Resin composition

Abstract

To provide a resin composition or the like which gives a cured product having a low linear thermal expansion coefficient, high elongation at break, and excellent crack resistance.SOLUTION: The resin composition contains (A) an epoxy resin, (B) a catechol-based curing agent, and (C) an inorganic filler. The content of the component (C) is 50 mass% or more based on 100 mass% of a nonvolatile component in the resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition. The present invention further relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition, and a catechol-based resin. [Background technology]

[0002] Printed wiring boards are generally provided with an insulating layer, which is formed by curing a resin composition. Known examples of such resin compositions include the resin composition disclosed in Patent Document 1. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-66792 Summary of the Invention [Problem to be solved by the invention]

[0004] The insulating layer of a printed wiring board is required to have a low coefficient of linear thermal expansion to reduce warpage. Furthermore, as electronic components become smaller and more highly functional, insulating layers are becoming thinner, making them more susceptible to cracking and other defects. To prevent this, insulating layers are required to have excellent mechanical properties, specifically, excellent elongation at break and crack resistance.

[0005] The present invention aims to provide a resin composition that provides a cured product having a low coefficient of linear thermal expansion, high elongation at break, and excellent crack resistance; a resin sheet having a resin composition layer that includes the resin composition; a printed wiring board that includes an insulating layer formed from a cured product of the resin composition; a semiconductor device that includes the printed wiring board; and a catechol-based resin. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using a compound having a specific structure, and have thus completed the present invention.

[0007] That is, the present invention includes the following. [1] (A) epoxy resin, (B) a catechol-based curing agent, and (C) a resin composition comprising an inorganic filler, A resin composition, wherein the content of component (C) is 50% by mass or more when the total nonvolatile components in the resin composition is 100% by mass. [2] The resin composition according to [1], further comprising (D) a curing agent (excluding those corresponding to component (B)). [3] The resin composition according to [1] or [2], wherein the component (B) has one or more catechol structures. [4] The resin composition according to any one of [1] to [3], wherein the component (B) comprises any one of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3): [ka] In formula (B-1), R 11 each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R 12 each independently represents a single bond or a divalent hydrocarbon group which may have a substituent, and R 12 may be bonded to the benzene ring in formula (B-1) to form a ring. 13 each independently represents an amide bond, a carbonyl group, -C(=O)O-, -OC(=O)O-, -O-, or -NR a -, or a divalent group selected from the group consisting of two or more thereof; R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 14 represents a k-valent hydrocarbon group having 2 to 100 carbon atoms which may have a heteroatom, and k represents an integer of 1 to 5. In formula (B-2), R 21 , and R 23 each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R 22 represents a divalent hydrocarbon group which may have a substituent, and R 22 may be bonded to the benzene ring in formula (B-2) to form a ring. In formula (B-3), R 31 represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; ring B represents a ring structure condensed with the benzene ring in formula (B-3); R 32 each independently represents an aryl group which may have a substituent, or an alkyl group which may have a substituent. 1 represents an integer of 0 to 2. [5] R in formula (B-1) 11 , R in formula (B-2) 21 , and R 23 and R in formula (B-3) 31 represents a hydrogen atom or a hydroxy group. [6] R in formula (B-1) 13 are each independently -NR a -C(=O)-, -C(=O)-NR a -, -OC(=O)-, -C(=O)-O-, -NR a -C(=O)-O-, -OC(=O)-NR a - or -O-, and -NR a -C(=O)-, -C(=O)-NR a -, -C(=O)-O-, or -NR a The resin composition according to [4] or [5], [7] R in formula (B-1) 12 The resin composition according to any one of [4] to [6], wherein represents a single bond, an alkylene group which may have a substituent, or an alkenylene group which may have a substituent. [8] In formula (B-2), R 22represents an alkylene group which may have a substituent, and the alkylene group may be bonded to the benzene ring in formula (B-2) to form a ring. The resin composition according to any one of [4] to [7]. [9] R in formula (B-1) 14 The resin composition according to any one of [4] to [8], wherein represents a divalent to pentavalent hydrocarbon group having 2 to 100 carbon atoms which may have a heteroatom.

[10] The resin composition according to any one of [4] to [9], wherein k in formula (B-1) represents an integer of 1 to 3.

[11] The resin composition according to any one of [4] to

[10] , wherein ring B in formula (B-3) is any one of a δ-valerolactone structure, a 4-oxy-2-cyclohexenone structure, and a 2-oxy-5-cyclohexenone structure.

[12] The resin composition according to any one of [1] to

[11] , which is used to form an insulating layer.

[13] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to

[12] .

[14] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to

[12] .

[15] A semiconductor device comprising the printed wiring board according to

[14] .

[16] A catechol-based resin containing any one of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3). [ka] In formula (B-1), R 11 each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R 12 each independently represents a single bond or a divalent hydrocarbon group which may have a substituent, and R 12 may be bonded to the benzene ring in formula (B-1) to form a ring. 13 each independently represents an amide bond, a carbonyl group, -C(=O)O-, -OC(=O)O-, -O-, or -NRa -, or a divalent group selected from the group consisting of two or more thereof; R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 14 represents a k-valent hydrocarbon group having 2 to 100 carbon atoms which may have a heteroatom, and k represents an integer of 1 to 5. In formula (B-2), R 21 , and R 23 each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R 22 represents a divalent hydrocarbon group which may have a substituent, and R 22 may be bonded to the benzene ring in formula (B-2) to form a ring. In formula (B-3), R 31 represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; ring B represents a ring structure condensed with the benzene ring in formula (B-3); R 32 each independently represents an aryl group which may have a substituent, or an alkyl group which may have a substituent. 1 represents an integer of 0 to 2. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition that provides a cured product having a low linear thermal expansion coefficient, high elongation at break, and excellent crack resistance; a resin sheet having a resin composition layer that includes the resin composition; a printed wiring board that includes an insulating layer formed from a cured product of the resin composition; a semiconductor device that includes the printed wiring board; and a catechol-based resin. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is an IR chart of the catechol-based resin (1). [Figure 2] FIG. 2 is a 1H-NMR chart (heavy solvent: deuterated methanol) of the catechol-based resin (1). [Figure 3]FIG. 3 is a 1H-NMR chart of the catechol-based resin (1) (heavy solvent: deuterated dimethyl sulfoxide). DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0011] As used herein, the term "optionally substituted" in reference to a compound or group means both a case where the hydrogen atoms of the compound or group are not substituted with substituents, and a case where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0012] In this specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group.

[0013] Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0014] The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0015] The number of carbon atoms in the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0016] The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

[0017] The alkenyl group used as a substituent is a monovalent unsaturated hydrocarbon group having one carbon-carbon double bond, and may be either linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 6. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

[0018] The number of carbon atoms in the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0019] The aryl group used as a substituent is a group in which one hydrogen atom on the aromatic ring has been removed from an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

[0020] The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

[0021] The number of carbon atoms in the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkyl group include phenyl-C1-C 12 Alkyl groups, naphthyl-C1-C 12 Alkyl groups and anthracenyl-C1-C 12 Examples of suitable alkyl groups include:

[0022] The number of carbon atoms in the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C1-C 12 Alkoxy group, and naphthyl-C1-C 12 Examples include alkoxy groups.

[0023] The monovalent heterocyclic group used as a substituent refers to a group in which one hydrogen atom has been removed from the heterocycle of a heterocyclic compound. The number of carbon atoms in the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and even more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocycle include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.

[0024] The alkylidene group used as a substituent refers to a group in which two hydrogen atoms have been removed from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a sec-butylidene group, an isobutylidene group, a tert-butylidene group, a pentylidene group, a hexylidene group, a heptylidene group, an octylidene group, a nonylidene group, and a decylidene group.

[0025] The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

[0026] The acyloxy group used as a substituent refers to a group represented by the formula: -OC(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

[0027] The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

[0028] Before describing the resin composition of the present invention in detail, the "catechol-based resin" that can be used in the resin composition of the present invention will be described.

[0029] [Catechol-based resin] The catechol-based resin of the present invention is a resin containing one or more catechol structures, and more preferably two or more catechol structures. There is no particular upper limit, but it preferably contains 10 or less catechol structures, more preferably 5 or less catechol structures, and even more preferably 3 or less catechol structures.

