Photosensitive resin composition, method for producing patterned cured product, cured product, and electronic component

Abstract

A photosensitive resin composition containing: a polyimide precursor having a polymerizable unsaturated bond; at least one type of solvent selected from the group consisting of 3-methoxy-N, N'-dimethylpropanamide and 3-butoxy-N, and N'-dimethylpropanamide; and N-phenyldiethanolamine.

Description

Photosensitive resin composition, method for producing patterned cured product, cured product, and electronic component

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

[0002] Highly heat-resistant organic materials such as polyimide resins are widely used as protective film materials for semiconductor integrated circuits (LSIs). Protective films (cured films) using such polyimide resins can be obtained by applying a resin composition containing an unsaturated polyimide precursor to a substrate, drying the resin composition, and then heating and curing the resulting resin film. In recent years, there has been a demand for resin compositions that do not contain N-methyl-2-pyrrolidone (NMP) from the perspectives of reducing environmental pollution, health, and ensuring device reliability. For example, Patent Document 1 discloses a resin composition that contains a specific amount of an amide compound having a specific structure, such as 3-methoxy-N,N'-dimethylpropanamide, relative to the resin.

[0003] Patent No. 6935982

[0004] However, when the solvent type was changed from NMP to 3-methoxy-N,N'-dimethylpropanamide or the like, it was found that the reactivity during exposure or curing changed, resulting in large variations in the elongation properties of the cured film. Variations in elongation properties can be a factor in inducing cracks, peeling, etc. of the cured film in the package.

[0005] In view of the above-described conventional circumstances, an object of one embodiment of the present disclosure is to provide a photosensitive resin composition that has excellent elongation characteristics when formed into a cured film even when an NMP alternative solvent is used, and that can suppress variation in elongation characteristics, as well as a cured product using the photosensitive resin composition, a method for producing a patterned cured product, and an electronic component.

[0006] Specific means for achieving the above object are as follows: <1> A photosensitive resin composition containing a polyimide precursor having a polymerizable unsaturated bond, at least one solvent selected from the group consisting of 3-methoxy-N,N'-dimethylpropanamide and 3-butoxy-N,N'-dimethylpropanamide, and N-phenyldiethanolamine. <2> The photosensitive resin composition according to <1>, wherein the polyimide precursor having a polymerizable unsaturated bond has a structural unit represented by the following general formula (1): (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; R ６ and R ７ at least one of which has a polymerizable unsaturated bond.) <3> The photosensitive resin composition according to <1> or <2>, further comprising at least one of a crosslinking agent and a photopolymerization initiator. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the content of the N-phenyldiethanolamine is 0.1 parts by mass or more per 100 parts by mass of the polyimide precursor. <5> A method for producing a patterned cured product, comprising the steps of: applying the photosensitive resin composition according to any one of <1> to <4> onto a substrate and drying to form a photosensitive resin film; patternwise exposing the photosensitive resin film to obtain a resin film; developing the resin film after the patternwise exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film. <6> A cured product obtained by curing the photosensitive resin composition according to any one of <1> to <4>. <7> The cured product according to <6>, which is a patterned cured product. <8> The cured product according to <6>, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film. <9> An electronic part, comprising the cured product according to any one of <6> to <8>.

[0007] According to one embodiment of the present disclosure, it is possible to provide a photosensitive resin composition that has excellent elongation characteristics when formed into a cured film and can suppress variation in elongation characteristics even when an NMP alternative solvent is used, as well as a cured product using the photosensitive resin composition, a method for producing a patterned cured product, and an electronic component.

[0008] 1A to 1C are diagrams illustrating a manufacturing process for an electronic component according to an embodiment of the present disclosure.

[0009] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0010] In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another staged numerical range. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in a composition, the content or amount of each component refers to the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire region when the region in which the layer or film is present is observed, as well as cases where the layer or film is formed only over a portion of the region. In the present disclosure, the term "(meth)acryloyl group" refers to at least one of an acryloyl group and a methacryloyl group, and the term "(meth)acryloyloxy group" refers to at least one of an acryloyloxy group and a methacryloyloxy group. In the present disclosure, the average thickness of a layer or film is a value obtained by measuring the thickness of five points on the target layer or film and calculating the arithmetic mean value. The thickness of a layer or film can be measured using a micrometer, a scanning stylus meter, an optical interference film thickness measuring device, or the like. In the present disclosure, when the thickness of a layer or film can be measured directly, it is measured using an optical interference film thickness measuring device. 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 target using an electron microscope.

[0011] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond, at least one solvent selected from the group consisting of 3-methoxy-N,N'-dimethylpropanamide and 3-butoxy-N,N'-dimethylpropanamide (hereinafter also referred to as the "specific solvent"), and N-phenyldiethanolamine. According to the photosensitive resin composition having the above configuration, even when an NMP alternative solvent is used, the cured film exhibits excellent elongation properties and can suppress variation in elongation properties. The reason for this is not clear, but is presumed to be as follows.

[0012] When a photosensitive resin composition is applied to a substrate to form a film, which is then exposed to light to form a cured film, light does not easily reach the bottom of the film under low exposure conditions. Therefore, the photocuring reaction does not proceed sufficiently at the bottom of the film, which may result in a low molecular weight or heterogeneity of the cured polymer. In contrast, N-phenyldiethanolamine acts as a sensitizer, and the photocuring reaction proceeds sufficiently at the bottom of the film, even when an NMP alternative solvent is used. Therefore, it is presumed that a highly oriented cured film is formed even under low exposure conditions, and variation in elongation properties is suppressed.

[0013] It is assumed that if the affinity between the polyimide precursor and the remaining solvent is low, the polyimide precursor will aggregate as a single molecule, reducing the frequency of collisions between the functional groups of one molecule and the functional groups of another molecule, resulting in heterogeneous polymerization. Therefore, when an alternative solvent is used, the problem of affinity between the polyimide precursor and the solvent is more likely to become apparent than in the case of NMP. However, by using N-phenyldiethanolamine in combination with a specific solvent, N-phenyldiethanolamine acts as a sensitizer as described above, and it is therefore assumed that the problem caused by such affinity is also solved.

[0014] Each component contained in the photosensitive resin composition of the present disclosure will be described below. The photosensitive resin composition of the present disclosure is preferably a negative photosensitive resin composition.

[0015] (Unsaturated Polyimide Precursor) The photosensitive resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond (hereinafter, may be referred to as an "unsaturated polyimide precursor"). Examples of the polymerizable unsaturated bond include a carbon-carbon double bond.

[0016] The unsaturated polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound, or may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0017] The unsaturated polyimide precursor preferably has a structural unit represented by the following general formula (1).

[0018]

[0019] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７ each 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.

