Resin composition, cured product, method for producing cured product, and electronic component

Abstract

This resin composition comprises: a polyimide precursor having a polymerizable unsaturated bond; and a crosslinking agent having a polymerizable unsaturated bond, wherein the curing shrinkage rate of said resin composition when heated and cured under the conditions of 170ºC and 2 hours is at most 17%.

Description

Resin composition, cured product, method for producing cured product, and electronic component

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

[0002] Polyimide resins, which combine excellent heat resistance with electrical and mechanical properties, are widely used as materials for resin films used as surface protection films, interlayer insulating films, and the like for elements in semiconductor devices. In recent years, miniaturization and stacking of packaging technologies to protect semiconductor elements have progressed to improve the functionality of electronic devices such as AI (Artificial Intelligence) and smartphones. Furthermore, miniaturization, stacking, and multi-layering of the rewiring layers that make up semiconductor devices are also required. Therefore, photosensitive polyimide materials that can ensure flatness when multi-layered are required as rewiring materials. Furthermore, to improve the performance of electronic devices, components with low heat resistance are sometimes used in semiconductor devices, and there is a demand for reducing the heating temperature (i.e., the curing temperature of the photosensitive polyimide material) when fabricating semiconductor devices. A negative-tone photosensitive resin composition containing a polyamide-imide precursor resin having a specific structure, a photopolymerization initiator, and a solvent has been proposed as a resin composition capable of forming a resin film by patterned exposure (see, for example, Patent Document 1).

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2023-153029

[0004] However, resin films formed using photosensitive polyimide materials sometimes fail to ensure sufficient flatness. The present disclosure has been made in consideration of the above-described conventional circumstances, and an object of one embodiment of the present disclosure is to provide a resin composition capable of forming a resin film with ensured flatness. Another embodiment of the present disclosure is to provide a cured product obtained using the resin composition, a method for producing the cured product, and an electronic component.

[0005] Specific means for achieving the above object are as follows. <1> A resin composition containing a polyimide precursor having a polymerizable unsaturated bond and a crosslinking agent having a polymerizable unsaturated bond, wherein the resin composition has a cure shrinkage of 17% or less when heat-cured at 170°C for 2 hours. <2> The resin composition according to <1>, further containing a thermal polymerization initiator. <3> The resin composition according to <1> or <2>, further containing a photopolymerization initiator. <4> The resin composition according to any one of <1> to <3>, wherein the polyimide precursor has a structural unit represented by the following general formula (1):

[0006]

[0007] (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 groups has a polymerizable unsaturated bond.) <5> The resin composition according to <4>, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E'):

[0008] <6> The resin composition according to <4> or <5>, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H′):

[0009]

[0010] <7> A cured product of the resin composition according to any one of <1> to <6>. <8> A method for producing a cured product, the method comprising the steps of forming a layer of the resin composition according to any one of <1> to <6> on a substrate and curing the layer of the resin composition. <9> An electronic component comprising a cured product of the resin composition according to any one of <1> to <6>.

[0011] According to one embodiment of the present disclosure, there is provided a resin composition capable of forming a resin film with ensured flatness. According to another embodiment of the present disclosure, there are provided a cured product obtained using the resin composition, a method for producing the cured product, and an electronic component.

[0012] 1A and 1B are diagrams illustrating a manufacturing process of an electronic component according to an embodiment of the present disclosure; FIG. 1C shows a cross-sectional SEM image of a flatness evaluation substrate produced using the resin composition of Example 15; and FIG. 1D shows a cross-sectional SEM image of a flatness evaluation substrate produced using the resin composition of Comparative Example 4.

[0013] Modes for carrying out the present disclosure are described in detail below. However, the present disclosure is not limited to the following embodiments. In the present disclosure, components (including elementary steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure. 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 the 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 numerical range described in stages. Furthermore, in the 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 a composition contains multiple substances corresponding to each component, 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 this disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire area when the layer or film is observed, as well as cases where the layer or film is formed only over a portion of the area. In this disclosure, the thickness of a layer or film is determined by measuring the thickness at five points on the layer or film in question and calculating the arithmetic mean value. The thickness of a layer or film can be measured using an optical interference film thickness measuring device or the like. In this disclosure, if 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.

