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

Abstract

This photosensitive resin composition contains a polyimide precursor having a polymerizable unsaturated bond and a polymerizable monomer having a functionality of three or more. The i-line transmittance of a 7 μm-thick photosensitive resin film obtained by heating the photosensitive resin composition at 100°C for 120 seconds and then at 110°C for 120 seconds is 30% or less.

Description

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

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

[0002] Conventionally, surface protective films and interlayer insulating films for semiconductor elements have been made of polyimides, polybenzoxazoles, and the like, which have excellent heat resistance as well as electrical and mechanical properties. In recent years, photosensitive resin compositions in which these resins themselves are given photosensitivity have been used, and their use can simplify the manufacturing process of patterned cured products and shorten the complicated manufacturing process (see, for example, Patent Document 1).

[0003] JP 2009-265520 A

[0004] As semiconductor elements become more highly functional, the redistribution layers are becoming finer, and high resolution is also required for polyimides that form insulating films. 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 can achieve high resolution, a patterned cured product using the photosensitive resin composition, a method for producing the patterned cured product, and an electronic component.

[0005] Specific means for achieving the above object are as follows: <1> A photosensitive resin composition comprising a polyimide precursor having a polymerizable unsaturated bond, a tri- or higher functional polymerizable monomer, and a photopolymerization initiator, wherein the photosensitive resin composition is heated at 100°C for 120 seconds and then at 110°C for 120 seconds to form a 7 μm-thick photosensitive resin film having an i-line transmittance of 30% or less. <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 ７at least one of which has a polymerizable unsaturated bond.) <3> The photosensitive resin composition according to <1> or <2>, further comprising at least one selected from the group consisting of a sensitizer and an ultraviolet absorber. <4> The photosensitive resin composition according to <1> or <2>, wherein the photopolymerization initiator comprises an oxime compound. <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 patterned cured product obtained by curing the photosensitive resin composition according to any one of <1> to <4>. <7> The patterned cured product according to <6>, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film. <8> An electronic component comprising the patterned cured product according to <6> or <7>.

[0006] According to one embodiment of the present disclosure, it is possible to provide a photosensitive resin composition capable of achieving high resolution, a patterned cured product using the photosensitive resin composition, a method for producing the patterned cured product, and an electronic component.

[0007] 1A is a cross-sectional FIB-SEM photograph of a via pattern formed using the photosensitive resin composition of Example 1, and FIG. 1B is a cross-sectional SEM photograph of a via pattern formed using the photosensitive resin composition of Comparative Example 1, illustrating a manufacturing process for an electronic component according to an embodiment of the present disclosure.

[0008] 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.

[0009] 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.

[0010] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure is a photosensitive resin composition containing a polyimide precursor having a polymerizable unsaturated bond and a tri- or higher functional polymerizable monomer, and when the photosensitive resin composition is heated at 100°C for 120 seconds and then at 110°C for 120 seconds, the i-line transmittance of a 7 μm-thick photosensitive resin film obtained is 30% or less. Hereinafter, the "polyimide precursor having a polymerizable unsaturated bond" is also referred to as an "unsaturated polyimide precursor," and the "tri- or higher functional polymerizable monomer" is also referred to as a "specific polymerizable monomer."

[0011] The photosensitive resin composition described above allows for high resolution. While the reason for this is unclear, it is presumed to be as follows: Conventional photosensitive resin compositions use bifunctional monomers as polymerizable monomers. Bifunctional monomers polymerize to form linear polymers, resulting in low crosslink density in the cured film. Therefore, the pattern obtained by developing this cured film swells in the developer, making it difficult to obtain a high-resolution pattern. On the other hand, trifunctional or higher functional polymerizable monomers are highly reactive and react with small amounts of radicals generated from the photopolymerization initiator by light reflected from the substrate onto unexposed areas, resulting in a pattern shape that differs from the intended shape. In particular, when the pattern is thinned, cured material may form at the bottom of the pattern, or bridged cured material (so-called microbridges) may form above the bottom in the thickness direction, resulting in significant defects in the pattern shape.