[0030] The catechol-based resin preferably contains any one of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3). [ka] In formula (B-1), R 11 each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R 12 each independently represents a single bond or a divalent hydrocarbon group which may have a substituent, and R12 may be bonded to the benzene ring in formula (B-1) to form a ring. 13 each independently represents an amide bond, a carbonyl group, -C(=O)O-, -OC(=O)O-, -O-, or -NR a -, or a divalent group selected from the group consisting of two or more thereof; R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 14 represents a k-valent hydrocarbon group having 2 to 100 carbon atoms which may have a heteroatom, and k represents an integer of 1 to 5. In formula (B-2), R 21 , and R 23 each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R 22 represents a divalent hydrocarbon group which may have a substituent, and R 22 may be bonded to the benzene ring in formula (B-2) to form a ring. In formula (B-3), R 31 represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; ring B represents a ring structure condensed with the benzene ring in formula (B-3); R 32 each independently represents an aryl group which may have a substituent, or an alkyl group which may have a substituent. 1 represents an integer of 0 to 2.

[0031] In formula (B-1), R 11 each independently represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

[0032] R 11The optionally substituted alkyl group represented by may be linear, branched, or cyclic. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0033] R 11 The alkoxy group represented by the formula (I) may have a substituent and may be linear, branched, or cyclic. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of such alkoxy groups include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group.

[0034] R 11 When the alkyl group and alkoxy group represented by the formula (I) have a substituent, examples of the substituent include a hydroxy group.

[0035] Among them, R 11 is preferably a hydrogen atom or a hydroxy group, and more preferably a hydrogen atom.

[0036] In formula (B-1), R 12 each independently represents a single bond or a divalent hydrocarbon group which may have a substituent, and R 12 may be bonded to the benzene ring in formula (B-1) to form a ring.

[0037] R 12The optionally substituted divalent hydrocarbon group represented by is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, even more preferably a divalent hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a divalent hydrocarbon group having 2 carbon atoms. The divalent hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. The divalent hydrocarbon group may be linear, branched, or cyclic, with linear or branched hydrocarbon groups being preferred, and linear groups being more preferred. Examples of the optionally substituted divalent hydrocarbon group include an optionally substituted divalent aliphatic hydrocarbon group and an optionally substituted divalent aromatic hydrocarbon group, with an optionally substituted divalent aliphatic hydrocarbon group being preferred. Specific examples of the optionally substituted divalent hydrocarbon group include an optionally substituted alkylene group, an optionally substituted alkenylene group, an optionally substituted alkynylene group, and an optionally substituted arylene group. Among these, from the viewpoint of significantly achieving the effects of the present invention, the optionally substituted divalent hydrocarbon group is preferably an optionally substituted alkylene group or an optionally substituted alkenylene group.

[0038] The alkylene group, which may have a substituent, may be linear, branched, or cyclic, with linear or branched hydrocarbon groups being preferred, and linear being more preferred. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclohexylene group, a 2,3-dimethylbutylene group, and a 2,6-dimethylheptylene group.

[0039] The alkenylene group, which may have a substituent, may be linear, branched, or cyclic, and is preferably a linear or branched hydrocarbon group, more preferably a linear one. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 or 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, and a decenylene group.

[0040] The alkynylene group, which may have a substituent, may be linear, branched, or cyclic, and is preferably a linear or branched hydrocarbon group, more preferably a linear one. The alkynylene group is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 6 carbon atoms, and even more preferably an alkynylene group having 2 or 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, and a decynylene group.

[0041] The optionally substituted arylene group is preferably an arylene group having 6 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the arylene group include a phenylene group and a naphthylene group.

[0042] Among them, R 12 is preferably a single bond, an alkylene group which may have a substituent, or an alkenylene group which may have a substituent, and more preferably a single bond, an ethylene group, or an ethenylene group.

[0043] In formula (B-1), R 13 each independently represents an amide bond, a carbonyl group, -C(=O)O-, -OC(=O)O-, -O-, or -NR aR represents a divalent group selected from the group consisting of -, or a combination of two or more thereof. a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0044] R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represents a hydrogen atom.

[0045] An amide bond is -C(=O)-NR b - or -NR b is a group represented by -C(=O)-, and R b Ha-NR a -R in a is the same as

[0046] Examples of divalent groups selected from the group consisting of a combination of two or more of these include groups consisting of a combination of an amide bond and an ether bond. Specific examples of groups consisting of a combination of an amide bond and an ether bond include -NR b -C(=O)-O-, -OC(=O)-NR b -etc.

[0047] Among them, R 13 Each of the groups independently represents -NR b -C(=O)-, -C(=O)-NR b -, -OC(=O)-, -C(=O)-O-, -NR b -C(=O)-O-, -OC(=O)-NR b -, -O-, or -NR a -, preferably -NR b -C(=O)-, -C(=O)-NR b -, -C(=O)-O-, or -NR b - is more preferable. In this case, R a and R b each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the preferred ranges of which are as described above.

[0048] In formula (B-1), k represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 2.

[0049] In formula (B-1), R 14 represents a k-valent hydrocarbon group having 2 to 100 carbon atoms which may have a heteroatom, preferably a k-valent hydrocarbon group having 3 to 80 carbon atoms which may have a heteroatom, and more preferably a k-valent hydrocarbon group having 5 to 50 carbon atoms which may have a heteroatom. 14 represents a divalent to pentavalent hydrocarbon group having 2 to 100 carbon atoms which may have a heteroatom, preferably a divalent to pentavalent hydrocarbon group having 5 to 80 carbon atoms which may have a heteroatom, and more preferably a divalent to pentavalent hydrocarbon group having 10 to 50 carbon atoms which may have a heteroatom. Examples of heteroatoms that the k-valent hydrocarbon group may have include an oxygen atom and a sulfur atom, with an oxygen atom being preferred. Such k-valent hydrocarbon groups which may have a heteroatom are preferably k-valent groups selected from the group consisting of k-valent aliphatic hydrocarbon groups, k-valent aromatic hydrocarbon groups, oxygen atoms, sulfur atoms, hydroxy groups, or combinations of two or more of these. Among these, R 14 is preferably a k-valent group selected from the group consisting of an alkylene group which may have a substituent, a heteroalkylene group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, an oxygen atom, a sulfur atom, a carbonyl group, or a combination of two or more thereof, and more preferably a k-valent group selected from the group consisting of an alkylene group which may have a substituent, a heteroalkylene group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, an oxygen atom, a hydroxy group, or a combination of two or more thereof.

[0050] The alkylene group, which may have a substituent, may be linear, branched, or cyclic, with linear or cyclic being preferred. The alkylene group is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 30 carbon atoms, and even more preferably an alkylene group having 1 to 20 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkylene group include a 1,1-dimethylmethylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclohexylene group, a methylcyclohexylene group, and a methylcyclohexylene-methylene-methylcyclohexylene group, with a methylene group, an ethylene group, a 1,1-dimethylmethylene group, a methylcyclohexylene group, and a methylcyclohexylene-methylene-methylcyclohexylene group being preferred. The term "methylcyclohexylene-methylene-methylcyclohexylene group" refers to a group in which two methylcyclohexylene groups are bonded via a methylene group, and is specifically the group shown below (in the formula, * represents a bond). [ka]

[0051] The heteroalkylene group, which may have a substituent, may be linear, branched, or cyclic, with cyclic being preferred. The heteroalkylene group is preferably a heteroalkylene group having 1 to 50 carbon atoms, more preferably a heteroalkylene group having 1 to 30 carbon atoms, and even more preferably a heteroalkylene group having 1 to 20 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of heteroalkylene groups include a methyleneoxymethylene group, a methyleneoxyethylene group, an ethyleneoxyethylene group, an ethyleneoxymethyleneoxyethylene group, a methylenethiomethylene group, a methylenethioethylene group, an ethylenethioethylene group, and a group obtained by removing two hydrogen atoms from tetrahydropyran, with a group obtained by removing two hydrogen atoms from tetrahydropyran being preferred.

[0052] The optionally substituted arylene group is preferably an arylene group having 6 to 50 carbon atoms, more preferably an arylene group having 6 to 30 carbon atoms, and even more preferably an arylene group having 6 to 20 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group, and a phenylene group is preferred.

[0053] The optionally substituted heteroarylene group is preferably a heteroarylene group having 3 to 50 carbon atoms, more preferably a heteroarylene group having 3 to 30 carbon atoms, and even more preferably a heteroarylene group having 5 to 20 carbon atoms. The number of carbon atoms in the substituent is not included in the number of carbon atoms. Examples of the optionally substituted heteroarylene group include groups obtained by removing two hydrogen atoms from pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, chromone, etc., and preferably a group obtained by removing two hydrogen atoms from furan or a group obtained by removing two hydrogen atoms from chromone.

