosure as described above. The cured products may be interlayer insulating films, cover coat layers, surface protective films, passivation films, buffer coat films, etc. The cured products may be patterned cured products.

[0215] An example of the manufacturing process for a semiconductor device, which is an electronic component of the present disclosure, will be described with reference to the drawings. Figure 1 is a manufacturing process diagram for a multilayer wiring structure semiconductor device, which is an electronic component according to one embodiment of the present disclosure. In Figure 1, a semiconductor substrate 1, such as a Si substrate having circuit elements, is covered with a protective film 2, such as a silicon oxide film, except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0216] Next, a photosensitive resin layer 5, such as a chlorinated rubber-based or phenol novolac-based resin, is formed on the interlayer insulating film 4, and a window 6A is provided so that a predetermined portion of the interlayer insulating film 4 is exposed by known photographic etching techniques.

[0217] The interlayer insulating film 4 with window 6A exposed is selectively etched to create window 6B. Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed through window 6B.

[0218] Furthermore, a second conductor layer 7 is formed using a known photoetching technique, and an electrical connection is made with the first conductor layer 3. When forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

[0219] Next, the window 6C is opened by pattern exposure using the photosensitive resin composition of this disclosure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductive layer 7 from external stress, alpha rays, etc., and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film 4 can also be formed using the photosensitive resin composition of this disclosure.

[0220] The embodiments of this disclosure will now be described in detail with reference to examples, but the embodiments of this disclosure are not limited to these examples.

[0221] <Examples 1-11 and Comparative Examples 1 and 2> [Components of the photosensitive resin composition] ・Unsaturated polyimide precursor: An unsaturated polyimide precursor composed of pyromellitic dianhydride (PMDA) and 4,4'-oxydiphthalic anhydride (ODPA) in a molar ratio of 3:1 as the acid component, and 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) as the amine component. ・Crosslinking agent 1: Tetraethylene glycol dimethacrylate (TEGDMA) (Boiling point at 5 mmHg: 200°C) ・Crosslinking agent 2: Allyl methacrylate (AMA) (Boiling point at 760 mmHg: 144°C) ・Crosslinking agent 3: Triallyl isocyanurate (TAIC) (Boiling point at 5 mmHg: 149°C) ・Crosslinking agent 4: Ethoxylated pentaerythritol tetraacrylate (ATM-4E) (Boiling point at 5 mmHg: 130°C or higher) • Crosslinking agent 5: Isoprenyl methacrylate (IPEMA) (boiling point at 760 mmHg: 180°C) • Stabilizer: 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide (Taobn, Hampford Research Inc.) • Photopolymerization initiator: 2-[(benzoyloxy)imino]-1-[4-(phenylthio)phenyl]octan-1-one (Irgacure OXE-01 BASF) • Sensitizer: 4,4'-bis(diethylamino)benzophenone • UV absorber: Curcumin • Solvent 1: 3-Methoxy-N,N'-dimethylpropanamide (product name "KJCMPA-100", manufactured by KJ Chemicals Co., Ltd.) • Solvent 2: γ-butyrolactone (GBL) • Imidization promoter: N-phenyldiethanolamine (NPDA)

[0222] The unsaturated polyimide precursor was synthesized as follows: 1046 g of N'N-dimethylpropionamide (DMPr) was placed in a 3 L separable flask, and while stirring, 64.771 g (209 mmol) of 4,4'-oxydiphthalic anhydride (ODPA, Manac Co., Ltd.) and 68.311 g (313 mmol) of pyromellitic anhydride (PMDA, HOPE Co., Ltd.) were added and dissolved. Further, 0.24 g (5.2 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO, Fujifilm Wako Pure Chemical Corporation) was added and dissolved, followed by 0.28 g (2.6 mmol) of benzoquinone (BQ, Fujifilm Wako Pure Chemical Corporation), and then 6.79 g (52.2 mmol) of 2-hydroxyethyl methacrylate (HEMA, Fujifilm Wako Pure Chemical Corporation). The mixture was then stirred at 40°C for 1 hour to obtain the reaction solution. In addition, 95.301 g (449 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP, Wakayama Seika Kogyo Co., Ltd.) was dissolved in 714 g of DMPr to prepare a DMAP solution. The DMAP solution was added dropwise while stirring the reaction solution at 35°C, and then stirred at 30°C for 3 hours. Next, 190.950 g (1096 mmol) of methanesulfonic anhydride (MSAA, Fujifilm Wako Pure Chemical Industries, Ltd.) was added under ice cooling. After stirring for 1 hour while continuing ice cooling, 234.04 g (1931 mmol) of 5-ethyl-2-methylpyridine (EMP) was added dropwise. After continuing to stir for 1 hour, 169.82 g (1305 mmol) of HEMA was added dropwise. After stirring for 15 hours while heating at 40°C, the mixture was cooled to room temperature. The reaction solution was added to purified water, the precipitate was collected, washed with purified water, and then dried under reduced pressure to obtain a polymer as an unsaturated polyimide precursor. The weight-average molecular weight (Mw) of the obtained polymer was 27,000.