[0012] In the photosensitive resin composition of the present disclosure, the use of a tri- or higher functional monomer increases the crosslink density, suppressing swelling in a developer, while reducing the amount of i-rays reaching the substrate, thereby suppressing light reflected from the substrate toward unexposed areas and suppressing polymerization reactions in the unexposed areas, presumably resulting in high resolution.

[0013] The photosensitive resin composition of the present disclosure is heated at 100°C for 120 seconds and then at 110°C for 120 seconds to obtain a 7 μm-thick photosensitive resin film (hereinafter referred to as "photosensitive resin film") having an i-line transmittance of 30% or less, preferably 25% or less, more preferably 20% or less, and even more preferably 18% or less. From the viewpoint of transmittance, the i-line transmittance of the photosensitive resin film is preferably 5% or more, more preferably 10% or more. The i-line transmittance is measured according to the method described in the examples.

[0014] The i-line transmittance of the photosensitive resin film can be adjusted by adding an ultraviolet absorber, a sensitizer, a compound having i-line absorbing ability and adjusting the amount thereof added, selecting the type of photopolymerization initiator, unsaturated polyimide precursor, etc. and adjusting the amount thereof added, etc. For example, when a rust inhibitor has i-line absorbing ability, the rust inhibitor corresponds to a compound having i-line absorbing ability.

[0015] 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.

[0016] (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.

[0017] 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.

[0018] The unsaturated polyimide precursor preferably has a structural unit represented by the following general formula (1).

[0019]

[0020] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７each 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026]

[0027] 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.

[0028] 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 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. C preferably contains an ether bond, and is preferably an ether bond.

[0029] 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.

[0030] 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.

[0031]

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] In formulae (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043]

[0044] 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.

[0045] 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 combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include the following: A combination in which X is a group represented by formula (E) and Y is a group represented by formula (H) A combination in which X is a group represented by formula (F) and Y is a group represented by formula (H) A combination in which X is a group represented by formula (E) and Y is a group represented by formulas (G) and (H) A combination in which X is a group represented by formulas (A) and (E) and Y is a group represented by formula (H) A combination in which X is a group represented by formulas (E) and (F) and Y is a group represented by formula (H) Among the above combinations, the combination in which X is a group represented by formula (E) and Y is a group represented by formula (H) is preferred.

[0046] 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 ７In addition, 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 part of the unsaturated double bond moiety is eliminated by the compound (C).

[0047] 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, and among these, an ethyl group, an isobutyl group, and a t-butyl group are preferred.

[0048]

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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. ｘ The number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0053] In general formula (1), R６ 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).

[0054] 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%.

[0055] The group represented by formula (2) is preferably a group represented by the following formula (2').

[0056]

[0057] 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.

[0058] In formula (2'), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0059] 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%.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] Having a structural unit represented by general formula (1), and R in general formula (1) ６ and R ７ The compound in which at least one of the groups 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.

[0064] 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.

[0065] 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, R in the compound represented by R—OH represents a monovalent organic group, and specific examples and preferred examples are the same as R in 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.

[0066] 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).

[0067] The above-mentioned compound contained in the unsaturated polyimide precursor is prepared by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH 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 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.

[0068] 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:

[0069]

[0070] 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.

[0071] The compound represented by R—OH used in the synthesis of the above-mentioned compound 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.

[0072] 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, and more preferably 10,000 to 100,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0073] 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.

[0074]

[0075] 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.

[0076] 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.

[0077]

[0078] 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).

[0079] 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.

[0080] 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.

[0081] 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 applied to a substrate, heated at 100°C for 120 seconds, and then heated at 110°C for 120 seconds to remove the solvent and the like.