[0054] Examples of the k-valent group selected from the group consisting of combinations of two or more of these include a group in which one or more arylene groups are bonded to one or more oxygen atoms and one or more alkylene groups, a group in which one or more heteroarylene groups are bonded to one or more arylene groups, a group in which one or more arylene groups are bonded to one or more alkylene groups and one or more carbonyl groups, a group in which one or more arylene groups are bonded to one or more carbonyl groups and one or more heteroalkylene groups, and a group in which one or more arylene groups are bonded to one or more alkylene groups. Of these, a group in which one or more arylene groups are bonded to one or more oxygen atoms and one or more alkylene groups, a group in which one or more heteroarylene groups are bonded to one or more arylene groups, a group in which one or more arylene groups are bonded to one or more alkylene groups and one or more carbonyl groups, and a group in which one or more arylene groups are bonded to one or more carbonyl groups and one or more heteroalkylene groups are preferred. Specific examples of the k-valent group selected from the group consisting of a combination of two or more of these groups include the groups represented by the following (i) to (viii), in which "*" represents a bond.

[0055] [ka] [ka]

[0056] R 14 When the alkylene group, heteroalkylene group, arylene group, and heteroarylene group represented by the formula (I) have a substituent, examples of the substituent include a hydroxy group.

[0057] Examples of the compound represented by formula (B-1) include, but are not limited to, the compounds represented by the following formulas (1) to (10). [ka] [ka] [ka]

[0058] In formula (B-2), R 21 and R 23 each independently represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and R in formula (B-1) 11 is the same as

[0059] In formula (B-2), R 22 represents a divalent hydrocarbon group which may have a substituent, and R 22may bond with the benzene ring in formula (B-2) to form a ring. The divalent hydrocarbon group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a divalent hydrocarbon group having 1 to 6 carbon atoms. The divalent hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. The divalent hydrocarbon group may be linear, branched, or cyclic. Examples of the divalent hydrocarbon group that may have a substituent include a divalent aliphatic hydrocarbon group that may have a substituent and a divalent aromatic hydrocarbon group that may have a substituent, with a divalent aliphatic hydrocarbon group that may have a substituent being preferred. Specific examples of the divalent hydrocarbon group that may have a substituent include an alkylene group that may have a substituent, an alkenylene group that may have a substituent, an alkynylene group that may have a substituent, and an arylene group that may have a substituent. Among these, an alkylene group that may have a substituent is preferred as the divalent hydrocarbon group that may have a substituent, from the viewpoint of significantly achieving the effects of the present invention. The alkylene group which may have a substituent may be bonded to the benzene ring in formula (B-2) to form a ring.

[0060] R 22 The alkylene group which may have a substituent, the alkenylene group which may have a substituent, the alkynylene group which may have a substituent, and the arylene group which may have a substituent, which are represented by the formula (B-1), include R 12 is the same as the alkylene group which may have a substituent, the alkenylene group which may have a substituent, the alkynylene group which may have a substituent, and the arylene group which may have a substituent, represented by the formula (I).

[0061] R 22 may be bonded to the benzene ring in formula (B-2) to form a ring. 22The ring structure that may be formed by catechol may be a spiro ring or a fused ring. Examples of the ring structure include a group that forms a cyclopentane ring, a group that forms a 2,2-dimethylcyclopentane ring, and a group that forms a cyclohexane ring, and a group that forms a 2,2-dimethylcyclopentane ring is preferred.

[0062] Examples of the compound represented by formula (B-2) include, but are not limited to, the compounds represented by the following formulas (11) and (12). [ka]

[0063] In formula (B-3), R 31 represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and R in formula (B-1) 11 is the same as

[0064] Ring B represents a ring structure fused with the benzene ring in formula (B-3). The ring structure represented by ring B may be a monocyclic ring or a fused ring, with a monocyclic ring being preferred. Ring B may be either a lactone structure or a cyclic ketone structure, with a cyclic ketone structure being preferred. Ring B is preferably a 3- to 10-membered ring, more preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0065] Examples of the lactone structure include an α-acetolactone structure, a β-propiolactone structure, a γ-butyrolactone structure, a δ-valerolactone structure, and an ε-caprolactone structure, with the δ-valerolactone structure being preferred.

[0066] The cyclic ketone structure may be a heteroatom-containing cyclic ketone structure containing a heteroatom such as an oxygen atom or a sulfur atom. Examples of the cyclic ketone structure include a cyclopropanone structure, a cyclopentanone structure, a cyclohexanone structure, a 4-oxycyclohexanone structure, a 4-oxy-2-cyclohexenone structure, and a 2-oxy-5-cyclohexenone structure, and the 4-oxy-2-cyclohexenone structure and the 2-oxy-5-cyclohexenone structure are preferred.

[0067] Ring B may have a substituent. Examples of the substituent include the above-mentioned substituents, and among them, a hydroxy group is preferable.

[0068] Ring B is preferably any one of a δ-valerolactone structure, a 4-oxy-2-cyclohexenone structure, and a 2-oxy-5-cyclohexenone structure. Specific examples of ring B include those represented by the formula (R 32 -1)~(R 32 In the following formula, the dashed line indicates the position where the group is fused with the benzene ring in formula (B-3). [ka]

[0069] In formula (B-3), R 32 each independently represents an aryl group which may have a substituent, or an alkyl group which may have a substituent.

[0070] R 32 The optionally substituted aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 12 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group, with a phenyl group being preferred.

[0071] R 32The optionally substituted alkyl group represented by may be linear, branched, or cyclic. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0072] R 32 When the aryl group and alkyl group represented by the formula (I) have a substituent, examples of the substituent include a hydroxy group.

[0073] In formula (B-3), l represents an integer of 0 to 2, and preferably represents 0 or 1.

[0074] Examples of the compound represented by formula (B-3) include, but are not limited to, the compounds represented by the following formulas (13) to (16). [ka]

[0075] From the viewpoint of significantly obtaining the effects of the present invention, the molecular weight of the catechol-based resin is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less, and is preferably 50 or more, more preferably 100 or more, even more preferably 200 or more.

[0076] From the viewpoint of significantly achieving the effects of the present invention, the active group equivalent (hydroxy group equivalent) of the catechol-based resin is preferably 30 g / eq or more, more preferably 50 g / eq or more, even more preferably 80 g / eq or more, and is preferably 1000 g / eq or less, more preferably 800 g / eq or less, even more preferably 500 g / eq or less. The active group equivalent is the mass of the resin containing one equivalent of active groups.

[0077] The method for producing the catechol-based resin is not particularly limited. For example, the catechol-based resin can be obtained by reacting a catechol-containing carboxylic acid with any one of a polyamine compound, a polyphenol compound, and a polyol compound. Alternatively, for example, the catechol-based resin can be obtained by reacting a catechol-containing amine compound with a dicarboxylic acid.

[0078] From the viewpoints of energy saving, cost saving, and environmental conservation, it is preferable to synthesize the catechol-based resin using plant-derived raw materials. For example, the catechol-containing carboxylic acid, polyphenol compound, and dicarboxylic acid dichloride can be derived from plant-derived biomass raw materials. Examples of raw materials derived from plant-derived biomass raw materials include caffeic acid, protocatechuic acid, gallic acid, daidzein, resveratrol, isophthalic acid, and 2,5-furandicarboxylic acid.

[0079] From the viewpoint of reducing the environmental load, the biomass ratio of the catechol-based resin is preferably 0.5% or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more. There is no particular upper limit, but it is preferably 100% by mass or less, more preferably 75% by mass or less, and even more preferably 50% by mass or less, 30% by mass or less, or 10% by mass or less. The biomass ratio is the proportion of biomass-derived components contained in a compound. The Japan Organics Recycling Association defines biomass as any renewable organic resource derived from a living organism, excluding fossil resources (however, it does include inorganic resources such as shells produced directly by living organisms). Based on this definition, the biomass ratio of the raw materials used in the blending is a value calculated using the following formula: Biomass ratio (mass%) = (weight of biological components in a substance / weight of substance) x 100

[0080] Catechol-containing carboxylic acids are compounds in which a carboxyl group is bonded to a catechol, such as caffeic acid, protocatechuic acid, and gallic acid.

