Polyphenol resin, resin composition, cured product thereof, and uses thereof

Abstract

Provided is a novel polyhydric phenolic resin that provides a cured product having excellent toughness. The polyhydric phenolic resin (X) contains a polydiene skeleton, and is characterized by containing a structural unit represented by formula (1). (In formula (1), Rp1 and Rp3 each independently represent a hydrogen atom, a methyl group, or an ethyl group, Rp2 represents a hydrogen atom, a methyl group, or a bond, one of X1 and X2 represents a hydroxy group while the other represents a monovalent group represented by formula (2), and * represents a bond. The C-C bond structure in formula (1) is a portion of the polydiene skeleton. In formula (2), each RS independently represents a substituent, * represents a bond, and n represents a number from 0 to 4.)

Description

[Technical Field]

[0001] The present invention relates to a polyhydric phenol resin, a method for producing the polyhydric phenol resin, a resin composition containing the polyhydric phenol resin, and uses thereof, such as a cured product, a resin sheet, a prepreg, a printed wiring board, a semiconductor chip package, and a semiconductor device. [Background technology]

[0002] Phenolic resins are widely used in automobile parts such as brakes, electronic parts such as semiconductor chip packages and printed wiring boards, due to their excellent mechanical strength and heat resistance.

[0003] For example, compounds containing phenolic resins and curing agents such as hexamine or methylolmelamine, or compounds containing epoxy resins as curing agents, can be cured by heating to obtain strong cured products. Phenolic resins are also used as raw materials for epoxy resins. Furthermore, compounds containing phenolic resins and photosensitive agents such as photoacid generators or naphthoquinone diazide compounds are also used as photoresists for semiconductors and liquid crystal displays.

[0004] Common phenolic resins are phenol-formaldehyde resins, including phenol novolac resins, which are polycondensates of phenols and formaldehyde. By adjusting the molecular weight or changing the type of phenol, such as to cresol or alkylphenol, improvements can be made in moldability, heat resistance, and mechanical properties. However, phenolic resins have inherent drawbacks, such as poor flexibility and being hard and brittle when cured. One way to improve this is to add flexibility-imparting materials such as rubber components, but this often results in adverse effects such as reduced mechanical strength.

[0005] As improvements from the viewpoint of molecular structure, Patent Document 1 proposes an alicyclic skeleton nodular phenolic resin obtained by polyaddition reaction of dicyclopentadiene and phenol, Patent Document 2 proposes an aralkyl phenolic resin having xylylene as the nodular group, and Patent Document 3 proposes a biphenyl aralkyl resin having a biphenyl skeleton as the nodular group. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 03-179021 [Patent Document 2] Japanese Patent Application Publication No. 63-238151 [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-040053 Summary of the Invention [Problem to be solved by the invention]

[0007] The modified phenolic resins described in Patent Documents 1 to 3 have a molecular weight of the linking group that polynucleates the phenol monomer that is significantly larger than that of phenol-formaldehyde resins, and are intended to reduce the functional group density. However, the effect of improving flexibility is small in all of them, and they are unable to impart sufficiently satisfactory toughness to the cured product.

[0008] An object of the present invention is to provide a novel polyhydric phenol resin that gives a cured product exhibiting good toughness. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that a polyhydric phenol resin having the following structure can provide a cured product exhibiting good toughness, and have thus completed the present invention.

[0010] That is, the present invention includes the following. [1] A polyhydric phenol resin (X) containing a polydiene skeleton, A polyhydric phenol resin (X) containing a structural unit represented by the following formula (1): [ka] (In formula (1), R p1 and R p3 each independently represents a hydrogen atom, a methyl group, or an ethyl group, R p2 represents a hydrogen atom, a methyl group, or a bond, X 1 and X 2 one of which represents a hydroxy group, and the other represents a monovalent group represented by the following formula (2): * indicates a bond, where the CC bond structure in formula (1) is part of the polydiene skeleton. [ka] In formula (2), R S each independently represents a substituent, * indicates a bond, n is a number from 0 to 4. [2] A structural unit A represented by the following formula (A), one or more structural units B selected from a structural unit B1 represented by the following formula (B1) and a structural unit B2 represented by the following formula (B2), The polyhydric phenol resin (X) according to [1], [ka] (In the formula, R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, R S and n are the same as above.) [3] The polyhydric phenol resin (X) according to [1] or [2], further comprising a structural unit C represented by the following formula (C): [ka] (In the formula, R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group. [4] The polyhydric phenol resin (X) according to [2] or [3], wherein the molar ratio of the structural unit A to the structural unit B (structural unit A:structural unit B) is in the range of 15:85 to 85:15. [5] The polyhydric phenol resin (X) according to [3] or [4], wherein the molar ratio of the structural unit B to the structural unit C (structural unit B:structural unit C) is in the range of 20:80 to 100:0. [6] The polyhydric phenol resin (X) according to any one of [1] to [5], wherein the polydiene skeleton is a polybutadiene skeleton. [7] The polyhydric phenol resin (X) according to any one of [1] to [6], which has a phenolic hydroxyl group equivalent in the range of 200 to 1000 g / eq. [8] The polyhydric phenol resin (X) according to any one of [3] to [7], which has an epoxy group equivalent of 3000 g / eq. or more. [9] The polyhydric phenol resin (X) according to any one of [3] to [8], wherein the molar ratio of epoxy groups to phenolic hydroxyl groups (epoxy groups:phenolic hydroxyl groups) is in the range of 80:20 to 0:100.