[0223] The weight-average molecular weight of the polymer was measured by gel permeation chromatography (GPC) using a calibration curve based on TSKgel standard polystyrene (Tosoh Corporation). The apparatus and conditions are shown below. The measurement sample was prepared by dissolving 2 mg of the sample in 1 mL of eluent (tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (v / v)), and then filtering it through a PTFE membrane filter with a pore size of 1 μm. Apparatus: Shimadzu Corporation, Prominence Column: Resonaq Corporation, Gelpak GL S300MDT-5 Eluent: THF / DMF = 1 / 1 (v / v), lithium bromide 0.03 mol / L, phosphoric acid 0.06 mol / L Flow rate: 1.0 mL / min Measurement wavelength: 270 nm Injection volume: 10 μL

[0224] [Preparation of Photosensitive Resin Compositions] Each component listed in Tables 1 and 2 was blended in the amounts listed in Tables 1 and 2 to obtain a homogeneous solution. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 1 μm to obtain the photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 and 2. The amounts of each component in the table are based on parts by mass. In the table, "-" means that the component is not present.

[0225] [Preparation of Patterned Resin Films] Using a coating and developing apparatus (ACT-8, Tokyo Electron Limited), each photosensitive resin composition was coated onto a Si wafer by spin coating, and pre-baked (PB) at 100°C for 2 minutes, and then at 110°C for 2 minutes, to obtain a photosensitive resin film with a thickness of 8 to 12 μm. The development time was set to 0.5 to 2 times the time it took for the obtained photosensitive resin film to completely dissolve when immersed in cyclopentanone. In addition, a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed to an exposure dose of 100 mJ / cm using an i-line stepper NES2W-06 (manufactured by Nikon Engineering Co., Ltd.). ２ ~1100mJ / cm ２The resin film was then exposed by irradiating a photomask for via formation with a diameter of 1 μm to 100 μm. After exposure, the resin film was paddle-developed with cyclopentanone for the development time described above, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

[0226] [Manufacturing of Patterned Cured Products] The obtained patterned resin film was heated in an inert gas oven INL-60N1-S (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere at 280°C for 2 hours to obtain a patterned cured product.

[0227] [Evaluation of Photosensitivity] The patterned resin film was observed with an optical microscope and evaluated according to the following criteria: A: No cracks were observed, and via openings of 6 μm or less were confirmed. B: No cracks were observed, and via openings of more than 6 μm and less than or equal to 15 μm were confirmed. C: Cracks were observed, or via openings of 15 μm or less were not confirmed.

[0228] [Evaluation of Elastic Modulus] A resin composition was spin-coated onto a silicon wafer to form a film with a cured thickness of 10 μm. This film was then exposed to an MA / BA-8 from Suss Microtec Co., Ltd. at an exposure dose of 400 mJ / cm². ２ Exposure was performed through a mask. Thirty minutes after exposure, the wafer was paddle-developed with cyclopentanone, and then rinsed with propylene glycol monomethyl ether acetate to obtain a strip-shaped patterned resin film. The obtained patterned resin film was heated in a vertical diffusion furnace manufactured by Koyo Thermo Systems under a nitrogen atmosphere at 280°C for 2 hours to obtain a polyimide film consisting of a cured resin composition. The silicon wafer on which the polyimide film was formed was immersed in a 4.9 mass% hydrofluoric acid solution, and the polyimide film was peeled off from the silicon wafer to obtain a polyimide film with an average thickness of 10 μm. Subsequently, the strip-shaped polyimide film was tested in a Shimadzu AGS-X 100N tensile testing apparatus at room temperature (approximately 25°C) at a speed of 5 mm / min, and the tensile modulus was calculated from the S-S curve and film thickness. The average value for n=10 was used as the value of the modulus. The modulus was evaluated using the following indicators. (Unit: GPa) A: 5.5 or higher B: 5.0 or higher but less than 5.5 C: Less than 5.0

[0229]

[0230]