[0081] The polyamine compound is a compound having two or more amino groups capable of reacting with the carboxyl group of the catechol-containing carboxylic acid. Examples of the polyamine compound include 2,2'-dimethyl-4,4'-methylenedicyclohexylamine and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0082] The polyphenol compound is a compound having two or more hydroxy groups capable of reacting with the carboxyl group of the catechol-containing carboxylic acid. Examples of the polyphenol compound include daidzein and resveratrol.

[0083] Dicarboxylic acid dichlorides are compounds having two or more chlorine atoms capable of reacting with the carboxyl groups of catechol-containing carboxylic acids. Examples of dicarboxylic acid dichlorides include isophthalic acid dichloride and 2,5-furandicarboxylic acid dichloride.

[0084] The catechol-containing amine compound is a compound in which an amino group is bonded to a catechol, and examples of the catechol-containing amine compound include 3,4-dihydroxybenzylamine.

[0085] Examples of dicarboxylic acids include isophthalic acid and 2,5-furandicarboxylic acid.

[0086] In producing the catechol-based resin, if necessary, a condensing agent such as 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide may be used in the presence or absence of 1-hydroxy-7-azabenzotriazole, N,N-diisopropylethylamine, or the like, in the presence or absence of a base such as triethylamine.

[0087] In producing the catechol-based resin, a solvent may be used as needed, such as dichloromethane or N,N-dimethylformamide.

[0088] The reaction temperature in the production of the catechol-based resin may be, for example, in the range of 0 to 80° C. The reaction time may be, for example, in the range of 30 minutes to 8 hours.

[0089] After the reaction is completed, if necessary, purification steps such as washing with water, filtration, chromatography, etc. may be carried out to remove by-product salts and excess starting materials from the system.

[0090] [Resin composition] The resin composition of the present invention comprises (A) an epoxy resin, (B) a catechol-based curing agent, and (C) an inorganic filler, and the content of component (C) is 50% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. This resin composition can provide a cured product with a low coefficient of linear thermal expansion, high elongation at break, and excellent crack resistance.

[0091] The resin composition may contain (D) a curing agent, (E) a curing accelerator, (F) a thermoplastic resin, and (G) other additives in combination with (A) an epoxy resin, (B) a catechol-based curing agent, and (C) an inorganic filler.

[0092] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). The epoxy resin is a thermosetting resin having an epoxy group. The epoxy resin may be used alone or in combination of two or more types.

[0093] Examples of epoxy resins include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, and phenolphthalimidine-type epoxy resins. The epoxy resin may be used alone or in combination of two or more.

[0094] The resin composition preferably contains an epoxy resin having two or more epoxy groups per molecule as the epoxy resin. The proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile components of the epoxy resin.

[0095] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as the epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0096] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0097] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure, and more preferred are bisphenol A type epoxy resins and naphthalene type epoxy resins.

[0098] Specific examples of liquid epoxy resins include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US," "828EL," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630," "630LSD," and "604" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol-type epoxy resin) manufactured by ADEKA Corporation; and "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) manufactured by ADEKA Corporation. epoxy resins); "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation; "JP-100" and "JP-200" (epoxy resins having a butadiene structure (epoxidized polybutadiene resin) manufactured by Nippon Soda Co., Ltd.); and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These may be used alone or in combination of two or more.

[0099] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0100] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins; more preferred are bixylenol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, dicyclopentadiene-type epoxy resins, and naphthalene-type epoxy resins; and even more preferred are bixylenol-type epoxy resins, biphenyl-type epoxy resins, and naphthalene-type epoxy resins.

[0101] Specific examples of solid epoxy resins include DIC Corporation's "HP4032H" (naphthalene-type epoxy resin); DIC Corporation's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC Corporation's "N-690" (cresol novolac-type epoxy resin); DIC Corporation's "N-695" (cresol novolac-type epoxy resin); DIC Corporation's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene-type epoxy resins); and DIC Corporation's "EXA-7311." "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4" manufactured by Nippon Steel Chemical & Material Co., Ltd. 100V" (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "Y" manufactured by Mitsubishi Chemical Corporation Examples include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0102] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio thereof (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:10, and particularly preferably 1:0.1 to 1:7.

[0103] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., even more preferably 80 g / eq. to 2,000 g / eq., and particularly preferably 110 g / eq. to 1,000 g / eq. The epoxy equivalent represents the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0104] The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0105] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0106] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are taken as 100 mass%, and the non-volatile components mean all non-volatile components in the resin composition excluding the solvent.

[0107] <(B) Catechol-based curing agent> The resin composition contains a (B) catechol-based curing agent as component (B). Component (B) does not include components that fall under component (A). The (B) catechol-based curing agent reacts with the (A) epoxy resin to cure the resin composition. The (B) catechol-based curing agent contained in the resin composition can be the catechol-based resin described above in the [Catechol-Based Resin] section.

[0108] Component (B) may be a commercially available product, such as tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 7,8-dihydroxyflavone (manufactured by Fujifilm Wako Chemical Co., Ltd.), quercetin (manufactured by Tokyo Chemical Industry Co., Ltd.), baicalein (manufactured by Tokyo Chemical Industry Co., Ltd.), 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (manufactured by Tokyo Chemical Industry Co., Ltd.), nordihydroguaiaretic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,6,7-trihydroxycoumarin (manufactured by BOC Sciences), 2-(3,4-dihydroxyphenyl)-5,7-dihydroxy-4H-chromen-4-one (manufactured by Fujifilm Wako Chemical Co., Ltd.), or (-)-epigallocatechin 3-gallate (manufactured by Fujifilm Wako Chemical Co., Ltd.).

[0109] The quantitative ratio of component (A) to component (B), expressed as the ratio of [total number of epoxy groups in component (A)] to [total number of active groups in component (B)], is preferably in the range of 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and even more preferably 1:0.05 to 1:0.3. Here, the "total number of epoxy groups in component (A)" refers to the sum of all values obtained by dividing the mass of the nonvolatile components of component (A) present in the resin composition by the epoxy equivalent. Furthermore, the "number of active groups in component (B)" refers to the sum of all values obtained by dividing the mass of the nonvolatile components of component (B) present in the resin composition by the active group equivalent. By maintaining the quantitative ratio of component (A) to component (B) within this range, the effects of the present invention can be significantly achieved.

[0110] From the viewpoint of obtaining a cured product having a low coefficient of linear thermal expansion and excellent elongation and crack resistance, the content of component (B) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, when the total amount of non-volatile components in the resin composition is taken as 100% by mass.

[0111] <(C) Inorganic filler> The resin composition contains an inorganic filler as component (C). By including component (C) in the resin composition, the linear thermal expansion coefficient of the cured product can be reduced.

[0112] (C) Inorganic fillers are inorganic compounds. Examples of (C) inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. The (C) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0113] (C) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Company, Limited; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "Cellphears" and "MGH-005" manufactured by Taiheiyo Cement Corporation; and "Sferique" and "BA-1" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0114] (C) The inorganic filler may be a biomass-derived inorganic filler. It is preferable that the biomass-derived inorganic filler is produced from a plant raw material. For example, plants of the Equisetaceae and Poaceae families have the property of absorbing and accumulating silicon components from the ground. Therefore, by burning these plants, silica can be produced as combustion ash (Patent Publication No. 6389349). Commercially available biomass-derived inorganic fillers may be used. An example of a commercially available biomass-derived inorganic filler is "Ethical Silica" manufactured by MIT, which is biomass silica produced from rice husks.

[0115] The average particle size of the (C) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably 1.5 μm or less. The lower limit of the average particle size of the (C) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (C) inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and ultrasonically dispersing for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution analyzer, with blue and red light source wavelengths used, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell system, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0116] The specific surface area of the (C) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of the inorganic filler (C) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, and even more preferably 30m 2 / g or less, particularly preferably 10m 2The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0117] The (C) inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. The surface treatment agent may be used alone or in any combination of two or more.

[0118] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0119] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0120] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Preferably less than 0.8 mg / m 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0121] (C) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used as the carbon analyzer.

[0122] From the viewpoint of obtaining a cured product with a low linear thermal expansion coefficient, the content of the (C) inorganic filler is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0123] <(D) Hardener (excluding those corresponding to component (B))> The resin composition may further contain a (D) curing agent as an optional component in combination with the above-described (A) to (C) components. The (D) curing agent as this (D) component does not include those corresponding to the above-described (A) to (C) components. One type of (D) component may be used alone, or two or more types may be used in combination.