[10] The polyhydric phenol resin (X) according to any one of [1] to [9], which is a reaction product of an epoxy-modified polydiene compound (x1) and a mercaptophenol compound (x2).

[11] The polyhydric phenol resin (X) according to

[10] , wherein the epoxy-modified polydiene compound (x1) contains a structure represented by the following formula (x1): [ka] (In the formula, R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, a and c represent the average number of each structural unit.

[12] The polyhydric phenol resin (X) according to

[10] or

[11] , wherein the epoxy group equivalent of the epoxy-modified polydiene compound (x1) is in the range of 150 to 500 g / eq.

[13] The polyhydric phenol resin (X) according to any one of

[10] to

[12] , wherein the reaction molar ratio of the epoxy groups in the epoxy-modified polydiene compound (x1) to the mercaptophenol compound (x2) (epoxy groups:mercaptophenol compound) is in the range of 100:10 to 100:100.

[14] The polyhydric phenol resin (X) according to any one of

[10] to

[13] , wherein the content of the unreacted mercaptophenol compound (x2) is 10 mass % or less.

[15] A method for producing the polyhydric phenol resin (X) according to any one of [1] to

[14] , which comprises reacting an epoxy-modified polydiene compound (x1) with a mercaptophenol compound (x2).

[16] The method for producing the polyhydric phenol resin (X) according to

[15] , wherein the reaction temperature is in the range of 30 to 150°C.

[17] A method for producing the polyhydric phenol resin (X) according to

[15] or

[16] , which does not substantially use a reaction catalyst.

[18] A resin composition comprising the polyhydric phenol resin (X) according to any one of [1] to

[14] .

[19] The resin composition according to

[18] , which is a thermosetting resin composition or a photocurable resin composition.

[20] The resin composition according to

[18] or

[19] , further comprising a thermosetting resin.

[21] The resin composition according to any one of

[18] to

[20] , further comprising an inorganic filler.

[22] The resin composition according to any one of

[18] to

[21] , which is for use in an insulating layer of a printed wiring board.

[23] The resin composition according to any one of

[18] to

[21] , which is used for semiconductor encapsulation.

[24] A resin sheet comprising a support and a layer of the resin composition according to any one of

[18] to

[23] provided on the support.

[25] The resin sheet according to

[24] , wherein the support is a thermoplastic resin film or a metal foil.

[26] A prepreg obtained by impregnating a sheet-like fiber substrate with the resin composition according to any one of

[18] to

[23] .

[27] A cured product of the resin composition according to any one of

[18] to

[23] .

[28] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of

[18] to

[22] .

[29] A semiconductor chip package comprising an encapsulating layer made of a cured product of the resin composition according to any one of

[18] to

[21] and

[23] .

[30] The semiconductor chip package according to

[29] , which is a fan-out type package.

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

[28] or the semiconductor chip package according to

[29] or

[30] . [Effects of the Invention]

[0011] According to the present invention, a novel polyhydric phenol resin can be provided that gives a cured product exhibiting good toughness. [Brief explanation of the drawings]

[0012] [Figure 1a] FIG. 1a shows the 1H-NMR spectrum of the polyhydric phenol resin (1) in Example 1. [Figure 1b] FIG. 1b shows the 13C-NMR spectrum of the polyhydric phenol resin (1) in Example 1. [Figure 1c] FIG. 1c shows a GPC chart of the polyhydric phenol resin (1) in Example 1. [Figure 1d] FIG. 1d shows an IR chart of the polyhydric phenol resin (1) in Example 1. [Figure 2a] FIG. 2a shows a GPC chart of the polyhydric phenol resin (2) in Example 2. [Figure 2b] FIG. 2b shows an IR chart of the polyhydric phenol resin (2) in Example 2. [Figure 3a] FIG. 3a shows a GPC chart of the polyhydric phenol resin (3) in Example 3. [Figure 3b] FIG. 3b shows an IR chart of the polyhydric phenol resin (3) in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0013] <Terminology> 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.