[0020] The unsaturated polyimide precursor may have a plurality of structural units represented by the general formula (1), and X, Y, R in the plurality of structural units may be ６ and R ７ may be the same or different. ６ and R ７ are each independently a hydrogen atom or a monovalent organic group, the combination of which is not particularly limited. For example, R ６ and R ７ At least one of R may be a hydrogen atom and the rest may be a monovalent organic group described later, or they may be the same or different monovalent organic groups. ６ and R ７ The combinations may be the same or different.

[0021] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent on the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.

[0022] When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, more preferably 1 to 3 benzene rings, and even more preferably 1 or 2 benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be connected by a single bond, or may be connected by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater.) or a composite linking group comprising at least two of these linking groups. Furthermore, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0023] In the general formula (1), -COOR ６ The —COOR group and the —CONH— group are preferably in the ortho position relative to each other. ７ The group and the —CO— group are preferably in the ortho position relative to each other.

[0024] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulas (A) to (F). Among them, from the viewpoint of obtaining an insulating film that is excellent in flexibility and further suppresses the occurrence of voids at the bonding interface, a group represented by the following formula (E) is preferred, and in the formula (E) below, C is more preferably a group containing an ether bond, and even more preferably an ether bond. Formula (F) below has a structure in which C in formula (E) below is a single bond. It should be noted that the present disclosure is not limited to the specific examples below.

[0025]

[0026] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups that are not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represent a hydrogen atom, an alkyl group, or a phenyl group. Among these, A and B each independently preferably represent a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

[0027] In formula (E), C 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)—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａeach independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each 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 combining at least two of these. C preferably contains an ether bond, and is preferably an ether bond. C may also contain a structure represented by the following formula (C1):

[0028]

[0029] The alkylene group represented by C 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 C in formula (E) include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethylethylene group, a branched-chain alkylene groups such as 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene; and the like. Among these, a methylene group is preferred.

[0030] The halogenated alkylene group represented by C 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 C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) above has been substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0031] R contained in the silylene bond or siloxane bond Ａ or R Ｂ The alkyl group represented by R 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 the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0032] Specific examples of the tetravalent organic group represented by X may be groups represented by the following formulae (J) to (O).

[0033]

[0034] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, 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 bonding 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 the divalent aromatic group include a divalent aromatic hydrocarbon group (for example, an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (for example, a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.

[0035] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formula (G) and formula (H). Among these, from the viewpoint of obtaining an insulating film that is excellent in flexibility and in which the generation of voids at the bonding interface is further suppressed, the group represented by the following formula (H) is preferred, and among these, in the following formula (H), D is more preferably a group containing a single bond or an ether bond, even more preferably a group containing a single bond or an ether bond, particularly preferably a group containing an ether bond, and extremely preferably an ether bond.

[0036]

[0037] In formulas (G) to (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 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)—), a silylene bond (—Si(R Ａ ) ２-; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each 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 combining at least two of them. D may also be a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as the specific examples of C in formula (E). As D in formula (H), each independently is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, or the like.

[0038] 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0039] 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 a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0040] 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 contained 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, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0041] In formulae (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0042] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, and a divalent group having a polyalkylene oxide structure.

[0043] 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 a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0044] 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 a cyclopropylene group and a cyclohexylene group.

[0045] 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. Of these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene 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 of one type or two or more types.

[0046] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of the divalent group 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, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, and an n-dodecyl group. Among these, a methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent in the aryl group include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Of these, a phenyl group is 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 of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0047] The group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H"), or formula (H'"), and from the viewpoint of having a flexible skeleton and excellent bonding properties, a group represented by the following formula (H') or formula (H") is more preferred.

[0048]

[0049] In formula (H'''), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0050] In general formula (1), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited. Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include the following: A combination where X is a group represented by formula (E) and Y is a group represented by formula (H) A combination where X is a group represented by formula (F) and Y is a group represented by formula (H) A combination where X is a group represented by formula (E) and Y is a group represented by formulas (G) and (H) A combination where X is a group represented by formulas (A) and (E) and Y is a group represented by formula (H) A combination where X is a group represented by formula (A) and Y is a group represented by formula (H)

[0051] R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, provided that at least one of them 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 a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably contains 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 above is a group represented by general formula (2). When the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-line transmittance is high, and a good cured product tends to be formed even when cured at a low temperature of 400°C or less. Furthermore, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond moiety is eliminated by imidization.

[0052] Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group, with the ethyl group, the isobutyl group, and the t-butyl group being preferred.

[0053]

[0054] In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group.

[0055] R in general formula (2) ８ ~R １０ The aliphatic hydrocarbon group represented by R has 1 to 3 carbon atoms, preferably 1 or 2. ８ ~R １０ Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0056] R in general formula (2) ８ ~R １０ As a combination of ８ and R ９ is a hydrogen atom, and R １０ is preferably a hydrogen atom or a methyl group.

[0057] R in general formula (2) ｘ is a divalent linking group, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups. ｘThe number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0058] In general formula (1), R ６ and R ７ At least one of R is preferably a group represented by the general formula (2), ６ and R ７ It is more preferable that both of the above are groups represented by the general formula (2).

[0059] When the unsaturated polyimide precursor contains a compound having a structural unit represented by the general formula (1), the R ６ and R ７ The ratio of the group R represented by general formula (2) to the total 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 is not particularly limited and may be 100 mol%. The proportion may be 0 mol% or more and less than 60 mol%.

[0060] The group represented by formula (2) is preferably a group represented by the following formula (2').

[0061]

[0062] In general formula (2'), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0063] In formula (2'), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0064] The content of the structural unit represented by general formula (1) contained in the 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, based on the total structural units. The upper limit of the content is not particularly limited, and may be 100 mol%.

[0065] The unsaturated polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The unsaturated polyimide precursor may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0066] 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 acid. dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-oxydiphthalic 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}propane dianhydride 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornane tetracarboxylic acid dianhydride, 2,2-bis{4-(4'-phenoxy)phenyl}propane tetracarboxylic acid dianhydride, and the like.Among these, 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, at least one selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride is more preferred, and from the viewpoint of bonding at lower temperatures, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride is even more preferred. The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[0067] Specific examples of the diamine compound 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, 2,4'-diaminodiphenyl ether, and 2,4'-diaminodiphenyl ether. , 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-amino (aminophenyl)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 of the diamine compound include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Preferred diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. Among these, at least one compound 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 preferred, and from the viewpoint of having a flexible skeleton and excellent adhesiveness, at least one compound selected from the group consisting of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane is even more preferred. The diamine compounds may be used alone or in combination of two or more.