[0124] Examples of component (D) include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. Among these, from the viewpoint of significantly achieving the effects of the present invention, component (D) is preferably one or more of phenol-based curing agents, naphthol-based curing agents, and active ester-based curing agents, and it is particularly preferable that component (D) contains an active ester-based curing agent.

[0125] As the phenol-based curing agent and naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred.

[0126] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170," "SN180," "SN190," "SN475," "SN485," "SN495," "SN-495V," "SN375," and "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "TD-2090," "LA-7052," "LA-7054," "LA-1356," "LA-3018-50P," and "EXB-9500" manufactured by DIC Corporation.

[0127] The active ester curing agent is not particularly limited, but compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0128] Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, or an active ester compound containing a benzoylated product of phenol novolac is preferred, and among these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0129] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB-9451," "EXB-9460," "EXB-9460S," "HPC-8000-65T," "HPC-8000H-65TM," and "HPC-8000L-65TM" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure, such as "EXB-9416-70BK," "EXB-8100L-65T," "EXB-8150-65T," "EXB-8150L-65T," "HPC-8150-60T," "HPC-8150-62T," and "HP-B-8151-62T" (manufactured by DIC Corporation); and phenol novolac. Examples of active ester compounds containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), active ester curing agents that are acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester curing agents that are benzoated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and an active ester compound containing a styryl group includes "PC1300-02-65MA" (manufactured by Air Water Inc.).

[0130] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0131] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer), all of which are manufactured by Lonza Japan.

[0132] Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Inc.

[0133] When a curing agent is included as component (D), the ratio of component (A) to components (B) and (D) is preferably 1:0.01 to 1:5, more preferably 1:0.05 to 1:3, and even more preferably 1:0.1 to 1:2, in terms of the ratio of [total number of epoxy groups in component (A)] to [total number of active groups in components (B) and (D)]. Here, the "number of active groups in components (B) and (D)" refers to the total value obtained by dividing the mass of the nonvolatile components (B) and (D) present in the resin composition by the active group equivalent. By keeping the ratio of components (B) and (D) to component (A) within this range, the effects of the present invention can be significantly achieved.

[0134] When a curing agent is included as component (D), the ratio of component (A) to all components (D) is preferably 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and even more preferably 1:0.05 to 1:0.3, in terms of the ratio of [total number of epoxy groups in component (A)] to [total number of active groups in component (D)]. Here, the "number of active groups in component (D)" refers to the total value obtained by dividing the mass of the nonvolatile components of component (D) present in the resin composition by the active group equivalent. By maintaining the ratio of component (A) to component (D) within this range, the effects of the present invention can be significantly achieved.

[0135] From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (D) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0136] <(E) Curing accelerator> The resin composition may further contain an optional component (E) curing accelerator in combination with the above-described components (A) to (C). This component (E) curing accelerator does not include components (A) to (D). The curing accelerator (E) functions as a curing catalyst that accelerates the curing of the epoxy resin (A).

[0137] As the (E) curing accelerator, a compound that accelerates the curing of the epoxy resin can be used. Examples of such (E) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. One type of (E) curing accelerator may be used alone, or two or more types may be used in combination.

[0138] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium tetra-p-tolylborate. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine aromatic phosphines such as benzene, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether;

[0139] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as toluene bis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0140] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0141] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct Examples of imidazole compounds include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins. Commercially available imidazole curing accelerators include "1B2PZ," "2E4MZ," "2MZA-PW," "2MZ-OK," "2MA-OK," "2MA-OK-PW," "2PHZ," "2PHZ-PW," "Cl1Z," "Cl1Z-CN," "Cl1Z-CNS," and "C11Z-A" manufactured by Shikoku Chemicals Corporation; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0142] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0143] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. Commercially available amine curing accelerators may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0144] From the viewpoint of significantly obtaining the effects of the present invention, the content of the (E) curing accelerator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.03% by mass or more, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0145] From the viewpoint of significantly achieving the effects of the present invention, the total content of the components (A), (B), (D), and (E) (thermosetting resin content) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 35% by mass or less, when the total non-volatile components in the resin composition is taken as 100% by mass.

[0146] <(F)Thermoplastic resin> The resin composition of the present invention may further contain a thermoplastic resin (F) as an optional component. The thermoplastic resin (F) as component (F) does not include those corresponding to the above-mentioned components (A) to (E).

[0147] The resin composition may contain, as the (F) thermoplastic resin, a particulate thermoplastic resin that maintains a particulate form in the resin composition, or a non-particulate thermoplastic resin that is contained in the resin composition in a mixed or dissolved form. Of these, the resin composition preferably contains a non-particulate thermoplastic resin from the viewpoint of significantly achieving the effects of the present invention.

[0148] Examples of non-particulate thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and polyamide resins. In one embodiment, the (B) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resins and phenoxy resins, and more preferably contains a phenoxy resin. Furthermore, the thermoplastic resins may be used alone or in combination of two or more.

[0149] Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0150] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0151] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0152] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd.; and S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series, manufactured by Sekisui Chemical Co., Ltd.

[0153] Examples of polyolefin resins include ethylene copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0154] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0155] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imides) manufactured by Hitachi Chemical Co., Ltd.

[0156] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0157] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0158] A specific example of the polyphenylene ether resin is NORYL SA90 manufactured by SABIC, etc. A specific example of the polyetherimide resin is ULTEM manufactured by GE, etc.

[0159] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0160] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0161] Examples of polyamide resins include nylon 6 and nylon 66. The polyamide resin is preferably a biomass-derived polyamide resin. Examples of biomass-derived polyamide resins include "Vegichem Green V335" manufactured by Tsuno Foods Co., Ltd.

[0162] Examples of particulate thermoplastic resins include rubber particles, polyamide fine particles, and silicone particles, with rubber particles being preferred.

[0163] As the rubber particles, commercially available products may be used, such as "EXL2655" manufactured by Dow Chemical Japan, and "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

[0164] From the viewpoint of significantly achieving the effects of the present invention, the weight average molecular weight (Mw) of the (F) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0165] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the (F) thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0166] <(G) Other additives> In addition to the components described above, the resin composition may further contain other additives as optional components. Examples of such additives include elastomers (excluding those corresponding to component (F)), thickeners, antifoaming agents, leveling agents, adhesion promoters, and flame retardants. These may be used alone or in combination of two or more in any ratio.

[0167] The resin composition can be produced, for example, by mixing the above-mentioned components in any order. Furthermore, heating and / or cooling may be performed by appropriately adjusting the temperature during the process of mixing the components. Furthermore, stirring may be performed using a stirring device such as a mixer during or after mixing the components to uniformly disperse the components. Furthermore, the resin composition may be subjected to a degassing treatment, if necessary.

[0168] <Physical properties and applications of resin compositions> The resin composition contains component (B), and the content of component (C) is 50% by mass or more when the non-volatile components in the resin composition are 100% by mass. Therefore, it is possible to obtain a cured product with a low coefficient of linear thermal expansion and excellent elongation at break and crack resistance.

[0169] A cured product obtained by curing the resin composition at 190°C for 90 minutes exhibits the characteristic of a low linear thermal expansion coefficient. Therefore, an insulating layer with a low linear thermal expansion coefficient is obtained. The thermal expansion coefficient of the cured product of the resin composition is preferably less than 30 ppm / °C. The lower limit is not particularly limited, but may be, for example, 0.001 ppm / °C or more. The linear thermal expansion coefficient can be measured by the method described in the examples below.

[0170] A cured product obtained by curing the resin composition at 190°C for 90 minutes exhibits the characteristic of high elongation at break. Therefore, when an insulating layer is formed using this cured product, an insulating layer with excellent mechanical strength can be obtained. The elongation at break is preferably 1.0% or more. The upper limit is not particularly limited, but can be, for example, 10% or less. The elongation at break can be measured by the method described in the examples below.

[0171] The cured product obtained by curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits excellent crack resistance. Therefore, when an insulating layer is formed using this cured product, an insulating layer with excellent crack resistance can be obtained. Specifically, the resin composition is laminated on an inner layer substrate on which a wiring pattern has been formed, and the cured product is obtained by thermal curing. The surface of the cured product is roughened to obtain a sample. 100 sections on the pattern of the sample inner layer substrate are checked for cracks along the pattern shape, and the number of sections on the pattern without cracks is counted. The percentage of crack-free sections out of the 100 sections is calculated as the "yield." In this case, the yield is preferably less than 60%, more preferably less than 40%, and even more preferably less than 20%. The lower limit is not particularly limited, but can be 0% or more. Crack resistance can be measured by the method described in the Examples below.