[0082] (Polymerizable Monomer) The photosensitive composition of the present disclosure contains a trifunctional or higher functional polymerizable monomer (specific polymerizable monomer). In the present disclosure, the functional group in the polymerizable monomer refers to a group capable of reacting with the polymerizable unsaturated bond of the unsaturated polyimide precursor. The specific polymerizable monomer has three or more such functional groups, and may have four or more. The number of functional groups in the specific polymerizable monomer is preferably eight or less, more preferably six or less, and even more preferably five or less. The number of functional groups in the specific polymerizable monomer is preferably three or four. The specific polymerizable monomer may be used alone or in combination of two or more.

[0083] Examples of the functional group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. From the viewpoint of polymerization reactivity, a (meth)acryloyl group and a vinyl group are preferred, and a (meth)acryloyl group is more preferred.

[0084] The specific polymerizable monomer is preferably a compound represented by the following general formula (6).

[0085] R in formula (6) ｘ and R ８ ~R １０ is R in formula (2). ｘ and R ８ ~R １０ are synonymous with each other. ｘ are each independently -(CH ２ ) ｑ -, and q has the same meaning as q in general formula (2'). In formula (6), n represents an integer of 3 to 6, preferably 3 to 5, and more preferably 3 or 4. In formula (6), each p independently represents an integer of 0 or 1 or more, preferably 0 to 30, more preferably 0 to 20, and even more preferably 0 to 5.

[0086] In formula (6), A is an n-valent organic group. A may be linear, cyclic, or branched. Examples of the n-valent organic group include an n-valent hydrocarbon group that may contain an oxygen atom, an n-valent group derived from bisphenol, an n-valent group derived from fluorene, an n-valent group derived from tricyclodecane, and an n-valent group derived from an isocyanuric group.

[0087] Examples of the n-valent hydrocarbon group which may contain an oxygen atom include an n-valent aliphatic hydrocarbon group which may contain an oxygen atom, and an n-valent aromatic hydrocarbon group which may contain an oxygen atom, and an n-valent aliphatic hydrocarbon group which may contain an oxygen atom is preferred.

[0088] Examples of the n-valent aliphatic hydrocarbon group which may contain an oxygen atom include the following.

[0089]

[0090] In the above chemical formula, * indicates the position at which the compound is linked to the structure enclosed in parentheses in formula (6). Each n independently represents an integer of 0 or 1 or more, and is preferably 0 or 1.

[0091] In the above chemical formula, each R independently represents a hydrogen atom or a (meth)acryloyl group (—O—CO—CH═CH ２ , -O-CO-CCH ３ =CH ２ Each n independently represents an integer of 0 or 1 or more, preferably 0 or 1. m represents an integer of 2 or more. * represents a position connecting to the structure enclosed in parentheses in formula (6), or a hydroxyl group.

[0092] Among these, A in formula (6) is preferably an n-valent aliphatic hydrocarbon group which may contain an oxygen atom or an n-valent group derived from an isocyanuric group, and more preferably an n-valent aliphatic hydrocarbon group which may contain an oxygen atom or an n-valent group derived from an isocyanuric group.

[0093] Specific examples of the specific polymerizable monomer include tris-(2-acryloxyethyl)isocyanurate and ethoxylated pentaerythritol tetraacrylate.

[0094] The specific polymerizable monomer may be obtained by synthesis or may be a commercially available product, such as NK Ester A-9300 (trifunctional) and ATM-4E (tetrafunctional) manufactured by Shin-Nakamura Chemical Co., Ltd.

[0095] As the polymerizable monomer, in addition to the specific polymerizable monomer, a bifunctional polymerizable monomer may be used in combination. The functional group in the bifunctional polymerizable monomer may be the functional group described for the specific polymerizable monomer, and a (meth)acryloyl group and a phenylethynyl group are preferred, and a (meth)acryloyl group is more preferred. The bifunctional polymerizable monomer may be an alicyclic polymerizable monomer or a linear polymerizable monomer.

[0096] The aliphatic cyclic skeleton contained in the alicyclic polymerizable monomer 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.