[0068] Having a structural unit represented by general formula (1), and R ６ and R ７ The compound A, in which at least one of the above is a monovalent organic group, 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)) is reacted with a compound represented by R—OH in an organic solvent to form a diester derivative, and then the diester derivative and H ２ N-Y-NH ２ (b) A condensation reaction is carried out between a tetracarboxylic acid dianhydride and a diamine compound represented by the formula: ２ N-Y-NH ２ In an organic solvent, a polyamic acid solution is obtained by reacting a diamine compound represented by the formula: R--OH with the polyamic acid solution, and the compound represented by R--OH is added to the polyamic acid solution and reacted in the organic solvent to introduce an ester group.

[0069] R in general formula (1) ６ and R ７Since at least one of these has a polymerizable unsaturated bond, at least one of R—OH in which R has a polymerizable unsaturated bond is used.

[0070] Here, H ２ N-Y-NH ２ In the diamine compound represented by the formula (1), Y is the same as Y in the general formula (1), and specific examples and preferred examples are also the same. In addition, in the compound represented by R—OH, R represents a monovalent organic group, and specific examples and preferred examples are the same as R in the general formula (1). ６ and R ７ The same applies to the case of the tetracarboxylic acid dianhydride represented by the general formula (8), H ２ N-Y-NH ２ The diamine compound represented by the formula (I) and the compound represented by R—OH may each be used alone or in combination of two or more.

[0071] Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropanamide, with 3-methoxy-N,N-dimethylpropanamide being preferred. An unsaturated polyimide precursor may be synthesized by allowing a dehydration condensation agent to act on a polyamic acid solution together with a compound represented by R—OH. The dehydration condensation agent preferably includes at least one selected from the group consisting of trifluoroacetic anhydride, N,N′-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0072] The compound A contained in the unsaturated polyimide precursor is prepared by reacting a compound represented by R—OH with a tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, which is then converted into an acid chloride by reacting with a chlorinating agent such as thionyl chloride, and then reacting with a chlorinating agent such as thionyl chloride to form an acid chloride. ２ N-Y-NH ２ The compound A contained in the unsaturated polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, and then reacting the diester derivative with a carbodiimide compound in the presence of H２ N-Y-NH ２ The compound can be obtained by reacting a diamine compound represented by the following formula with a diester derivative.

[0073] The compound A contained in the unsaturated polyimide precursor is a compound represented by the following general formula (8) and a tetracarboxylic acid dianhydride represented by the following general formula (8). ２ N-Y-NH ２ The polyamic acid is then isoimidized in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then reacted with a compound represented by R—OH to obtain a polyamic acid. Alternatively, a compound represented by R—OH may be reacted in advance with a part of a tetracarboxylic dianhydride to obtain a partially esterified tetracarboxylic dianhydride and H ２ N-Y-NH ２ Alternatively, the compound may be reacted with a diamine compound represented by the following formula:

[0074]

[0075] In the general formula (8), X is the same as X in the general formula (1), and specific examples and preferred examples are also the same.

[0076] The compound represented by R—OH used in the synthesis of the compound A contained in the unsaturated polyimide precursor is R ｘ The compound represented by R-OH may be a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'), or a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'). Specific examples of the compound 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, and among these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0077] The molecular weight of the unsaturated polyimide precursor is not particularly limited, and for example, the weight average molecular weight is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 10,000 to 50,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

[0078] The photosensitive resin composition of the present disclosure may further contain a dicarboxylic acid, and the unsaturated polyimide precursor contained in the photosensitive resin composition may have a structure formed by reaction of some of the amino groups in the unsaturated polyimide precursor with carboxy groups in the dicarboxylic acid. For example, when synthesizing the unsaturated polyimide precursor, some of the amino groups of a diamine compound may be reacted with carboxy groups in the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula: In this case, when synthesizing the unsaturated polyimide precursor, by reacting some of the amino groups of the diamine compound with carboxy groups in the dicarboxylic acid, methacrylic groups derived from the dicarboxylic acid can be introduced into the unsaturated polyimide precursor.

[0079]

[0080] The photosensitive resin composition of the present disclosure 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 volatiles due to dehydration cyclodehydration during imide ring formation, which tends to suppress the generation of voids. The polyimide resin referred to here refers to a resin having an imide skeleton in all or part of the resin skeleton. It is preferable that the polyimide resin be soluble in a solvent in the photosensitive resin composition using the unsaturated polyimide precursor.

[0081] The polyimide resin is not particularly limited as long as it is a polymer compound having a plurality of structural units containing imide bonds, and preferably contains, for example, a compound having a structural unit represented by the following general formula (X): This tends to provide a semiconductor device having an insulating film that exhibits high reliability.

[0082]

[0083] In general formula (X), X represents a tetravalent organic group, and Y represents a divalent organic group. Preferred examples of the substituents X and Y in general formula (X) are the same as the preferred examples of the substituents X and Y in general formula (1).

[0084] When the photosensitive resin composition of the present disclosure contains a polyimide resin, the proportion of the polyimide resin relative to the total of the unsaturated polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or may be 10% by mass to 20% by mass.

[0085] The photosensitive resin composition of the present disclosure may contain a resin other than the unsaturated polyimide precursor and the polyimide resin. Examples of the other resin include, from the viewpoint of heat resistance, novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. The other resin may be used alone or in combination of two or more.

[0086] In the photosensitive resin composition of the present disclosure, the content of the unsaturated polyimide precursor relative to the total amount of solids is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass. The solids content refers to the residue when the photosensitive resin composition is dried at 200 to 400°C.

[0087] (Solvent) The photosensitive resin composition of the present disclosure contains at least one solvent selected from the group consisting of 3-methoxy-N,N'-dimethylpropanamide and 3-butoxy-N,N'-dimethylpropanamide.

[0088] Commercially available 3-methoxy-N,N'-dimethylpropanamide products include those under the trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.), and commercially available 3-butoxy-N,N'-dimethylpropanamide products include those under the trade name "KJCBPA-100" (manufactured by KJ Chemicals Co., Ltd.).

[0089] The solvent may contain a solvent other than the specific solvent. From the viewpoint of suppressing variations in elongation properties when the cured product is obtained, the ratio of the total amount of the specific solvent to the total amount of solvents is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, extremely preferably 99% by mass or more, and may even be 100% by mass. The other solvents may be used alone or in combination of two or more.

[0090] Other solvents include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, and the like.

[0091] Examples of ester solvents 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, and butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), and alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate). 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate; methyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate; ethyl 2-alkoxy-2-methylpropionates such as ethyl 2-ethoxy-2-methylpropionate; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

[0092] Examples of ether solvents 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 ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP). Examples of hydrocarbon solvents include limonene. Examples of aromatic hydrocarbon solvents include toluene, xylene, and anisole. Examples of sulfoxide solvents include dimethyl sulfoxide.