[0014] In the present disclosure, "(meth)acryloyl" means "acryloyl" and "methacryloyl". In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms of the substituent. When embodiments are described in the present disclosure with reference to drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each drawing are conceptual, and the relative size relationships between the components are not limited to these.

[0015] <Resin Composition> The resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond and a crosslinking agent having a polymerizable unsaturated bond. When the resin composition is heat-cured at 170°C for 2 hours, the curing shrinkage is 17% or less. The resin composition of the present disclosure enables the formation of a resin film with ensured flatness. Although the reason for this is unclear, curing the polyimide precursor generally imidizes the polyimide precursor, causing the resin film to shrink during curing. If the curing shrinkage during resin film formation is large, when the resin film is formed on an uneven surface, such as a substrate or resin film provided with vias, slits, metal wiring, etc., the resin film is likely to have poor flatness due to the surface unevenness. Forming metal wiring on a resin film with an uneven surface can result in pattern defects. After extensive research, the inventors discovered that the flatness of the resin film can be ensured by reducing the curing shrinkage to 17% or less, and thus completed the present invention.

[0016] In the present disclosure, the cure shrinkage of the resin composition refers to a value obtained by the method described in the Examples. The cure shrinkage of the resin composition is preferably 15% or less, more preferably 13% or less, even more preferably 10% or less, and particularly preferably 8% or less. The cure shrinkage of the resin composition may be 0% or more.

[0017] Each component contained in the resin composition of the present disclosure will be described below. The resin composition of the present disclosure is preferably a negative photosensitive resin composition (i.e., a resin composition that forms a pattern by removing unexposed areas).

[0018] (Unsaturated Polyimide Precursor) The resin composition of the present disclosure contains an unsaturated polyimide precursor. Examples of the polymerizable unsaturated bond contained in the unsaturated polyimide precursor include a carbon-carbon double bond.

[0019] The unsaturated polyimide precursor preferably has a structural unit represented by the following general formula (1): This tends to give a cured product that exhibits high reliability.

[0020]

[0021] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group; R ６ and R ７ The unsaturated polyimide precursor may have a plurality of structural units represented by the general formula (1), and X, Y, and 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, and R ６ and R ７ As described above, when the unsaturated polyimide precursor has a plurality of structural units represented by the general formula (1), the R 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 one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, 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 represent 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 these, a group represented by the following formula (E) is preferred 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. C in formula (E) 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(RＢ ) 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. C is preferably a group containing 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 a cured product 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 single bond or a group containing an ether bond, even more preferably a group containing an ether bond, and particularly 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 comprising at least two of them in combination. 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 preferably represents 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 where X is a group represented by formula (E) and Y is a group represented by formula (H) A combination where X is a group represented by formula (F) and Y is a group represented by formula (H) A combination where X is a group represented by formula (E) and Y is a group represented by formulas (G) and (H) A combination where X is a group represented by formulas (A) and (E) and Y is a group represented by formula (H) A combination where X is a group represented by formulas (E) and (F) and Y is a group represented by formula (H) The tetravalent organic group represented by X in general formula (1) is preferably a group represented by formula (E') below. The divalent organic group represented by Y in general formula (1) is preferably a group represented by formula (H') below. Among the above combinations, a combination in which X is a group represented by formula (E) and Y is a group represented by formula (H) is preferred, and a combination in which X is a group represented by the following formula (E') and Y is a group represented by the following formula (H') is more preferred.

[0046]

[0047] 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 a polymerizable unsaturated bond, more preferably a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). In this case, R ６ and R ７At least one of the above is a group represented by general formula (2). When the monovalent organic group contains an organic group having a polymerizable unsaturated bond, preferably a group represented by the following general formula (2), the i-line transmittance is high, and a good cured product tends to be formed even when cured at a low temperature of 400°C or less. Furthermore, when the monovalent organic group contains an organic group having a polymerizable unsaturated bond, preferably a group represented by the following general formula (2), at least a portion of the polymerizable unsaturated bond moiety is eliminated by imidization.

[0048] 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.

[0049]

[0050] 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.