[0097] The alicyclic polymerizable monomer is preferably a compound represented by the following general formula (3).

[0098]

[0099] 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 1 or 2. n1 R １ and n2 R ２ At least two of the above are groups represented by the following general formula (3-1).

[0100]

[0101] In general formula (3-1), R １Ａ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.

[0102] R １ and R ２Specific 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.

[0103] The compound represented by general formula (3) may be a compound represented by the following formula (3A) or (3B).

[0104]

[0105] 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.

[0106] The linear polymerizable monomer is preferably a compound represented by the following general formula (4) or (5).

[0107]

[0108] 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.

[0109] R in general formula (4) or general formula (5) ３ As R in the general formula (4), a methyl group is preferable. ４ 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 tetramethylene group, a hexamethylene group, and an octamethylene group. ５Specific 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.

[0110] Specific examples of linear polymerizable monomers 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. Of these, tetraethylene glycol dimethacrylate is preferred.

[0111] The proportion of the specific polymerizable monomer relative to the total content of polymerizable monomers is not particularly limited and can be appropriately adjusted in consideration of the i-line transmittance of the photosensitive resin film, film properties, etc. For example, the proportion of the specific polymerizable monomer relative to the total content of polymerizable monomers may be 5% by mass or more, 15% by mass or more, or 50% by mass or more. Furthermore, the proportion of the specific polymerizable monomer relative to the total content of polymerizable monomers may be 100% by mass or less, 80% by mass or less, or 70% by mass or less.

[0112] From the viewpoint of high resolution, the total content of the polymerizable monomers is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and even more preferably 10 parts by mass to 40 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0113] (Photopolymerization initiator) The photosensitive composition of the present disclosure contains 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. The photopolymerization initiator may be used alone or in combination of two or more.

[0114] Examples of the photopolymerization initiator include an oxime compound, an acylphosphine oxide compound, and an acyldialkoxymethane compound.

[0115] 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).

[0116]

[0117] 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.

[0118] 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.

[0119] 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.

[0120]

[0121]

[0122] 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 R １７ 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.

[0123] 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.

[0124]

[0125]

[0126] In general formula (10A), R ２１ is an alkyl group having 1 to 12 carbon atoms, and R ２２ and R ２３are 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. ２３ is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group or an ethoxy group. 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.

[0127]

[0128]

[0129] 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 ２５are 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.

[0130]

[0131] As the photopolymerization initiator, among the above, from the viewpoint of resolution, it is preferable to use at least one selected from the group consisting of compounds represented by general formula (9A), compounds represented by general formula (9B), and compounds represented by general formula (10A), it is more preferable to use at least one selected from the group consisting of compounds represented by general formula (9A) and compounds represented by general formula (9B), it is even more preferable to use a compound represented by general formula (9B), and it is particularly preferable to use a compound represented by formula (9B-1).

[0132] The compound represented by formula (9B-1) decomposes upon exposure to i-line, and the decomposition product has a higher i-line transmittance than the compound represented by formula (9B-1) before decomposition. Therefore, when a coating film of the photosensitive resin composition is exposed to i-line, the i-line transmittance is low at the beginning of exposure, suppressing light reflection on the substrate. Then, as exposure irradiation progresses, the i-line transmittance increases, and the i-line reaches the bottom of the coating film close to the substrate. As a result, the rectangularity of the cross-sectional pattern shape is improved, resulting in an excellent pattern shape.

[0133] When the compound represented by formula (10A) is used as the photopolymerization initiator, it is preferable to use a sensitizer described later in combination with the compound, from the viewpoint of adjusting the i-line transmittance of the photosensitive resin film.

[0134] 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.

[0135] (Sensitizer, UV absorber) The photosensitive resin composition may further contain at least one selected from the group consisting of a sensitizer and a UV absorber. By further containing at least one selected from the group consisting of a sensitizer and a UV absorber, the i-line transmittance of the photosensitive resin film may be adjusted.