[0093] In view of the initial objective of being NMP-free, the content of NMP relative to the total amount of the photosensitive resin composition is preferably 0.1 mass % or less, more preferably 0.001 mass % or less, and even more preferably 0.0005 mass % or less.

[0094] The content of the solvent can be appropriately adjusted depending on the viscosity of the photosensitive resin composition, and may be, for example, 100 parts by mass or more relative to 100 parts by mass of the unsaturated polyimide precursor. From the viewpoint of reducing the drying energy required for forming a coating film, it is not necessary to contain more solvent than necessary, and for example, the content of the solvent may be 1,000 parts by mass or less relative to 100 parts by mass of the unsaturated polyimide precursor.

[0095] (N-Phenyldiethanolamine) The photosensitive resin composition of the present disclosure contains N-phenyldiethanolamine. The content of N-phenyldiethanolamine relative to 100 parts by mass of the unsaturated polyimide precursor is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, particularly preferably 1.0 parts by mass or more, extremely preferably 2.0 parts by mass or more, and most preferably 2.5 parts by mass or more. Furthermore, the content of N-phenyldiethanolamine relative to the unsaturated polyimide precursor is preferably 20 parts by mass or less, preferably 15 parts by mass or less, and preferably 12 parts by mass or less.

[0096] (Crosslinking Agent) The photosensitive resin composition may contain a crosslinking agent that can be crosslinked or polymerized by heating. In the process of applying, exposing, and developing the photosensitive resin composition and then subjecting it to heat treatment, the crosslinking agent compound reacts with the unsaturated polyimide precursor to form a crosslink, or the crosslinking agent compound itself polymerizes. This increases the strength of the resulting cured film even at a relatively low curing temperature, for example, a curing temperature of 200°C or less, and can improve mechanical properties, chemical resistance, flux resistance, etc. The crosslinking agent may be used alone or in combination of two or more.

[0097] The N-phenyldiethanolamine contained in the photosensitive resin composition of the present disclosure is presumed to function as a sensitizer, facilitating the photocrosslinking reaction by the crosslinking agent at the bottom of the film even under conditions of low exposure dose. The crosslinking agent polymer produced by the photocrosslinking reaction is eliminated and functions as a plasticizer, which can lower the glass transition temperature, and is therefore expected to have the effect of promoting polymer cyclization. Therefore, it is presumed that the use of a crosslinking agent together with N-phenyldiethanolamine promotes the cyclization reaction at the bottom of the film as well, forming a highly oriented cured film and more effectively suppressing variation in elongation properties.

[0098] From the viewpoint of enhancing resolution, the crosslinking agent preferably contains a crosslinking agent having a vinyl group in which the α-position is a hydrocarbon group (hereinafter also referred to as a "vinyl crosslinking agent").

[0099] The hydrocarbon group at the α-position is *-CH ２ Examples of such unsaturated groups include -, *-CH<, and *-C≡. * indicates the bonding position with the polymerizable double bond. The vinyl crosslinking agent may have a polymerizable unsaturated bond other than a vinyl group in which the α-position is a hydrocarbon group, such as a (meth)acryloyl group.

[0100] From the viewpoint of a balance between improvement in crosslink density, improvement in exposure sensitivity, and improvement in resolution, the vinyl crosslinking agent preferably has 2 to 4 polymerizable unsaturated bonds, and more preferably has 2 or 3 polymerizable unsaturated bonds.

[0101] From the viewpoint of suppressing the linear expansion coefficient when formed into a cured film, the molecular weight of the vinyl crosslinking agent is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less. The lower limit of the molecular weight of the vinyl crosslinking agent is not particularly limited, but may be 150 or more, or may be 200 or more.

[0102] Examples of the vinyl crosslinking agent include those represented by the following general formulas (I) to (VII).

[0103]

[0104] In general formula (I), R represents an organic group, which may contain a (meth)acryloyl group.

[0105] In general formula (II), n represents an integer of 1 to 6, preferably an integer of 2 to 4, and more preferably 3. The positions of the n vinyl groups are not particularly limited. For example, when n is 2, they may be at any of the ortho, meta, and para positions, with the ortho positions being preferred. For example, when n is 3, they may be at any of the 1,2,3 positions, 1,2,4 positions, 1,2,5 positions, and 1,3,5 positions, with the 1,2,4 positions being preferred.

[0106] In general formula (III), R １ each independently represents an allyl group or an organic group other than an allyl group, and at least one R １ is an allyl group. １ The number of allyl groups represented by R is 1 to 4, preferably 2 to 4, and １ It is more preferable that all of R are allyl groups.１ Examples of the organic group represented by the formula include a hydrocarbon group and a (meth)acryloyl group.

[0107] In general formula (IV), R ２ each independently represents an organic group other than a vinyl group or an allyl group, and at least one R ２ is a vinyl group. ２ The number of vinyl groups represented by the two R ２ Preferably, both R and R are vinyl groups. ２ Examples of the organic group represented by the formula include a hydrocarbon group and a (meth)acryloyl group.

[0108] In general formula (V), R ３ each independently represents an allyl group or an organic group other than an allyl group, and at least one R ３ is an allyl group. ３ The number of allyl groups represented by R is 1 to 4, preferably 2 to 4, and ３ It is more preferable that all of R are allyl groups. ３ Examples of the organic group represented by the formula include a hydrocarbon group and a (meth)acryloyl group.

[0109] In general formula (VI), R ４ each independently represents an allyl group or an organic group other than an allyl group, and at least one R ４ is an allyl group. ４ The number of allyl groups represented by R is 1 to 4, preferably 2 to 4, and ４ It is preferred that all of R ４ Examples of the organic group represented by the formula include a hydrocarbon group and a (meth)acryloyl group.

[0110] In general formula (VII), R ５ each independently represents an allyl group or an organic group other than an allyl group, and at least one R ５ is an allyl group. ５ The number of allyl groups represented by the formula (I) is 1 to 3, preferably 2 to 3, and more preferably 2.

[0111] Specific examples of vinyl crosslinking agents include the following compounds:

[0112]

[0113] In the above chemical formula, R １ represents a hydrogen atom or a monovalent organic group, R ２ has a single bond or a divalent linking group.

[0114] A crosslinking agent other than the vinyl crosslinking agent may be used in combination. From the viewpoint of improving resolution, the proportion of the vinyl crosslinking agent in the total amount of crosslinking agents is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 99% by mass or more, and may be 100% by mass.

[0115] Examples of crosslinking agents other than vinyl crosslinking agents include crosslinking agents having a (meth)acryloyl group (hereinafter also referred to as "(meth)acryloyl crosslinking agent"). Examples of the (meth)acryloyl crosslinking agent include alicyclic crosslinking agents and linear crosslinking agents.