[0051] R in general formula (2) ８ ~R １０ The carbon number of the aliphatic hydrocarbon group represented by R is 1 to 3, and 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.

[0052] 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.

[0053] 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.

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

[0055] 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 more than 0 mol% and less than 60 mol%.

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

[0057]

[0058] 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.

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

[0060] 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%.

[0061] 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.

[0062] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic 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.

[0063] 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.

[0064] 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 above is a monovalent organic group can be obtained, for example, by the following method (a) or (b): (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R—OH in an organic solvent to form a diester derivative, and then the diester derivative and H ２ N-Y-NH ２ (b) A condensation reaction is carried out between a tetracarboxylic acid dianhydride and a diamine compound represented by the formula: ２ N-Y-NH ２ In an organic solvent, a polyamic acid solution is obtained by reacting a diamine compound represented by the formula: R--OH with the polyamic acid solution, and the compound represented by R--OH is added to the polyamic acid solution and reacted in the organic solvent to introduce an ester group.

[0065] R in general formula (1) ６ and R ７ Since 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.

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

[0067] 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).

[0068] 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 H ２ N-Y-NH ２The compound can be obtained by reacting a diamine compound represented by the following formula with a diester derivative.

[0069] 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:

[0070]

[0071] 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.

[0072] 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.

[0073] The molecular weight of the unsaturated polyimide precursor is not particularly limited, and for example, the weight-average molecular weight is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 10,000 to 50,000. The weight-average molecular weight of the unsaturated polyimide precursor can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

[0074] The resin composition of the present disclosure may further contain a dicarboxylic acid. The unsaturated polyimide precursor contained in the 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 of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acryloyl 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 of the dicarboxylic acid, methacrylic groups derived from the dicarboxylic acid can be introduced into the unsaturated polyimide precursor.

[0075]

[0076] (Polyimide Resin) The 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 cyclization during imide ring formation, and therefore the generation of voids tends to be suppressed. 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 is soluble in the solvent contained in the resin composition.

[0077] 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.

[0078]

[0079] 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).

[0080] When the resin composition contains an unsaturated polyimide precursor and 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.

[0081] The resin composition of the present disclosure may contain other resins that do not fall under the category of unsaturated polyimide precursors and polyimide resins as resin components. Examples of other resins include, from the viewpoint of heat resistance, novolac resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, and polyvinyl chloride resins. The other resins may be used alone or in combination of two or more.

[0082] In the resin composition, the content of the unsaturated polyimide precursor relative to the total amount of resin components 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.

[0083] (Crosslinking Agent) The resin composition of the present disclosure contains a crosslinking agent having a polymerizable unsaturated bond. The crosslinking agent may be used alone or in combination of two or more. Examples of the polymerizable unsaturated bond contained in the crosslinking agent include a carbon-carbon double bond.

[0084] The crosslinking agent may be a compound having two or more groups containing a polymerizable unsaturated bond (hereinafter also referred to as functional groups) in one molecule. From the viewpoint of polymerization reactivity, the functional group is preferably a (meth)acryloyl group or a vinyl group, and more preferably a (meth)acryloyl group.

[0085] Examples of bifunctional crosslinking agents include allyl methacrylate, 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, trimethylolpropane diacrylate, tricyclodecane dimethanol diacrylate, and tricyclodecane dimethanol dimethacrylate.

[0086] Examples of trifunctional crosslinking agents include trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, tris-(2-acryloxyethyl)isocyanurate, and tris-(2-methacryloxyethyl)isocyanurate.

[0087] Examples of tetrafunctional or higher crosslinking agents include pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tetrakisacrylate tetrayltetrakis(methyleneoxyethylene), and 1,3,4,6-tetraallyl glycoluril.

[0088] In one embodiment, the content of the crosslinking agent is preferably 1 part by mass to 50 parts by mass, more preferably 3 parts by mass to 50 parts by mass, and even more preferably 5 parts by mass to 40 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor. In another embodiment, the content of the crosslinking agent may be adjusted so that the ratio (B / A) of the number A of polymerizable unsaturated bonds in the unsaturated polyimide precursor contained in the resin composition to the number B of polymerizable unsaturated bonds in the crosslinking agent contained in the resin composition is in the range of 0.2 to 1.4.