[0172] The resin composition of the present invention is suitable as a resin composition for insulating applications, and particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition is suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). The resin composition is also suitable as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) to form a conductor layer (including a rewiring layer) formed on an insulating layer. The resin composition can also be used in a wide range of applications where a resin composition can be used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages.

[0173] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to this embodiment is also suitable as a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulation layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0174] The above-mentioned resin composition can also be used when the printed wiring board is a circuit board with built-in components.

[0175] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0176] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 75 μm or less, and even more preferably 50 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product of the resin composition that has excellent insulating properties even when the cured product is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0177] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0178] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0179] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0180] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0181] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0182] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0183] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0184] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0185] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0186] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0187] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0188] [Printed wiring board] A printed wiring board according to one embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0189] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Step of curing the resin composition layer to form an insulating layer

[0190] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Furthermore, intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board are also included in the "inner layer substrate." When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0191] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (such as a SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0192] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0193] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0194] After lamination, the laminated resin sheets may be smoothed under atmospheric pressure, for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that the lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0195] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0196] In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and the conditions employed for forming an insulating layer of a printed wiring board may be used. The resin composition layer may be cured by irradiation with active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

[0197] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0198] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0199] The method for producing a printed wiring board may further include the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0200] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0201] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0202] Examples of swelling solutions used in the roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Examples of alkaline solutions include sodium hydroxide solutions and potassium hydroxide solutions. Examples of commercially available swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0203] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0204] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0205] In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably less than 200 nm, even more preferably 100 nm or less, and even more preferably less than 100 nm. The lower limit is not particularly limited and may be, for example, 1 nm or more, 2 nm or more, etc. The root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and may be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0206] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0207] The conductor layer may have a single layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0208] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0209] The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a semi-additive method, a full-additive method, or the like. From the viewpoint of ease of production, the conductor layer is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method will be described below.

[0210] A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0211] [Semiconductor Devices] A semiconductor device according to one embodiment of the present invention includes the above-described printed wiring board, and can be manufactured using the above-described printed wiring board.

[0212] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0213] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure, unless otherwise specified.

[0214] <Synthesis Example 1> Synthesis of catechol-based resin (1) Caffeic acid (1.44 g, 8 mmol) (derived from coffee beans, manufactured by INDOFINE Chemical Company, Inc.), 2,2'-dimethyl-4,4'-methylenedicyclohexylamine (1 mL, 4 mmol), 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide (1.53 g, 8 mmol), 1-hydroxy-7-azabenzotriazole (1.09 g, 8 mmol), and N,N-diisopropylethylamine (2.1 mL, 12 mmol) were mixed with N,N-dimethylformamide (20.0 mL) and stirred overnight at 40 °C. The reaction mixture was neutralized with 0.1% aqueous trifluoroacetic acid and purified by high-performance liquid chromatography (water-acetonitrile, each containing 0.1% trifluoroacetic acid) to yield 1.2 g of catechol-based resin (1).

[0215] The obtained catechol-based resin (1) was measured by infrared spectroscopy (IR) using an IR measurement device (PIKE Technologies' "GladiATR"). The IR chart is shown in Figure 1. In addition, the mass spectrum (ESI) showed m / z = 563 (M + H). + The spectrum was observed. 1 H-NMR (methanol-heavy) chart and Figure 3 1 The H-NMR (deuterated dimethyl sulfoxide) chart is shown in Figure 1. As a result, it was confirmed that the obtained polyester resin had the following molecular structure. [ka]

[0216] <Synthesis Example 2> Synthesis of catechol-based resin (2) In Synthesis Example 1, 1.44 g of caffeic acid was changed to 1.46 g of 3,4-dihydroxyhydrocinnamic acid. Except for the above, the same procedure as in Synthesis Example 1 was carried out to obtain a catechol-based resin (2) having the following structure. [ka]

[0217] <Synthesis Example 3> Synthesis of catechol-based resin (3) In Synthesis Example 1, 1.44 g of caffeic acid was changed to 1.23 g of protocatechuic acid (manufactured by Green Chemicals Co., Ltd.) Except for the above, the same procedures as in Synthesis Example 1 were carried out to obtain a catechol-based resin (3) having the following structure. [ka]

[0218] <Synthesis Example 4> Catechol-based resin (4) In Synthesis Example 1, 1.44 g of caffeic acid was changed to 1.36 g of gallic acid (manufactured by Sumitomo Pharma Food & Chemical Co., Ltd.) Except for the above, the same procedure as in Synthesis Example 1 was carried out to obtain a catechol-based resin (4) having the following structure. [ka]

[0219] <Synthesis Example 5> Catechol-based resin (5) In Synthesis Example 1, 1 mL (4 mmol) of 2,2'-dimethyl-4,4'-methylenedicyclohexylamine was changed to 1.64 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Except for the above, the same procedure as in Synthesis Example 1 was carried out to obtain a catechol-based resin (5) having the following structure. [ka]

[0220] <Synthesis Example 6> Synthesis of catechol-based resin (6) (Process 1) Caffeic acid (1.44 g, 8 mmol) (derived from coffee beans, manufactured by INDOFINE Chemical Company, Inc.), potassium carbonate (1.66 g, 12 mmol), and benzyl bromide (3.8 mL, 32 mmol) were added to acetone (240 mL) and stirred overnight under reflux. After returning to room temperature, potassium hydroxide (269 mg, 4.8 mmol) was added and stirred for approximately 10 hours. The solvent was evaporated under reduced pressure, followed by addition of water and washing with diethyl ether. The aqueous layer was neutralized with 2 mol / L hydrochloric acid, extracted with diethyl ether, and the resulting organic layer was dried over sodium sulfate. The desiccant was filtered off, the solvent was evaporated, and the residue was recrystallized from methanol to yield 2.59 g of (E)-3-(3,4-bis(benzyloxy)phenyl)acrylic acid.

[0221] (Process 2) Dichloromethane (200 mL) was added to (E)-3-(3,4-bis(benzyloxy)phenyl)acrylic acid (2.59 g, 7.2 mmol) obtained in step 1, daidzein (915 mg, 3.6 mmol) (derived from soybean, manufactured by Wako Pure Chemical Industries, Ltd.), 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide (1.38 g, 7.2 mmol), 1-hydroxy-7-azabenzotriazole (0.981 g, 7.2 mmol), and N,N-diisopropylethylamine (1.8 mL, 10 mmol) and stirred overnight at room temperature. Water was added, and the mixture was extracted with dichloromethane. The resulting organic layer was dried over sodium sulfate. The desiccant was filtered off, and the solvent was evaporated. Then, methanol (200 mL) was added to 10% palladium on carbon (0.40 g) and stirred overnight at 35°C under a hydrogen atmosphere. The catalyst was filtered off, and the residue obtained by concentrating the filtrate under reduced pressure was neutralized with a 0.1% aqueous solution of trifluoroacetic acid and purified by high performance liquid chromatography (water-acetonitrile, each containing 0.1% trifluoroacetic acid) to obtain a catechol-based resin (6) having the following structure. [ka]

[0222] <Synthesis Example 7> Synthesis of catechol-based resin (7) In Synthesis Example 6, 915 mg of daidzein was changed to 548 mg of resveratrol (derived from grape skin extract, manufactured by Techno Science Co., Ltd.) Except for the above, the same procedure as in Synthesis Example 6 was repeated to obtain a catechol resin (7) having the following structure. [ka]

[0223] <Synthesis Example 8> Synthesis of catechol-based resin (8) In Synthesis Example 1, 1) 1.44 g of caffeic acid was replaced with 1.76 g of 3,4-dihydroxybenzylamine hydrobromide, 2) 1 mL (4 mmol) of 2,2'-dimethyl-4,4'-methylenedicyclohexylamine was converted to 1.33 g of isophthalic acid. Except for the above, the same procedure as in Synthesis Example 1 was carried out to obtain a catechol-based resin (8) having the following structure. [ka]

[0224] <Synthesis Example 9> Synthesis of catechol-based resin (9) In Synthesis Example 8, 1.33 g of isophthalic acid was changed to 1.25 g of 2,5-furandicarboxylic acid. Except for the above, the same procedure as in Synthesis Example 8 was carried out to obtain a catechol-based resin (9) having the following structure. [ka]