[0116] The aliphatic cyclic skeleton contained in the alicyclic crosslinking agent is not particularly limited, and examples thereof include a tricyclodecane skeleton, a cyclohexane skeleton, a cyclopentane skeleton, a 1,3-adamantane skeleton, a hydrogenated bisphenol A skeleton, a hydrogenated bisphenol F skeleton, a hydrogenated bisphenol S skeleton, an isobornyl skeleton, etc. Among these, a tricyclodecane skeleton is preferred.

[0117] The alicyclic crosslinking agent is preferably a compound represented by the following general formula (3).

[0118]

[0119] In general formula (3), R １ and R ２ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following general formula (3-1): n1 represents 0 or 1, n2 represents an integer of 0 to 2, and n1+n2 is 2 or 3. n1 R １ and n2 R ２ At least two of the above are groups represented by the following general formula (3-1).

[0120]

[0121] In general formula (3-1), R １Ａ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.

[0122] R １ and R ２ Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0123] The compound represented by general formula (3) may be a compound represented by the following formula (3A) or (3B).

[0124]

[0125] The compound represented by formula (3A) is available, for example, as A-DCP (tricyclodecane dimethanol diacrylate) from Shin-Nakamura Chemical Co., Ltd., and the compound represented by formula (3B) is available, for example, as DCP (tricyclodecane dimethanol dimethacrylate) from Shin-Nakamura Chemical Co., Ltd.

[0126] The linear crosslinking agent is preferably a compound represented by the following general formula (4) or (5).

[0127]

[0128] In general formula (4) or general formula (5), R ３ each independently represents a hydrogen atom or a methyl group, R ４ represents a linear alkylene group having 1 to 8 carbon atoms, R ５ represents a linear alkylene group having 1 to 8 carbon atoms, and p represents an integer of 2 to 5. ３ and R ５ may be the same or different.

[0129] R in general formula (4) or general formula (5) ３ As R in the general formula (4), a methyl group is preferable. ４Specific examples of the linear alkylene group having 1 to 8 carbon atoms represented by the formula (5) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group. ５ Specific examples of the linear alkylene group having 1 to 8 carbon atoms represented by the formula (5) include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a dimethylmethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group, with a methylethylene group and an ethylene group being preferred, and an ethylene group being more preferred. In general formula (5), p is preferably an integer of 3 or 4.

[0130] Specific examples of the linear 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, etc. Among these, tetraethylene glycol dimethacrylate is preferred.

[0131] The 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.

[0132] (Photopolymerization initiator) The photosensitive resin composition of the present disclosure may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that can generate radicals when irradiated with actinic rays. Examples of actinic rays include ultraviolet rays such as i-rays, visible light, and radioactive rays.

[0133] Examples of the photopolymerization initiator include an oxime compound, an acylphosphine oxide compound, and an acyldialkoxymethane compound.

[0134] Examples of the photopolymerization initiator include a compound represented by the following general formula (9A), a compound represented by the following general formula (9B), a compound represented by the following general formula (10A), and a compound represented by the following general formula (10B).

[0135]

[0136] In general formula (9A), R １１ is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. １２ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. １３ and R １４ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. １１ may be the same or different.

[0137] R １１ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. a1 is preferably 1. R １２ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group. １３ and R １４ are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

[0138] An example of the compound represented by general formula (9A) is a compound represented by the following formula (9A-1), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

[0139]

[0140]

[0141] In general formula (9B), R １５ is -OH, -COOH, -OCH ２ OH, —O(CH ２ ) ２ OH, -COOCH ２ OH or -COO(CH ２ ) ２ OH and R １６ and R１７ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group. b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R １５ may be the same or different. １５ is preferably —O(CH ２ ) ２ OH. b1 is preferably 0 or 1. R １６ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or a hexyl group. １７ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.

[0142] Examples of the compound represented by general formula (9B) include a compound represented by the following formula (9B-1), which is available as "IRGACURE OXE 01" manufactured by BASF Japan Ltd., and a compound represented by the following formula (9B-2), which is available as "NCI-930" manufactured by ADEKA Corporation.

[0143]

[0144]

[0145] In general formula (10A), R ２１ is an alkyl group having 1 to 12 carbon atoms, and R ２２ and R ２３ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R ２１ may be the same or different. c1 is preferably 0. R ２２ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. ２３is 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. An example of the compound represented by general formula (10A) is a compound represented by the following formula (10A-1), which is available as "G-1820 (PDO)" manufactured by Lambson.

[0146]

[0147]

[0148] In general formula (10B), R ２４ and R ２５ are each independently an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each independently an integer of 0 to 5, s and t are each independently an integer of 0 to 3, and the sum of s and t is 3. When d is an integer of 2 or more, R ２４ may be the same or different. When e is an integer of 2 or more, R ２５ may be the same or different. When s is an integer of 2 or more, the groups in the parentheses may be the same or different. When t is an integer of 2 or more, the groups in the parentheses may be the same or different. d is preferably 0. R ２５ are preferably each independently an alkyl group having 1 to 4 carbon atoms, and are preferably a methyl group. e is preferably an integer of 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 compounds represented by the following formula (10B-1), which is available as "IRGACURE TPO" manufactured by BASF Japan Ltd. Examples of compounds represented by formula (10B-2) include compounds represented by the following formula (10B-3), which is available as "IRGACURE 819" manufactured by BASF Japan Ltd.

[0149]

[0150] Among the above photopolymerization initiators, it is preferable to use a vinyl crosslinking agent in combination with a compound represented by formula (9B) or a compound represented by formula (9A-1) from the viewpoint of resolution.

[0151] The content of the 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, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0152] (Thermal Polymerization Initiator) From the viewpoint of accelerating the polymerization reaction, the photosensitive resin composition of the present disclosure may further contain a thermal polymerization initiator. As the thermal polymerization initiator, a compound that does not decompose when heated (dried) to remove the solvent during film formation, but decomposes when heated during curing to generate radicals and promotes the polymerization reaction between polymerizable monomers, or between an unsaturated polyimide precursor and a polymerizable monomer, is preferred. As the thermal polymerization initiator, a compound having a decomposition point of 110°C to 200°C is preferred, and from the viewpoint of promoting the polymerization reaction at a lower temperature, a compound having a decomposition point of 110°C to 175°C is more preferred.

[0153] Specific examples of the thermal polymerization initiator 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 dialkyl peroxides such as dicyclohexane. Examples of suitable peroxyesters include diacyl peroxides such as dibenzoyl peroxide and 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 peroxyesters include those sold under the trade names "Percumyl D," "Percumyl P," and "Percumyl H" (all manufactured by NOF Corporation).

[0154] When the photosensitive resin composition of the present disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 0.2 parts by mass to 20 parts by mass in order to ensure good flux resistance, and even more preferably 0.3 parts by mass to 10 parts by mass in order to suppress a decrease in solubility due to decomposition during drying.