[0089] (Ratio (B / A)) In the present disclosure, the ratio (B / A) of the number A of polymerizable unsaturated bonds in the unsaturated polyimide precursor contained in the resin composition to the number B of polymerizable unsaturated bonds in the crosslinking agent contained in the resin composition may be 0.2 or more, 0.3 or more, or 0.35 or more, from the viewpoint of suppressing cure shrinkage. Furthermore, the ratio (B / A) may be 1.4 or less, 1.1 or less, or 0.8 or less, from the viewpoint of high-resolution photosensitive characteristics (i.e., the ability to form patterns with small opening dimensions). In the present disclosure, the number A can be obtained by dividing the content (in grams) of the unsaturated polyimide precursor contained in the resin composition by the formula weight of the structural unit constituting the unsaturated polyimide precursor, and multiplying the result by the number of polymerizable unsaturated bonds contained in the structural unit. In the present disclosure, the number B can be obtained by dividing the content (in grams) of the crosslinking agent contained in the resin composition by the molecular weight of the crosslinking agent, and multiplying the result by the number of polymerizable unsaturated bonds contained in one molecule of the crosslinking agent.

[0090] <Other Components> The resin composition of the present disclosure may further include components other than the unsaturated polyimide precursor and the crosslinking agent. For example, the resin composition may include a thermal polymerization initiator, a metal chelating agent, a photopolymerization initiator, a stabilizer, a sensitizer, an ultraviolet absorber, a rust inhibitor, an antioxidant, a solvent, etc., which will be described later.

[0091] (Thermal Polymerization Initiator) The resin composition of the present disclosure may contain a thermal polymerization initiator from the viewpoint of improving the physical properties of the cured product. The thermal polymerization initiator may be used alone or in combination of two or more. The resin composition of the present disclosure may contain a thermal polymerization initiator having a one-minute half-life of 120°C to 190°C (preferably 130°C to 190°C, more preferably 140°C to 180°C) as the thermal polymerization initiator. When two or more thermal polymerization initiators are used in combination, the proportion of the thermal polymerization initiators having a one-minute half-life of 120°C to 190°C in the thermal polymerization initiator is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The one-minute half-life of the thermal polymerization initiator is determined by iodometric titration. When a commercially available thermal polymerization initiator is used, the catalog value provided by the manufacturer may be used.

[0092] Specific examples of the thermal polymerization initiator include t-butylperoxy 2-ethylhexyl monocarbonate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, and 2,2'-azobisbutyronitrile.

[0093] When the 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 15 parts by mass, more preferably 1 part by mass to 10 parts by mass, and even more preferably 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0094] (Metal Chelating Agent) The resin composition of the present disclosure may contain a metal chelating agent from the viewpoint of forming a three-dimensional crosslinked structure with the unsaturated polyimide precursor and further reducing the cure shrinkage rate. Examples of the metal chelating agent contained in the resin composition include a titanium chelating agent, a zirconium chelating agent, and an aluminum chelating agent. The metal chelating agent may be used alone or in combination with two or more types. Among these, a titanium chelating agent is preferred as the metal chelating agent from the viewpoint of compatibility with the polyimide and the unsaturated polyimide precursor.

[0095] Specific examples of titanium chelating agents include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, dodecylbenzenesulfonic acid titanium compounds, phosphate ester titanium complexes, titanium octylene glycolate, and titanium ethylacetoacetate.Specific examples of zirconium chelating agents include zirconium tetraacetylacetonate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium tetraacetylacetonate, and zirconium ethylacetoacetate.Specific examples of aluminum chelating agents include aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum trisethylacetoacetate.

[0096] When the resin composition of the present disclosure contains a metal chelating agent, the content of the metal chelating agent contained in the resin composition is preferably 0.1 to 10 parts by mass per 100 parts by mass of the unsaturated polyimide precursor. When the resin composition of the present disclosure contains a metal chelating agent, the content of the metal chelating agent contained in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more per 100 parts by mass of the unsaturated polyimide precursor. When the resin composition of the present disclosure contains a metal chelating agent, the content of the metal chelating agent contained in the resin composition is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less per 100 parts by mass of the unsaturated polyimide precursor. The proportion of the titanium chelating agent in the metal chelating agent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The proportion of the titanium chelating agent in the metal chelating agent may be 100% by mass.