[0136] [Ultraviolet absorber] The ultraviolet absorber preferably has an absorbance of 0.05 or more, more preferably 0.1 or more, at a concentration of 10 mg / L at 365 nm. Examples of ultraviolet absorbers include benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenyl cyanoacrylate compounds, benzothiazole compounds, azobenzene compounds, polyphenol compounds, and nickel complex salt compounds. The ultraviolet absorbers may be used alone or in combination of two or more.

[0137] 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.

[0138] Examples of salicylic acid ester compounds include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0139] 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.

[0140] Examples of diphenylacrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.

[0141] Examples of diphenyl cyanoacrylate compounds include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).

[0142] Examples of the azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.

[0143] 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 (curcumin), and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.

[0144] Examples of polyphenol compounds include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).

[0145] Among the above, it is preferable to use at least one ultraviolet absorber selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds.

[0146] 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.

[0147] 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.

[0148] [Sensitizer] The photosensitive resin composition of the present disclosure may contain a sensitizer. When the photosensitive resin composition contains a sensitizer, it is possible to maintain both the remaining film rate and good resolution over a wide range of exposure doses.

[0149] 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.

[0150] The sensitizer may be used alone or in combination of two or more. 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.

[0151] (Other Components) The photosensitive resin composition preferably further contains at least one selected from the group consisting of a stabilizer and a solvent. The photosensitive resin composition may also contain a rust inhibitor, an antioxidant, an imidization accelerator, a coupling agent, a thermal polymerization initiator, a surfactant, a leveling agent, an unavoidable component, etc.

[0152] [Solvent] Examples of the solvent include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, etc. The solvents may be used alone or in combination of two or more.

[0153] 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.

[0154] 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.

[0155] Among these, from the viewpoint of excellent solubility of each component and excellent coatability during photosensitive resin film formation, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide and N,N-dimethylacetamide, dimethyl sulfoxide, and the like are preferred.

[0156] Furthermore, as the solvent, a compound represented by the following general formula (11) may be used.

[0157]

[0158] In general formula (11), R ４１ ~R ４３ are each independently an alkyl group having 1 to 10 carbon atoms.

[0159] R in general formula (11) ４１ ~R ４３ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 3, and more preferably 1 or 3. ４１ ~R ４３Specific examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (11) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The compound represented by the formula (11) is preferably 3-methoxy-N,N-dimethylpropanamide (for example, the trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).

[0160] The content of the solvent can be adjusted appropriately depending on the viscosity of the photosensitive resin composition, and may be, for example, 100 parts by mass or more, 200 parts by mass or more, or 400 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 to form a coating film, it is not necessary to contain more solvent than necessary. For example, the content of the solvent relative to 100 parts by mass of the unsaturated polyimide precursor may be less than 100 parts by mass, 75 parts by mass or less, or 50 parts by mass or less.

[0161] From the viewpoint of reducing the environmental load, the proportion of N-methyl-2-pyrrolidone in the total amount of solvents is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably zero (0% by mass).

[0162] [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.

[0163] 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.

[0164] 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.

[0165] 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-hydroxybenzyl) 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-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-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.

[0166] 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.

[0167] [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.

[0168] 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.

[0169] 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.

[0170] Examples of hindered phenol compounds as antioxidants include 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, and 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. lion, 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-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione 1,3,5-tris(4-t-butyl-5,6-diethyl-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-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,Examples include 5-triazine-2,4,6-(1H,3H,5H)-trione and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0171] [Imidization Accelerator] The resin composition of the present disclosure may contain an imidization accelerator from the viewpoint of accelerating the imidization reaction.

[0172] Specific examples of the imidization accelerator include N-phenyldiethanolamine, 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 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.

[0173] 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.

[0174] [Coupling Agent] 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 the coupling agent 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. The coupling agents may be used alone or in combination of two or more.

[0175] 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.