[0155] (Imidization Accelerator) The resin composition of the present disclosure may contain a nitrogen-containing compound as an imidization accelerator from the viewpoint of accelerating the imidization reaction.

[0156] Specific examples of the nitrogen-containing compound include 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, and 4-aminoacetophenone, and among these, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. The nitrogen-containing compounds may be used alone or in combination of two or more.

[0157] When the resin composition of the present disclosure contains an imidization accelerator, the content of the imidization accelerator is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, and from the viewpoint of storage stability, is more preferably 0.3 parts by mass to 15 parts by mass, and even more preferably 0.5 parts by mass to 10 parts by mass.

[0158] (Sensitizer) The photosensitive resin composition of the present disclosure may contain a sensitizer. By containing a sensitizer in the photosensitive resin composition, it is possible to maintain both the remaining film rate and good resolution over a wide range of exposure doses. The sensitizer may be used alone or in combination of two or more.

[0159] Examples of sensitizers include Michler'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-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, benzyl dimethyl ketone, and the like. tar, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutylate, acridine orange, erythrosine, phenanthrenequinone, 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, and the like.

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

[0161] (Stabilizer) The photosensitive resin composition of the present disclosure may contain a stabilizer. When the photosensitive resin composition contains a stabilizer, the storage stability can be improved.

[0162] Examples of stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, and hindered phenol compounds.

[0163] The stabilizer may be used alone or in combination of two or more. By combining two or more stabilizers, photosensitive characteristics tend to be easily adjusted due to differences in reactivity. The hindered phenol compound may have both a stabilizer function and an antioxidant function described below, or may have only one of these functions.

[0164] 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'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 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-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) alcohol), 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 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-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-hydroxy N,N'-hexane-1,6-diylbis[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]non-2-ene-2,3-dioxide.

[0165] When the photosensitive resin composition of the present disclosure contains a stabilizer, the content of the stabilizer is preferably 0.05 parts by mass to 1.0 parts by mass, and more preferably 0.1 parts by mass to 0.8 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0166] (Antioxidant) The photosensitive resin composition of the present disclosure may contain an antioxidant from the viewpoint of suppressing a decrease in adhesiveness by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, etc. When the photosensitive resin composition of the present disclosure contains an antioxidant, oxidation of an electrode during an insulation reliability test can be suppressed.

[0167] Specific examples of the antioxidant include the compounds exemplified above as the hindered phenol compound, 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, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, etc. The antioxidant may be used alone or in combination of two or more.

[0168] When the photosensitive resin composition of the present disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0169] (Coupling Agent) The photosensitive resin composition of the present disclosure may contain a coupling agent. When a coupling agent is contained, the adhesion between the obtained cured product and a substrate can be further improved.

[0170] The coupling agent is not particularly limited, and examples thereof 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]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)methylsilane ... Examples of suitable coupling agents include silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane; and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate. These coupling agents may be used alone or in combination of two or more.

[0171] When the photosensitive resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, and even more preferably 2 parts by mass to 10 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0172] (Rust inhibitor) The photosensitive resin composition of the present disclosure may contain a rust inhibitor. By containing a rust inhibitor in the photosensitive resin composition, corrosion of copper and copper alloys and discoloration can be suppressed. Examples of the rust inhibitor include azole compounds and purine derivatives. The rust inhibitor may be used alone or in combination of two or more.

[0173] Specific examples of the azole compound 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, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and benzotriazole, 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, 1-methyl-1H-tetrazole, and the like.

[0174] 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 derivatives thereof.

[0175] When the photosensitive resin composition of the present disclosure contains a rust inhibitor, the content of the rust inhibitor is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, and even more preferably 0.5 parts by mass to 3 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0176] (UV absorber) The photosensitive resin composition of the present disclosure may contain an UV absorber. When the photosensitive resin composition contains an UV absorber, crosslinking of unexposed areas due to diffuse reflection during exposure tends to be suppressed. Examples of UV absorbers include benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, diphenylacrylate-based compounds, cyanoacrylate-based compounds, diphenylcyanoacrylate-based compounds, benzothiazole-based compounds, azobenzene-based compounds, polyphenol-based compounds, and nickel complex salt-based compounds. The UV absorbers may be used alone or in combination of two or more.

[0177] 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-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-( 2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol), and the like.

[0178] Examples of salicylic acid ester compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0179] 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.

[0180] Examples of diphenylacrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.

[0181] Examples of diphenyl cyanoacrylate compounds include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).

[0182] Examples of the azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0183] Examples of polyphenol compounds include pyrogallol, phloroglycine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, gossypetin, pelargonidin, cyanidin, aurantidin, luteolinidin, peonidin, rosinidin, (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.

[0184] Examples of polyphenol compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).

[0185] Among the above, it is preferable to use at least one selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds as the material ray absorber.

[0186] Furthermore, as the ultraviolet absorber, from the viewpoint of resolution, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-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, 1,7-bis (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione It is more preferable to use at least one selected from the group consisting of (4-hydroxyphenyl) -1,6-heptadiene-3,5-dione.

[0187] When the photosensitive resin composition of the present disclosure contains an ultraviolet absorber, the content of the 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, relative to 100 parts by mass of the unsaturated polyimide precursor, from the viewpoint of resolution. Furthermore, from the viewpoint of preventing insufficient photocuring inside the coating film, the content 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.

[0188] (Surfactant and Leveling Agent) The photosensitive resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent. When the photosensitive resin composition contains at least one of a surfactant and a leveling agent, it is possible to improve coatability (for example, suppression of striations (uneven film thickness)) and developability.

[0189] Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Commercially available products include those sold under the trade names "Megafac (registered trademark) F171," "F173," and "R-08" (all manufactured by DIC Corporation), those sold under the trade names "Fluorad FC430" and "FC431" (all manufactured by Sumitomo 3M Limited), and those sold under the trade names "Organosiloxane Polymer KP341," "KBM303," and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0190] The surfactants and leveling agents may be used alone or in combination of two or more.

[0191] When the photosensitive resin composition of the present disclosure contains at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, and even more preferably 0.05 parts by mass to 3 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0192] (Other Components) The photosensitive resin composition of the present disclosure may further contain other components and inevitable impurities. In the photosensitive resin composition of the present disclosure, the total amount of the unsaturated polyimide precursor, N-phenyldiethanolamine, crosslinking agent, photopolymerization initiator, and solvent may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. In addition, in the photosensitive resin composition of the present disclosure, the total amount of the unsaturated polyimide precursor, N-phenyldiethanolamine, crosslinking agent, photopolymerization initiator, solvent, stabilizer, sensitizer, UV absorber, rust inhibitor, antioxidant, and coupling agent 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.