[0097] (Photopolymerization initiator) The resin composition of the present disclosure may contain a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more. From the viewpoints of excellent exposure sensitivity and suppressing the occurrence of voids during bonding, it is preferable to contain an oxime-based photopolymerization initiator as the photopolymerization initiator. Specific examples of oxime-based photopolymerization initiators include 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, and 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime. , 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime), O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, 1-[4-(4-hydroxyethyloxy-phenylthio)phenyl]-1,2-propanedione-2-(O-acetyloxime), and the like.

[0098] When the resin composition contains a photopolymerization initiator, the total amount of the photopolymerization initiator is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 20 parts by mass, and even more preferably 5 parts by mass to 20 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0099] (Stabilizer) The resin composition of the present disclosure may contain a stabilizer. The stabilizers may be used alone or in combination of two or more.

[0100] 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.

[0101] When the resin composition 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, per 100 parts by mass of the unsaturated polyimide precursor.

[0102] (Sensitizer) The resin composition of the present disclosure may contain a sensitizer. The sensitizer may be used alone or in combination of two or more. Specific examples of the sensitizer include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone derivatives.

[0103] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0104] (Ultraviolet Absorber) The resin composition of the present disclosure may contain an ultraviolet absorber. When the resin composition contains an ultraviolet absorber, crosslinking of unexposed areas due to diffuse reflection during exposure tends to be suppressed.

[0105] Examples of the ultraviolet absorber include benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, diphenylacrylate-based compounds, cyanoacrylate-based compounds, diphenylcyanoacrylate-based compounds, benzothiazole-based compounds, azobenzene-based compounds, polyphenol-based compounds, nickel complex salt-based compounds, etc. The ultraviolet absorbers may be used alone or in combination of two or more.

[0106] When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 3 parts by mass, and even more preferably 0.2 parts by mass to 2 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0107] (Rust inhibitor) The resin composition of the present disclosure may contain a rust inhibitor from the viewpoint of inhibiting corrosion of metals such as copper and copper alloys and inhibiting discoloration of the metals. Examples of the rust inhibitor include azole compounds and purine derivatives. The rust inhibitor may be used alone or in combination of two or more.

[0108] 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.

[0109] 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.

[0110] When the resin composition 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.

[0111] (Antioxidant) The resin composition of the present disclosure may contain an antioxidant. The antioxidants may be used alone or in combination of two or more.

[0112] Specific examples of the antioxidant include hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0113] When the resin composition contains an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.

[0114] (Solvent) The resin composition of the present disclosure may contain a solvent. The solvent may be used alone or in combination of two or more. Specific examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone; and sulfoxides such as dimethyl sulfoxide.

[0115] When the resin composition contains a solvent, the content of the solvent is preferably 10 parts by mass to 10,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, and even more preferably 100 parts by mass to 500 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.

[0116] [Content of Main Component] In the resin composition of the present disclosure, the total content of the unsaturated polyimide precursor, the crosslinking agent, and the thermal polymerization initiator, metal chelating agent, photopolymerization initiator, stabilizer, and solvent that are used as needed may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.

[0117] <Cured Product> The cured product of the present disclosure can be obtained by curing the resin composition of the present disclosure. When the resin composition of the present disclosure is photosensitive, the cured product of the present disclosure can be obtained by exposing the resin composition to light and then heat-treating it. Examples of methods for imparting photosensitivity to a resin composition include a method of adding a photocurable component such as a photopolymerization initiator to the resin composition. 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.

[0118] <Method for Producing Cured Product> A method for producing a cured product according to the present disclosure includes the steps of forming a layer of the resin composition according to the present disclosure on a substrate and curing the layer of the resin composition.

[0119] The method for forming a layer of the resin composition on a substrate (hereinafter also referred to as a resin composition layer) is not particularly limited. For example, the method may involve applying the resin composition to the substrate using a spinner or the like, and drying it using a hot plate, an oven, or the like.