[0231] As shown in Table 1, in Examples 1 to 11, where crosslinking agents 1 and 2 were used in combination as crosslinking agents, both excellent photosensitivity and a high modulus of elasticity of the cured product were achieved. On the other hand, in Comparative Example 1, where only crosslinking agent 1 was used as the crosslinking agent, the modulus of elasticity was low, and in Comparative Example 2, where only crosslinking agent 2 was used as the crosslinking agent, the photosensitivity was poor. In Comparative Example 1, where only crosslinking agent 1 was used, the modulus of elasticity was 4.9 GPa, and in Comparative Example 2, where only crosslinking agent 2 was used, the modulus of elasticity was expected to be somewhere in between these two. However, in reality, the modulus of elasticity remained high at 5.8 GPa, and the photosensitivity was also excellent. Furthermore, in Examples 2 to 11, where the mixing ratio of crosslinking agent 1 and crosslinking agent 2 was changed, a high modulus of elasticity similar to that of Comparative Example 2 and excellent photosensitivity were obtained. From this, it is suggested that when crosslinking agent 1 and crosslinking agent 2 are used in combination, both the excellent photosensitivity provided by crosslinking agent 1 and the high modulus of elasticity provided by crosslinking agent 2 can be achieved at a high level.

[0232] As shown in Table 2, in Examples 12 to 17, where crosslinking agents 1 and 5 were used in combination as crosslinking agents, both excellent photosensitivity and a high modulus of elasticity of the cured product were achieved.

[0233] When comparing Examples 1, 3-7, which used crosslinking agent 2 with a boiling point of 144°C at 760 mmHg, with Examples 12-17, which used crosslinking agent 5 with a boiling point of 180°C at 760 mmHg, the former, with its lower boiling point, tended to have a higher elastic modulus.

[0234] The disclosure of international application PCT / JP2024 / 040036, filed on November 11, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated herein by reference.

[0235] 1. Semiconductor substrate 2. Protective film 3. First conductive layer 4. Interlayer insulating film 5. Photosensitive resin layer 6A, 6B, 6C windows 7. Second conductive layer 8. Surface protective film

Claims

A polyimide precursor having polymerizable unsaturated bonds, A first crosslinking agent having polymerizable groups and a boiling point of 130°C or higher at 5 mmHg, A second crosslinking agent having polymerizable groups and a boiling point of 200°C or less at 760 mmHg, Photopolymerization initiator, Solvents and, A photosensitive resin composition containing [the specified element]. 　 The photosensitive resin composition according to claim 1, wherein the polymerizable groups in the first crosslinking agent and the second crosslinking agent are each independently vinyl groups bonded to a (meth)acryloyl group or a hydrocarbon group. 　 The photosensitive resin composition according to claim 1, wherein the number of atoms in the main chain of the first crosslinking agent is 8 or more. 　 The first crosslinking agent is an alkylene group having 2 to 16 carbon atoms, or (R ａ O) ｎ１ It has a group represented by the formula, in which, R ａ Each of these is an alkylene group having 1 to 8 carbon atoms, n1 is an integer between 2 and 10. The photosensitive resin composition according to claim 1. 　 The photosensitive resin composition according to claim 1, wherein the first crosslinking agent is selected from the group consisting of tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and diethylene glycol dimethacrylate. 　 The photosensitive resin composition according to claim 1, wherein the number of atoms in the main chain of the second crosslinking agent is 5 to 12. 　 The photosensitive resin composition according to claim 1, wherein the second crosslinking agent has a vinyl group bonded to a hydrocarbon group. 　 The photosensitive resin composition according to claim 1, wherein the second crosslinking agent is selected from the group consisting of allyl methacrylate, allyl acrylate, vinyl methacrylate, and isoprenyl methacrylate. 　 The photosensitive resin composition according to claim 1, wherein the ratio of the first crosslinking agent to the total amount of the first crosslinking agent and the second crosslinking agent is 33% by mass to 66% by mass. 　 The photosensitive resin composition according to claim 1, wherein the polyimide precursor has a structural unit represented by the following general formula (1). In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, R ６ and R ７ At least one of them has a polymerizable unsaturated bond. 　 The photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of sensitizers, ultraviolet absorbers, and stabilizers. 　 The photosensitive resin composition according to any one of claims 1 to 11 is applied to a substrate and dried to form a photosensitive resin film, Obtaining a resin film by pattern exposure of the aforementioned photosensitive resin film, The resin film after pattern exposure is developed using a developer to obtain a patterned resin film. The aforementioned patterned resin film is heat-treated, A method for producing a patterned cured product, including the method described above. 　 A cured product of the photosensitive resin composition according to any one of claims 1 to 11. 　 The cured product according to claim 13, which is used as an interlayer insulating film, a cover coat layer, a surface protective film, a passivation film, or a buffer coat film. 　 An electronic component comprising the cured product described in claim 13.

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