[0193] <Cured Product> The cured product of the present disclosure can be obtained by curing the photosensitive resin composition of the present disclosure. The cured product of the present disclosure may be used as a patterned cured product or as a non-patterned cured product. The average thickness of the cured product is preferably 5 μm to 20 μm.

[0194] The breaking elongation of the cured product is preferably 25% or more, more preferably 35% or more, and even more preferably 50% or more. There is no particular upper limit to the breaking elongation of the cured product.

[0195] <Method for Producing Cured Product, and Electronic Component> The method for producing a patterned cured product of the present disclosure includes the steps of applying the photosensitive resin composition of the present disclosure onto a substrate and drying to form a photosensitive resin film, patternwise exposing the photosensitive resin film to light to obtain a resin film, developing the patterned exposed resin film with a developer to obtain a patterned resin film, and heat-treating the patterned resin film. This allows a patterned cured product to be obtained.

[0196] A method for producing a patternless cured product includes, for example, a step of forming a photosensitive resin film according to the present disclosure and a step of heat treatment. It may further include a step of exposing the film to light.

[0197] The substrate may be a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), or a TiO ２ Substrate, SiO ２Examples of the substrate include a metal oxide insulator substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0198] The method for applying the photosensitive resin composition of the present disclosure is not particularly limited, and can be carried out using a spinner or the like.

[0199] Drying can be carried out using a hot plate, an oven, or the like. The drying temperature is preferably 90°C to 150°C, and from the viewpoint of ensuring dissolution contrast, more preferably 90°C to 120°C. 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 of the present disclosure is formed into a film shape.

[0200] 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 30 μm.

[0201] The pattern exposure is performed by exposing the film to a predetermined pattern through a photomask, for example. The actinic ray to be irradiated may be ultraviolet light such as i-ray, visible light, or radiation, but i-ray is preferred. The exposure device may be a parallel exposure device, an aligner, a projection exposure device, a stepper, a scanner exposure device, or the like.

[0202] By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed areas are removed with a developer. As the developer, a good solvent for the photosensitive resin film can be used alone, or an appropriate mixture of a good solvent and a poor solvent can be used. 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.

[0203] A surfactant may be added to the developer in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.

[0204] The developing time can be, for example, twice the time required for the photosensitive resin film to be immersed and completely dissolved. The developing time varies depending on the unsaturated polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, even more preferably 20 seconds to 5 minutes.

[0205] After development, the resist may be washed with a rinse solution, such as distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, or propylene glycol monomethyl ether, which may be used alone or in appropriate mixtures, or in stepwise combinations.

[0206] A patterned cured product can be obtained by heat-treating the patterned resin film, where the unsaturated polyimide precursor undergoes a dehydration ring-closing reaction to form the corresponding polyimide resin.

[0207] The temperature of the heat treatment is preferably 250° C. or less, 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, devices can be produced with a high yield, and energy savings can be achieved in the process.

[0208] The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By keeping the heat treatment time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be sufficiently progressed. The heat treatment atmosphere may be air or an inert atmosphere such as nitrogen, and a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the patterned resin film.

[0209] Examples of equipment used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0210] The cured product of the present disclosure can be used as an interlayer insulating film, a cover coat layer, or a surface protective film. Furthermore, the cured product of the present disclosure can be used as a passivation film, a buffer coat film, etc. Highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (such as multi-die fan-out wafer-level packages) can be manufactured using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, and surface protective film.

[0211] An example of a manufacturing process for a semiconductor device, which is an electronic component according to the present disclosure, will be described with reference to the drawings. Figure 1 is a diagram illustrating a manufacturing process for a semiconductor device with a multilayer wiring structure, which is an electronic component according to an 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. An interlayer insulating film 4 is then formed on the semiconductor substrate 1.

[0212] Next, a photosensitive resin layer 5 such as a chlorinated rubber or phenol novolac resin is formed on the interlayer insulating film 4, and windows 6A are formed by known photoetching techniques so that predetermined portions of the interlayer insulating film 4 are exposed.

[0213] The interlayer insulating film 4 where the window 6A is exposed is selectively etched to provide a 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 the window 6B.

[0214] Furthermore, a second conductor layer 7 is formed using a known photolithography technique, and electrically connected to the first conductor layer 3. When forming a multilayer wiring structure having three or more layers, the above steps can be repeated to form each layer.

[0215] Next, the photosensitive resin composition of the present disclosure is used to open windows 6C by pattern exposure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductor 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 the present disclosure.

[0216] The present disclosure will be described in more detail below based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0217] [Examples 1 to 11 and Comparative Examples 1 to 4] Each component shown in Table 1 was mixed in the amount shown in Table 1 to prepare a uniform 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 11 and Comparative Examples 1 to 4. The amount of each component in Table 1 is based on parts by mass. In the table, "NPDA" stands for N-phenyldiethanolamine.

[0218]

[0219] Details of each component listed in Table 1 are as follows.

[0220] Unsaturated Polyimide Precursor I: 380 g of N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical Corporation) was placed in a 2 L separable flask, and 47.08 g (152 mmol) of 4,4'-oxydiphthalic anhydride (ODPA, Manac Corporation) was added and dissolved while stirring. Furthermore, 0.24 g (2.1 mmol) of DABCO (1,4-diazabicyclo[2.2.2]octane, Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added and dissolved, and 5.54 g (42.6 mmol) of 2-hydroxyethyl methacrylate (HEMA, Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added, followed by stirring at 30 °C for 1 hour to obtain a reaction solution. Separately, 27.4 g (129 mmol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP, Wakayama Seika Kogyo Co., Ltd.) was dissolved in 145 g of NMP to prepare a DMAP solution. The DMAP solution was added dropwise while stirring the reaction solution at 35°C, followed by stirring at 30°C for 3 hours. Next, 59.7 g (284 mmol) of TFAA (trifluoroacetic anhydride, Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise at 30°C. After stirring at 45°C for 2 hours, 0.08 g (0.74 mmol) of BQ (benzoquinone, Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and 40.4 g (310 mmol) of HEMA was added dropwise. After stirring for 15 hours, the mixture was cooled to room temperature. The reaction solution was poured into purified water, and the precipitate was collected, washed with purified water, and dried under reduced pressure to obtain unsaturated polyimide precursor I. The weight average molecular weight (Mw) of unsaturated polyimide precursor I was 25,000.

[0221] The weight-average molecular weight of the unsaturated polyimide precursor was calculated by gel permeation chromatography (GPC) using a calibration curve based on TSKgel standard polystyrene (Tosoh Corporation). The equipment 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 through a PTFE membrane filter with a pore size of 1 μm.