[0120] 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 insulating substrate, a silicon nitride substrate, a copper substrate, a copper alloy substrate, etc. The surface of the substrate on which the resin composition layer is formed may be made of two or more different materials.

[0121] The average thickness of the resin composition layer formed on the substrate is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, and even more preferably 7 μm to 30 μm.

[0122] The method for curing the resin composition layer formed on the substrate is not particularly limited. When the resin composition is photosensitive, the resin composition layer may be cured by exposure (and, if necessary, heat treatment after exposure). Exposure may be performed by pattern exposure (a method of performing exposure in a pattern consisting of exposed and unexposed areas). Pattern exposure is performed, for example, by exposing in a predetermined pattern through a photomask. Examples of actinic rays used for exposure include ultraviolet rays such as i-rays, visible light, and radiation, with i-rays being preferred. Examples of exposure devices that can be used include parallel exposure machines, aligners, projection exposure machines, steppers, scanner exposure machines, and the like.

[0123] A patterned resin film (patterned resin film) can be obtained by developing the exposed resin composition layer. Generally, when a negative-tone photosensitive resin composition is used, the unexposed areas are removed with a developer. As the developer, a good solvent for the resin film can be used alone, or an appropriate mixture of a good solvent and a poor solvent can be used. The developed patterned resin film may be washed with a rinse solution. 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.

[0124] The developed resin film may be subjected to a heat treatment (post-baking) to obtain a patterned cured product. By performing the heat treatment, for example, an unsaturated polyimide precursor contained in the developed resin film undergoes a dehydration ring-closing reaction to form a polyimide resin.

[0125] 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.

[0126] The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. 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.

[0127] 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.

[0128] The cured product of the present disclosure can be used, for example, as a resin film, specifically, a passivation film, a buffer coat film, an interlayer insulating film, a cover coat film, a surface protection film, etc.

[0129] <Electronic Component> The electronic component of the present disclosure includes the cured product of the present disclosure described above. The electronic component includes, for example, the cured product of the present disclosure as a resin film. Specific examples of the electronic component include semiconductor devices, various electronic devices, and stacked devices (such as multi-die fan-out wafer-level packages). In the electronic component, the member in contact with the cured product of the present disclosure may be made of two or more materials (for example, silicon and metal).

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] Next, the 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 resin composition of the present disclosure.

[0135] 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.

[0136] (Synthesis of Unsaturated Polyimide Precursor A-1) 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, Ltd.) was added and dissolved, and 5.54 g (42.6 mmol) of 2-hydroxyethyl methacrylate (HEMA, Fujifilm Wako Pure Chemical Industries, Ltd.) was added. This mixture was stirred at 30°C for 1 hour to obtain a reaction solution.

[0137] 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, 73.1 g (348 mmol) of TFAA (trifluoroacetic anhydride, Fujifilm Wako Pure Chemical Industries Co., 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 Co., 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. The collected precipitate was washed with purified water and then dried under reduced pressure to obtain a polyimide precursor having a polymerizable unsaturated bond. The weight average molecular weight (Mw) of the obtained polyimide precursor was 47,000.

[0138] The weight-average molecular weight of the polyimide precursor 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

[0139] (Synthesis of Unsaturated Polyimide Precursor A-2) Unsaturated Polyimide Precursor A-2 was synthesized in the same manner as Unsaturated Polyimide Precursor A-1, except that the amount of TFAA was changed to 65.6 g (312 mmol). The Mw of Unsaturated Polyimide Precursor A-2 was 40,000.

[0140] (Synthesis of Unsaturated Polyimide Precursor A-3) Unsaturated Polyimide Precursor A-3 was synthesized in the same manner as Unsaturated Polyimide Precursor A-1, except that the amount of TFAA was changed to 55.5 g (264 mmol). The Mw of Unsaturated Polyimide Precursor A-3 was 30,000.

[0141] (Synthesis of Unsaturated Polyimide Precursor A-4) Unsaturated Polyimide Precursor A-4 was synthesized in the same manner as Unsaturated Polyimide Precursor A-1, except that the amount of DMAP was changed to 24.2 g (114 mmol). The Mw of Unsaturated Polyimide Precursor A-4 was 15,000.