[0225] Example 1 An epoxy resin solution composition was prepared by stirring 20 parts of a biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269 g / eq.), 10 parts of a bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approximately 194 g / eq.), and 15 parts of a naphthalene-type epoxy resin ("ESN475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: approximately 332 g / eq.). This epoxy resin composition was treated with 2 parts of a triazine skeleton-containing phenolic curing agent (DIC Corporation's "LA-3018-50P," active group equivalent weight approximately 151 g / eq., non-volatile content 50% in 2-methoxypropanol solution), 26 parts of an active ester compound (DIC Corporation's "HPC-8000-65T," active ester group equivalent weight approximately 223 g / eq., non-volatile content 65% in toluene solution), 4 parts of the catechol resin (1) obtained in Synthesis Example 1, and an amine curing accelerator (4-dimethylaminomethylpropanol). A resin varnish was prepared by mixing 4 parts of dimethylaminopyridine (DMAP, MEK solution with 5% solids by mass), 120 parts of spherical silica (Admatechs' SO-C2, average particle size 0.5 μm) surface-treated with a silane coupling agent (Shin-Etsu Chemical's KBM-573), and 8 parts of phenoxy resin (Mitsubishi Chemical's YX7553BH30, 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass), and dispersing the mixture uniformly using a high-speed rotating mixer.

[0226] Next, a resin varnish was uniformly applied to the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) serving as a support, so that the thickness of the resin composition layer was 40 μm, and the film was dried at 80 to 120°C (average 100°C) for 5 minutes to produce a resin sheet with a support.

[0227] <Example 2> In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (2) obtained in Synthesis Example 2. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0228] Example 3 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (3) obtained in Synthesis Example 3. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0229] Example 4 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (4) obtained in Synthesis Example 4. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0230] <Example 5> In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (5) obtained in Synthesis Example 5. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0231] Example 6 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (6) obtained in Synthesis Example 6. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0232] Example 7 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (7) obtained in Synthesis Example 7. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0233] Example 8 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (8) obtained in Synthesis Example 8. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0234] Example 9 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of the catechol-based resin (9) obtained in Synthesis Example 9. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0235] Example 10 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of tannic acid is shown below. [ka]

[0236] Example 11 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of 7,8-dihydroxyflavone (manufactured by Fujifilm Wako Chemical Co., Ltd.). Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of 7,8-dihydroxyflavone is shown below. [ka]

[0237] Example 12 In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of quercetin (manufactured by Tokyo Chemical Industry Co., Ltd.). Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of quercetin is shown below. [ka]

[0238] Example 13 In Example 1, 1) 20 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent weight approximately 269 g / eq.) was replaced with 15 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828EL", epoxy equivalent weight approximately 180 g / eq.), 2) 15 parts of naphthalene type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ESN475V", epoxy equivalent weight approximately 332 g / eq.) was replaced with 20 parts of naphthylene ether type epoxy resin (DIC Corporation "HP-6000", epoxy equivalent weight approximately 250 g / eq.), 3) The amount of active ester compound (DIC Corporation's "HPC-8000-65T," active ester group equivalent weight approximately 223 g / eq., toluene solution with a non-volatile content of 65%) was changed from 26 parts to 15 parts. 4) 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of baicalein (manufactured by Tokyo Chemical Industry Co., Ltd.), 5) 10 parts of a bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan, cyanate equivalent weight approximately 232 g / eq., MEK solution with a non-volatile content of 75% by mass) was used. 6) Using 1 part of a 1% by mass MEK solution of cobalt (III) acetylacetonate (Tokyo Chemical Industry Co., Ltd.), 7) 2 parts of a triazine skeleton-containing phenolic curing agent (DIC Corporation's "LA-3018-50P," active group equivalent weight approximately 151 g / eq., 2-methoxypropanol solution with a non-volatile content of 50%) was not used. Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of baicalein is shown below. [ka]

[0239] Example 14 In Example 1, 1) 15 parts of naphthalene-type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ESN475V", epoxy equivalent weight approximately 332 g / eq.) was replaced with 10 parts of bisphenol A-type epoxy resin (Mitsubishi Chemical Co., Ltd. "828EL", epoxy equivalent weight approximately 180 g / eq.), 2) 5 parts of naphthylene ether type epoxy resin (DIC "HP-6000", epoxy equivalent weight approximately 250 g / eq.) was used. 3) The amount of triazine skeleton-containing phenolic curing agent (DIC Corporation "LA-3018-50P", active group equivalent weight approximately 151 g / eq., 2-methoxypropanol solution with non-volatile content of 50%) was changed from 2 parts to 10 parts. 4) 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (manufactured by Tokyo Chemical Industry Co., Ltd.), 5) 10 parts of naphthol-type hardener (Nippon Steel Chemical & Material Co., Ltd. "SN-485", hydroxyl group equivalent: approximately 205 g / eq.) 6) Using 2 parts of rubber particles ("Staphyloid AC3816N" manufactured by Aica Kogyo Co., Ltd.), 7) 26 parts of an active ester compound (DIC Corporation's "HPC-8000-65T," active ester group equivalent weight approximately 223 g / eq., toluene solution with a non-volatile content of 65%) was not used. Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane is shown below. [ka]

[0240] Example 15 In Example 1, 1) 15 parts of naphthalene-type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ESN475V", epoxy equivalent weight approximately 332 g / eq.) was replaced with 15 parts of dicyclopentadiene-type epoxy resin (DIC Corporation "HP-7200HH", epoxy equivalent weight approximately 280 g / eq.), 2) 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of nordihydroguaiaretic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3) The amount of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) was changed from 4 parts to 2 parts. 4) One part of an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industries, Ltd., 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 10% by mass) was used. Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of nordihydroguaiaretic acid is shown below. [ka]

[0241] Example 16 In Example 1, 1) 10 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent weight approximately 194 g / eq.) was replaced with 10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828EL", epoxy equivalent weight approximately 180 g / eq.), 2) 5 parts of phenolphthalimidine type epoxy resin (Nippon Kayaku Co., Ltd. "WHR-991S", epoxy equivalent: approximately 265 g / eq.) 3) The amount of naphthalene-type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ESN475V", epoxy equivalent weight approximately 332 g / eq.) was changed from 15 parts to 10 parts. 4) 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of 4,6,7-trihydroxycoumarin (manufactured by BOC Sciences), 5) The amount of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) was changed from 4 parts to 2 parts. 6) One part of an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industries, Ltd., 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 10% by mass) was used. Except for the above, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of 4,6,7-trihydroxycoumarin is shown below. [ka]

[0242] <Comparative Example 1> In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 4 parts of a naphthol-type curing agent ("SN-485" manufactured by Nippon Steel Chemical & Material Co., Ltd., hydroxyl group equivalent: approximately 205 g / eq.). A resin varnish and a resin sheet were prepared in the same manner as in Example 1, except for the above.

[0243] <Comparative Example 2> In Example 1, 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was changed to 2 parts of Resveratrol (manufactured by Tokyo Chemical Industry Co., Ltd.). Otherwise, a resin varnish and a resin sheet were prepared in the same manner as in Example 1. The structure of Resveratrol is shown below. [ka]

[0244] <Comparative Example 3> A resin varnish and a resin sheet were prepared in the same manner as in Example 1, except that 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 2 parts of Curcumin (manufactured by Tokyo Chemical Industry Co., Ltd.). The structure of Curcumin is shown below. [ka]

[0245] <Comparative Example 4> In Example 1, 1) 4 parts of the catechol-based resin (1) obtained in Synthesis Example 1 was replaced with 4 parts of a naphthol-type curing agent ("SN-485" manufactured by Nippon Steel Chemical & Material Co., Ltd., hydroxyl group equivalent: approximately 205 g / eq.), 2) The amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 120 parts to 180 parts. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0246] <Comparative Example 5> In Example 1, the amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 120 parts to 50 parts. A resin varnish and a resin sheet were prepared in the same manner as in Example 1 except for the above.

[0247] <Measurement of coefficient of linear thermal expansion (CTE) and elongation at break (mechanical strength) of cured product> (1) Preparation of cured product for evaluation A PET film (501010 manufactured by Lintec Corporation, 50 μm thick, 240 mm square) with a release-treated surface and an untreated surface was prepared. A glass cloth-based epoxy resin double-sided copper-clad laminate (R5715ES manufactured by Panasonic Corporation, 0.7 mm thick, 255 mm square) was placed on the untreated surface of the PET film, and the four sides were fixed with polyimide adhesive tape (10 mm wide).