[0176] [Rust inhibitor] The resin composition of the present disclosure may contain a rust inhibitor from the viewpoint of inhibiting corrosion and preventing discoloration of copper and copper alloys. The rust inhibitor is not particularly limited, and examples thereof include azole compounds and purine derivatives. The rust inhibitor may be used alone or in combination of two or more.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] [Surfactant and Leveling Agent] 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.).

[0181] The surfactants and leveling agents may be used alone or in combination of two or more.

[0182] 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.

[0183] [Thermal Polymerization Initiator] The photosensitive resin composition of the present disclosure may further contain a thermal polymerization initiator from the viewpoint of promoting the polymerization reaction. The thermal polymerization initiator is preferably 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. The thermal polymerization initiator is preferably a compound having a decomposition point of 110°C to 200°C, and more preferably a compound having a decomposition point of 110°C to 175°C from the viewpoint of promoting the polymerization reaction at lower temperatures.

[0184] 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).

[0185] 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.

[0186] [Content of Main Component] In the photosensitive resin composition of the present disclosure, the total amount of the unsaturated polyimide precursor, crosslinking agent, photopolymerization initiator, sensitizer, UV absorber, 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, crosslinking agent, photopolymerization initiator, sensitizer, UV absorber, solvent, stabilizer, imidization accelerator, 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.

[0187] <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 can be suitably used as a patterned cured product. The average thickness of the cured product is preferably 5 μm to 20 μm.

[0188] <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.

[0189] The substrate may be a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), or a TiO ２ Substrate, SiO ２ Examples of the substrate include a metal oxide insulator substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0190] 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.

[0191] 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.

[0192] The average thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, and even more preferably 7 μm to 30 μm.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the patterned resin film.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] [Examples 1 to 9 and Comparative Examples 1 to 7] Each component listed in Table 1 or Table 2 was mixed in the amount listed in Table 1 or Table 2 to prepare a uniform solution. The obtained 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 9 and Comparative Examples 1 to 7. The amount of each component listed in Tables 1 and 2 is based on parts by mass. In Tables 1 and 2, "-" means that the corresponding component is not contained. Details of each component listed in Tables 1 and 2 are as follows.

[0210] Synthesis of Polyimide Precursor Polymer 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 then dried under reduced pressure to obtain Polymer I as an unsaturated polyimide precursor. The weight average molecular weight (Mw) of Polymer I was 22,100.

[0211] The weight average molecular weight of the polymer was calculated by gel permeation chromatography (GPC) using a calibration curve based on TSKgel standard polystyrene (Tosoh Corporation). The apparatus and conditions are shown below. The measurement sample was prepared by dissolving 2 mg of 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. 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

[0212] Solvent: I: γ-butyrolactone II: N-methyl-2-pyrrolidone

[0213] Polymerizable Monomers I: Triethylene glycol dimethacrylate (bifunctional) II: Tricyclodecane dimethanol diacrylate (bifunctional) III: Polyethoxylated pentaerythritol tetraacrylate (tetrafunctional) IV: Tris-(2-acryloxyethyl) isocyanurate (trifunctional)

[0214] Photopolymerization initiator I: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime) II: 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone III: 1-phenyl-1,2-propanedione-2-[o-(ethoxycarbonyl)oxime]

[0215] Sensitizer: 4,4'-bis(diethylamino)benzophenone (EMK, Merck) Ultraviolet absorber: curcumin

[0216] (Measurement of i-line transmittance of photosensitive resin film) The obtained photosensitive resin composition was spin-coated onto quartz glass using a coating device, Spin Coater MS-B150 (manufactured by Mikasa Co., Ltd.), and pre-baked by heating at 100°C for 120 seconds and then at 110°C for 120 seconds to produce a photosensitive resin film with a thickness of 7 µm. The transmittance of the obtained photosensitive resin film at i-line (wavelength 365 nm) was measured using a U-3900H spectrophotometer (manufactured by Hitachi High-Tech Science Corporation).