[0142] (Synthesis of Unsaturated Polyimide Precursor A-5) Unsaturated Polyimide Precursor A-5 was synthesized in the same manner as Unsaturated Polyimide Precursor A-1, except that DMAP was changed to 22.8 g (114 mmol) of 4,4-diaminodiphenyl ether (ODA). The Mw of Unsaturated Polyimide Precursor A-5 was 34,000.

[0143] (Preparation of Resin Compositions) Resin compositions of Examples 1 to 23 and Comparative Examples 1 to 7 were prepared using the components and blending amounts shown in Tables 1 and 2. Specifically, a mixture of each component was kneaded overnight at room temperature (25°C) in a typical solvent-resistant container, and then pressure filtered using a 0.2 μm pore filter to obtain a resin composition. The blending amount of each component in Tables 1 and 2 is expressed in parts by mass. Furthermore, number A and number B were determined according to the method described above, and the ratio (B / A) was calculated. The results are shown in Tables 1 and 2.

[0144] The components in Tables 1 and 2 are as follows. GBL: γ-butyrolactone Crosslinker 1: triethylene glycol dimethacrylate Crosslinker 2: tricyclodecane dimethanol diacrylate Crosslinker 3: tris-(2-acryloxyethyl) isocyanurate Crosslinker 4: ethoxylated pentaerythritol tetraacrylate Crosslinker 5: 1,3,4,6-tetraallyl glycoluril Thermal polymerization initiator 1: dicumyl peroxide (one-minute half-life: 175°C) Thermal polymerization initiator 2: di(2-t-butylperoxyisopropyl)benzene (one-minute half-life: 175°C) Thermal polymerization initiator 3: t-butylperoxy 2-ethylhexyl monocarbonate (one-minute half-life: 161°C) Thermal polymerization initiator 4: t-hexyl peroxypivalate (one-minute half-life: 110°C) Thermal polymerization initiator 5: p-menthane hydroperoxide (one-minute half-life: 200°C) Photopolymerization initiator: 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) Metal chelating agent: titanium diisopropoxybis(ethylacetoacetate)

[0145] (Cure Shrinkage Evaluation) The obtained resin composition was spin-coated onto a 6-inch silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100°C for 120 seconds, and then dried (pre-baked) at 110°C for 120 seconds to form a resin film with a dry film thickness of 10 μm. The rotation conditions for spin coating were a fixed rotation time of 30 seconds, and the rotation speed was adjusted so that the dry film thickness would be 10 μm. In this evaluation, the range was 1000 rpm to 3000 rpm. The obtained resin film was immersed in cyclopentanone, and the development time was set to 1.2 times the time until the resin film was completely dissolved. In addition, a resin film was prepared in the same manner as above, and the obtained resin film was irradiated with 100 mJ / cm using an i-line stepper FPA-3000iW (manufactured by Canon Inc.). ２ ~1100mJ / cm ２ i-line at 100 mJ / cm ２The resin film was exposed by irradiating it with an exposure dose in increments. The exposed resin film was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a resin film. The development time was set to 1.2 times the time it took for the resin film to completely dissolve when the obtained resin film was immersed in cyclopentanone without exposure. The resin film was then heat-treated at 170°C for 2 hours to obtain a cured film. The exposure dose was 500 mJ / cm. ２ The cure shrinkage at this time was calculated using the following formula. The results are shown in Tables 1 and 2. Cure shrinkage (%) = (1 - (film thickness after curing) / (film thickness after development)) x 100 Film thickness was measured using an optical interference film thickness measuring device (VM-2200, manufactured by SCREEN). Film thickness measurements were carried out at five random locations.