[0222] 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

[0223] Unsaturated Polyimide Precursor II: An unsaturated polyimide precursor II was prepared, which had an amine component consisting of 4,4'-diaminodiphenyl ether (ODA) and m-phenylenediamine (MPD) in a molar ratio of 7:3, and an acid component consisting of 4,4'-oxydiphthalic anhydride (ODPA). The weight-average molecular weight (Mw) of the unsaturated polyimide precursor II was 23,000.

[0224] Unsaturated Polyimide Precursor III An unsaturated polyimide precursor III was prepared, which had a molar ratio of 3:1 between 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) as the amine component and pyromellitic dianhydride (PMDA) and 4,4'-oxydiphthalic anhydride (ODPA) as the acid components. The weight-average molecular weight (Mw) of the unsaturated polyimide precursor III was 39,000.

[0225] Unsaturated Polyimide Precursor IV: An unsaturated polyimide precursor IV was prepared, which had an amine component consisting of 4,4'-diaminodiphenyl ether (ODA) and 4,4'-oxydiphthalic anhydride (ODPA). The weight-average molecular weight (Mw) of the unsaturated polyimide precursor IV was 32,000.

[0226] Solvent: 3-methoxy-N,N'-dimethylpropanamide (trade name "KJCMPA-100", manufactured by KJ Chemicals Co., Ltd.; Crosslinker I: allyl methacrylate; Crosslinker II: triethylene glycol dimethacrylate; Photopolymerization initiator: 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (IRGACURE OXE 01, manufactured by BASF Japan).

[0227] (Preparation of Cured Film) Using a coating and developing apparatus (ACT-8, Tokyo Electron Limited), each photosensitive resin composition was applied onto a Si wafer by spin coating, and the wafer was prebaked (PB) at 100°C for 2 minutes and then at 110°C for 2 minutes to obtain a PB film having a film thickness of 15 μm. The PB film was exposed to light using a mask aligner (MA8, SUSS MicroTec). The exposure dose was 800 mJ / cm for Examples 1 to 7 and Comparative Examples 1 to 3. ２ , and 400 mJ / cm in Examples 8 to 11 and Comparative Example 4. ２ After exposure, development was carried out using cyclopentanone by a two-stage puddle method. The development time for each composition was determined as follows. An unexposed 15 μm PB film was prepared, and the time from when a developer was dropped onto this PB film until the interference fringes caused by development disappeared was measured, and the resulting time was taken as the development time. Development was carried out twice for the aforementioned development time. After development, the film was cured in a vertical diffusion furnace (μ-TF, Koyo Thermo Systems Co., Ltd.) at 230°C for 2 hours under a nitrogen atmosphere to produce a cured film.

[0228] (Tensile Test Method) The cured product prepared on a Si wafer was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid and peeled off from the Si wafer to obtain a sample for evaluation of mechanical properties. Tensile tests were performed on these samples using a Shimadzu AGS-X 100N autograph. Measurements were performed six times for each sample, with a chuck distance of 50 mm, a tensile speed of 40 mm / min, and a measurement temperature of 18°C ​​to 25°C. The elongation at break (%) was measured, and the average of the six measurements was also calculated. Next, a graph was created from the measured values, with the load on the horizontal axis and the elongation on the vertical axis. The tensile modulus (GPa) of each test piece was calculated from the tangent to the rising portion of the load-elongation curve. The tensile strength at break (MPa) at the time the sample broke was also calculated. The results are shown in Tables 2 to 16.

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] In the measurement of the breaking elongation of Examples 1 to 11 and Comparative Examples 1 to 4, the number of times that a breaking elongation of 40% or more was obtained out of six measurements, the percentage (%) of the breaking elongation (Evaluation 1), and the percentage (%) of the average value / maximum value of the breaking elongation (Variation, Evaluation 2) are summarized in Table 6.

[0245]

[0246] In the Comparative Examples, cured films with higher breaking elongation percentages were occasionally obtained, but on average, the breaking elongation percentages of the cured films of the Comparative Examples were lower than those of the cured films of the Examples. Furthermore, as shown in Table 17, the cured films obtained from the compositions of the Examples containing an unsaturated polyimide precursor, a specific solvent, and N-phenyldiethanolamine had smaller breaking elongation percentage variations, close to 100%, compared to the cured films obtained from the Comparative Examples not containing N-phenyldiethanolamine. Comparative Example 4 had smaller breaking elongation percentage variations, but its breaking elongation percentage was small to begin with.

[0247] Furthermore, a comparison of Examples 3 to 5 shows that the variation in elongation at break was suppressed even when the blending amount of N-phenyldiethanolamine was changed. In particular, Examples 4 and 5, in which the content of N-phenyldiethanolamine was 5 to 10 parts by mass per 100 parts by mass of unsaturated polyimide precursor, more effectively suppressed the variation in elongation at break than Example 3, in which the content of N-phenyldiethanolamine was 3 parts by mass. However, a comparison of Examples 1 to 3 shows that by adjusting the content of crosslinking agent, it is possible to bring the variation in elongation at break closer to that of Examples 4 and 5, even when the content of N-phenyldiethanolamine was 3 parts by mass.

[0248] Furthermore, as shown in Table 17, in the Examples, even when the type of unsaturated polyimide precursor was changed, the variation in the elongation at break was suppressed.

[0249] All publications, patent applications, and technical standards mentioned in this specification are incorporated by reference into this specification to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

[0250] REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductor layer 4 interlayer insulating film 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductor layer 8 surface protective film

Claims

1. A photosensitive resin composition comprising a polyimide precursor having a polymerizable unsaturated bond, at least one solvent selected from the group consisting of 3-methoxy-N,N'-dimethylpropanamide and 3-butoxy-N,N'-dimethylpropanamide, and N-phenyldiethanolamine.

2. The photosensitive resin composition according to claim 1, wherein the polyimide precursor having a polymerizable unsaturated bond has a structural unit represented by the following general formula (1): (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; R ６ and R ７ At least one of the above has a polymerizable unsaturated bond.

3. The photosensitive resin composition according to claim 1 or 2, further comprising at least one of a crosslinking agent and a photopolymerization initiator.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the N-phenyldiethanolamine is 0.1 parts by mass or more per 100 parts by mass of the polyimide precursor.

5. A method for producing a patterned cured product, comprising the steps of: applying the photosensitive resin composition according to any one of claims 1 to 4 onto a substrate and drying to form a photosensitive resin film; exposing the photosensitive resin film to a pattern to obtain a resin film; developing the resin film after the pattern exposure with a developer to obtain a patterned resin film; and heat-treating the patterned resin film.

6. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4.

7. The cured product according to claim 6, which is a patterned cured product.

8. The cured product according to claim 6, which is used as an interlayer insulating film, a cover coat layer or a surface protective film.

9. An electronic part comprising the cured product according to any one of claims 6 to 8.

Images