[0217] (Evaluation of Resolution) A photosensitive resin film with a thickness of 7 μm was obtained using the same method as in the measurement of i-line transmittance described above. The development time was set to 1.2 times the time it took for this photosensitive resin film to be immersed in cyclopentanone and completely dissolved. In addition, a photosensitive resin film was prepared using the same method as above, and the obtained photosensitive resin film was exposed to light using an i-line stepper FPA-3000iW (manufactured by Canon Inc.) at an exposure dose of 900 mJ cm. ２ The exposed resin film was puddle developed with cyclopentanone for the above-mentioned developing time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

[0218] The resulting patterned resin film was heated in a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) in a nitrogen atmosphere at 170° C. for 3 hours to obtain a patterned cured product (film thickness after curing: 5 μm).

[0219] The obtained patterned cured product was observed using an optical microscope, and the resolution was defined as the smallest diameter at which an opening was formed that exposed 55% or more of the substrate surface relative to the area of ​​the via mask dimensions. The results are shown in Table 2.

[0220] (Evaluation of post-development residual film ratio (FR)) A photosensitive resin film was obtained in the same manner as in the measurement of i-line transmittance described above. A patterned resin film was also obtained in the same manner as in the evaluation of resolution. The film thickness of the obtained photosensitive resin film (before development) and the patterned resin film (after development) was measured using a needle-contact profiler Dektak 150 (manufactured by Bruker), and the post-development residual film ratio was calculated using the following formula: Post-development residual film ratio (FR) % = film thickness of patterned resin film (after development) / film thickness of photosensitive resin film (before development) × 100

[0221]

[0222]

[0223] As shown in Table 1, using the photosensitive resin compositions of Examples 1 to 5, which contained a polyimide precursor having a polymerizable unsaturated bond and a tri- or higher functional polymerizable monomer and had a photosensitive resin film with an i-line transmittance of 30% or less, via patterns with a diameter of 6 μm or less could be formed. On the other hand, the photosensitive resin compositions of Comparative Examples 3 to 7, which did not contain a tri- or higher functional polymerizable monomer, were unable to form via patterns with a diameter of 6 μm or less. Furthermore, the photosensitive resin compositions of Comparative Examples 1 and 2, which contained a tri- or higher functional polymerizable monomer but had a photosensitive resin film with an i-line transmittance of more than 30%, were also unable to form via patterns with a diameter of 6 μm or less. Note that while solvent I was used in the examples and solvent II in the comparative examples, the solvent was removed by heating before measuring the i-line transmittance and before exposure, so the solvent had little effect on the measurement and evaluation.

[0224] As an example of the formed via pattern, Fig. 2(A) shows a cross-sectional SEM photograph of a via pattern formed using the photosensitive resin composition of Example 1, and Fig. 2(B) shows a cross-sectional SEM photograph of a via pattern formed using the photosensitive resin composition of Comparative Example 1. Note that this cross-sectional SEM photograph was taken after drilling with an ion beam (FIB) so that the cross section of the via pattern could be observed.

[0225] As shown in Fig. 2(A), a pattern with good rectangularity was formed all the way to the bottom in Example 1, whereas as shown in Fig. 2(B), it can be seen that microbridges occurred in Comparative Example 1. Comparative Example 1 contains a tri- or higher functional polymerizable monomer, and the i-line transmittance of the cured product exceeds 30%, which is thought to be why the polymerization reaction proceeded excessively due to i-line reflected by the substrate.

[0226] 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, a polymerizable monomer having three or more functionalities, and a photopolymerization initiator, wherein the photosensitive resin composition is heated at 100°C for 120 seconds and then at 110°C for 120 seconds to produce a 7 μm-thick photosensitive resin film having an i-line transmittance of 30% or less.

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 member selected from the group consisting of sensitizers and ultraviolet absorbers.

4. The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator comprises an oxime compound.

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

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

8. An electronic part comprising the patterned cured product according to claim 6 or 7.

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