[0248] Next, the resin varnishes produced in the examples and comparative examples were applied to the treated surface of the PET film using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and then dried at 80°C to 120°C (average 100°C) for 6 minutes to obtain a resin sheet. The sheet was then placed in an oven at 190°C and thermally cured for 90 minutes. After thermal curing, the polyimide adhesive tape was peeled off, the glass cloth-based epoxy resin double-sided copper-clad laminate was removed, and the PET film was peeled off to obtain a sheet-like cured product. The obtained cured product is referred to as the "cured product for evaluation."

[0249] (2) Measurement of the coefficient of linear thermal expansion The cured product for evaluation was cut into test pieces approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310") using the tensile load method. After mounting the test pieces in the analyzer, measurements were performed twice consecutively under the conditions of a load of 1 g and a heating rate of 5°C / min. In the second measurement, the average linear thermal expansion coefficient from 25°C to 150°C was calculated and evaluated based on the following criteria. 〇: Linear thermal expansion coefficient is less than 30 ppm / ℃ ×: Linear thermal expansion coefficient is 30 ppm / ℃ or more

[0250] (3) Measurement of elongation at break The cured products for evaluation were subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) and evaluated based on the following criteria. ◯: Elongation at break is 1.0% or more ×: Elongation at break is less than 1.0%

[0251] <Crack evaluation test> (1) Lamination of resin sheets An inner layer substrate (Hitachi Chemical Co., Ltd., "MCL-E700G"; conductor layer thickness: 35 μm, total thickness: 0.4 mm, residual copper ratio: 40%) was prepared. The inner layer substrate had a circuit conductor (copper) formed on both sides with a wiring pattern of line / space ratio (L / S) = 8 μm / 8 μm. Resin sheets with supports were laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, "CVP700") by vacuum suction at a temperature of 120°C for 30 seconds, followed by pressing from above the support via heat-resistant rubber at a temperature of 120°C and a pressure of 0.7 MPa for 30 seconds. Next, pressing was performed using a stainless steel end plate at atmospheric pressure at a temperature of 120°C and a pressure of 0.55 MPa for 60 seconds.

[0252] (2) Thermal curing of the resin composition layer The support was peeled off from the laminated resin sheet with the support. The substrate was placed in a 130°C oven and heated for 30 minutes, then transferred to a 170°C oven and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thus, a sample substrate with a layer structure of inner layer substrate / insulating layer was obtained. The sample substrate was then left to cool to room temperature (25°C).

[0253] (3) Roughening treatment The cooled sample substrate was immersed in a swelling solution, Swelling Dip Securiganth P (manufactured by Atotech Japan), at 60°C for 10 minutes. Next, it was immersed in a roughening solution, Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) (manufactured by Atotech Japan), at 80°C for 20 minutes. Finally, it was immersed in a neutralizing solution, Reduction Solution Securiganth P (manufactured by Atotech Japan), at 40°C for 5 minutes. The sample substrate was then dried at 80°C for 30 minutes.

[0254] (4) Evaluation of cracks The L / S pattern of the inner layer substrate was observed on the insulating layer surface of the sample substrate after the roughening treatment. 100 sections on the pattern of the inner layer substrate were checked for cracks on the surface along the pattern shape, and the number of sections on the pattern without cracks was counted. The percentage of sections without cracks out of the 100 sections was calculated as the "yield." The higher the yield, the better. The calculated yield was then scored according to the following criteria. 1 point: 0% or more but less than 20%. 2 points: 20% or more but less than 40%. 3 points: 40% or more but less than 60%. 4 points: 60% or more but less than 80%. 5 points: 80% or above. Furthermore, a score of 3 or more was judged as a cracking evaluation of "good", and a score of 2 or less was judged as a cracking evaluation of "poor".

[0255] [Table 1] [Table 2] In the table, the content of the thermosetting resin (total content of components (A), (B), (D), and (E)), the content of component (C), and the content of component (F) represent the content when the nonvolatile components in the resin composition are taken as 100% by mass.

Claims

1. (A) an epoxy resin, (B) a catechol-based curing agent, and (C) a resin composition comprising an inorganic filler, The component (B) contains at least one of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3), A resin composition for forming an insulating layer for forming an interlayer insulating layer of a printed wiring board or a conductor layer including a rewiring layer, wherein the content of component (C) is 50% by mass or more and 85% by mass or less, when the non-volatile components in the resin composition are 100% by mass. 【Chemical 1】 In formula (B-1), R 11 each independently represent a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; R 12 each independently represent a single bond or a divalent hydrocarbon group which may have a substituent; and R 12 may be bonded to the benzene ring in formula (B-1) to form a ring. R 13 each independently represent an amide bond, a carbonyl group, -C(═O)O-, -OC(═O)O-, -O-, -NR a -, or a divalent group selected from the group consisting of a combination of two or more thereof; R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 14 represents a divalent or trivalent group represented by any of the following formulae (i) to (vii). k represents an integer of 2 to 3. In formula (B-2), R 21 and R 23 each independently represent a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group which may have a substituent, and R 22 represents a divalent linear or branched saturated hydrocarbon group having 3 to 10 carbon atoms, and R 22 may bond to the benzene ring in formula (B-2) to form a spiro ring. In formula (B-3), R 31 represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, ring B represents a ring structure which is condensed with the benzene ring in formula (B-3) and represents a lactone structure or a cyclic ketone structure, R 32 each independently represents an aryl group which may have a substituent, or an alkyl group which may have a substituent, and 1 represents an integer of 0 to 2. 【Chemistry 2】 In formulas (i) to (vii), "*" represents a bond.

2. The resin composition according to claim 1, further comprising (D) a curing agent (excluding those corresponding to component (B)).

3. R in formula (B-1) １１ , R in formula (B-2) ２１ , and R ２３ and R in formula (B-3) ３１ The resin composition according to claim 1 , wherein represents a hydrogen atom or a hydroxy group.

4. R in formula (B-1) １２ The resin composition according to claim 1 , wherein represents a single bond, an alkylene group which may have a substituent, or an alkenylene group which may have a substituent.

5. The resin composition according to claim 1, wherein ring B in formula (B-3) is any one of a δ-valerolactone structure, a 4-oxy-2-cyclohexenone structure, and a 2-oxy-5-cyclohexenone structure.

6. The resin composition according to claim 1, wherein the content of the component (C) is 50% by mass or more and 80% by mass or less, when the total amount of nonvolatile components in the resin composition is 100% by mass.

7. The resin composition according to claim 1, wherein the average particle size of the component (C) is 0.01 μm or more and 5 μm or less.

8. The resin composition according to claim 2 , wherein the curing agent (D) comprises an active ester curing agent.

9. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of claims 1 to 8.

10. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 8.

11. A semiconductor device comprising the printed wiring board according to claim 10.

12. A catechol-based curing agent containing at least one of a compound represented by the following formula (B-1), a compound represented by the following formula (B-2), and a compound represented by the following formula (B-3): 【Chemistry 3】 In formula (B-1), R １１ each independently represents a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, or an optionally substituted alkoxy group; R １２ each independently represents a single bond or a divalent hydrocarbon group which may have a substituent, R １２ may be bonded to the benzene ring in formula (B-1) to form a ring. １３ each independently represents an amide bond, a carbonyl group, —C(═O)O—, —OC(═O)O—, —O—, or —NR ａ represents a divalent group selected from the group consisting of - or a combination of two or more thereof, and R ａ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １４ represents a divalent or trivalent group represented by the following formulas (i) to (vii), and k represents an integer of 2 or 3. In formula (B-2), R ２１ , and R ２３ each independently represents a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group which may have a substituent; R ２２ represents a divalent linear or branched saturated hydrocarbon group having 3 to 10 carbon atoms, R ２２ may be bonded to the benzene ring in formula (B-2) to form a spiro ring. In formula (B-3), R ３１ represents a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; ring B is a ring structure which is condensed with the benzene ring in formula (B-3) and represents a lactone structure or a cyclic ketone structure; R ３２ each independently represents an aryl group which may have a substituent, or an alkyl group which may have a substituent, and 1 represents an integer of 0 to 2. 【Chemistry 4】 In formulas (i) to (vii), "*" represents a bond.

13. The catechol-based curing agent according to claim 12, for incorporation into a resin composition for forming an insulating layer for forming an interlayer insulating layer of a printed wiring board or a conductor layer including a rewiring layer.

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