[0146] (Flatness Evaluation) Using the resin compositions of Example 15 and Comparative Example 4, flatness evaluation substrates were prepared by the following method. The obtained resin composition of Example 15 was spin-coated onto a 6-inch silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100°C for 120 seconds, and then dried (pre-baked) at 110°C for 120 seconds to form a resin film with a dry film thickness of 11.5 μm. The rotation conditions for spin coating were a fixed rotation time of 30 seconds, and the rotation speed was adjusted so that the dry film thickness would be 11.5 μm. In this evaluation, the range was 1000 rpm to 2000 rpm. The obtained resin film was immersed in cyclopentanone, and the development time was set to 1.2 times the time until the resin film was completely dissolved. Furthermore, a resin film was prepared in the same manner as above, and the obtained resin film was irradiated with 500 mJ / cm using an i-line stepper FPA-3000iW (manufactured by Canon Inc.). ２The i-line was irradiated through a line and space (line 30 μm, space 10 μm) mask for exposure. The exposed resin film was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a line and space (line 30 μm, space 10 μm) patterned resin film. The patterned resin film was then heat-treated at 170°C for 2 hours to obtain a cured film. Platinum was vapor-deposited on the surface of this cured film using a magnetron sputtering apparatus (MSP8in) manufactured by Vacuum Device Co., Ltd. (vapor deposition conditions: pressure inside the apparatus: 1 Pa, discharge current: 200 mA). The resin composition of Example 15 or Comparative Example 4 was spin-coated onto the cured film after platinum deposition using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100°C for 120 seconds, and then dried (pre-baked) at 110°C for 120 seconds to form a resin film with a dry thickness of 9.0 μm to 11.5 μm. The entire surface of this cured film was exposed to 500 mJ of light using an MA-8 manufactured by SUSS MicroTec without a mask. The exposed cured film was then heat-treated at 170°C for 2 hours to obtain a cured film. The amount of depressions in the cured film formed on the lines and spaces of the obtained cured film was measured by observing the cross section of the sample using a scanning electron microscope (SEM) device (SU3500) manufactured by Hitachi High-Tech Corporation (SEM acceleration voltage: 5.0 kV, imaging magnification: 2500x). FIG. 2 shows a cross-sectional SEM photograph of a flatness evaluation substrate produced using the resin composition of Example 15, and FIG. 3 shows a cross-sectional SEM photograph of a flatness evaluation substrate produced using the resin composition of Comparative Example 4. In the flatness evaluation substrate produced using the resin composition of Example 15, the thickness of the resin film measured from the surface of the substrate at the location where a 10 μm wide groove was provided was 16.4 μm. The depth of the recess in the resin film was 1.6 μm. In the flatness evaluation substrate produced using the resin composition of Comparative Example 4, the thickness of the resin film measured from the surface of the substrate at the location where a 10 μm wide groove was provided was 14.6 μm. The depth of the recess in the resin film was 3.4 μm. The smaller the depth of the recess in the resin film, the more preferable.

[0147]

[0148]

[0149] The depth of the recesses in the resin film for the resin composition of Example 15, which had a cure shrinkage rate of 8%, was 1.6 μm, indicating excellent flatness. From this, it can be inferred that the resin compositions of other Examples, which had a cure shrinkage rate of 17% or less, also had excellent flatness of the resin film. On the other hand, the depth of the recesses in the resin film for the resin composition of Comparative Example 4, which had a cure shrinkage rate of 25%, was 3.4 μm, indicating poor flatness. From this, it can be inferred that the resin compositions of other Comparative Examples, which had a cure shrinkage rate of more than 17%, also had poor flatness of the resin film.

Claims

1. A resin composition containing a polyimide precursor having a polymerizable unsaturated bond and a crosslinking agent having a polymerizable unsaturated bond, wherein the curing shrinkage rate when the resin composition is heat-cured at 170°C for 2 hours is 17% or less.

2. The resin composition according to claim 1, further comprising a thermal polymerization initiator.

3. The resin composition according to claim 1, further comprising a photopolymerization initiator.

4. The resin composition according to claim 1, wherein the polyimide precursor has a structural unit represented by the following general formula (1): (In general formula (1), X represents a tetravalent organic group, 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 groups has a polymerizable unsaturated bond.

5. The resin composition according to claim 4, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E'):

6. The resin composition according to claim 4, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H'):

7. A cured product of the resin composition according to any one of claims 1 to 6.

8. A method for producing a cured product, comprising the steps of forming a layer of the resin composition according to any one of claims 1 to 6 on a substrate, and curing the layer of the resin composition.

9. An electronic part comprising a cured product of the resin composition according to any one of claims 1 to 6.

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