[0014] In this specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkapolyenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy 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.

[0015] Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine atoms. The alkyl group used as a substituent may be either linear or branched. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. The alkenyl group used as a substituent may be either linear or branched. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 or 3. The alkynyl group used as a substituent may be either linear or branched. The alkynyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 or 3. The alkapolyenyl group used as a substituent may be either linear or branched, and the number of double bonds is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2. The alkapolyenyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 14, and even more preferably 3 to 12, or 3 to 6. The cycloalkyl group used as a substituent preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cycloalkenyl group used as a substituent preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The alkoxy group used as a substituent may be either linear or branched. The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 6. The cycloalkyloxy group used as a substituent preferably has 3 to 12 carbon atoms, more preferably 3 to 6. 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 aryl group used as a substituent preferably has 6 to 14 carbon atoms, more preferably 6 to 10. The aryloxy group used as a substituent preferably has 6 to 14 carbon atoms, more preferably 6 to 10. The arylalkyl group used as a substituent preferably has 7 to 15 carbon atoms, more preferably 7 to 11. The arylalkoxy group used as a substituent preferably has 7 to 15 carbon atoms, more preferably 7 to 11.The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound. The number of carbon atoms in the monovalent heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. 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), and 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 acyl group or acyloxy group is preferably 2 to 13, more preferably 2 to 7. 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.

[0016] In this specification, the term "polydiene skeleton" refers to a skeleton formed by diene polymerization of a conjugated diene compound such as 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, and 4-methyl-1,3-pentadiene. For example, butadiene-derived polydiene skeletons include cis-1,4-bonded polydiene skeletons, trans-1,4-bonded polydiene skeletons, and 1,2-bonded polydiene skeletons, while isoprene-derived polydiene skeletons include cis-1,4-bonded polydiene skeletons, trans-1,4-bonded polydiene skeletons, 1,2-bonded polydiene skeletons, and 3,4-bonded polydiene skeletons. Hereinafter, the type of polydiene skeleton may be specified according to the type of conjugated diene compound from which it is derived, such as a butadiene-derived polydiene skeleton being referred to as a "polybutadiene skeleton," an isoprene-derived polydiene skeleton being referred to as a "polyisoprene skeleton," and a pentadiene-derived polydiene skeleton being referred to as a "polypentadiene skeleton."

[0017] In this specification, the term "polydiene compound" refers to a compound having a polydiene skeleton. Here, the polydiene compound typically has multiple polydiene skeletons such as cis-1,4-bonds, trans-1,4-bonds, 1,2-bonds, and (in the case of isoprene, etc.) 3,4-bonds, and preferred embodiments for achieving the effects of the present invention will be described later.

[0018] In this specification, the term "epoxy-modified polydiene compound" refers to a compound in which at least a portion of the carbon-carbon double bonds of a polydiene compound have been modified to an epoxide structure.

[0019] As used herein, the term "mercaptophenol compound" refers to a phenol compound having a thiol group (SH-). In the mercaptophenol compound, the benzene ring may further have other substituents as long as it has a thiol group and a hydroxy group.

[0020] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0021] [Polyphenol resin (X)] The polyhydric phenol resin (X) of the present invention is a polyhydric phenol resin containing a polydiene skeleton, and is characterized by containing a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1)"). [ka] (In formula (1), R p1 and R p3 each independently represents a hydrogen atom, a methyl group, or an ethyl group, R p2 represents a hydrogen atom, a methyl group, or a bond, X 1 and X 2 one of which represents a hydroxy group, and the other represents a monovalent group represented by the following formula (2): * indicates a bond, where the CC bond structure in formula (1) is part of the polydiene skeleton. [ka] In formula (2), R S each independently represents a substituent, * indicates a bond, n is a number from 0 to 4.

[0022] The polyhydric phenol resin (X) of the present invention, which includes a polydiene skeleton and the structural unit (1), can provide a cured product exhibiting good toughness. As described below, the polyhydric phenol resin (X) of the present invention is synthesized by reacting the epoxy group of an epoxy-modified polydiene compound with the thiol group of a mercaptophenol compound. The structural unit (1) represents a phenol-modified site formed by reaction of the epoxy group of the epoxy-modified polydiene compound with the thiol group of the mercaptophenol compound. For example, in a 1,2-bonded polydiene skeleton, the structural unit (1) (in the formula, R p2 represents a hydrogen atom or a methyl group.) is contained in the side chain portion, and in the polydiene skeleton of cis-1,4-bond or trans-1,4-bond, the structural unit (1) (wherein R p2 indicates a bond. ) is included in the main chain.

[0023] In the structural unit (1), X 1 and X 2 One of the groups represents a hydroxy group, and the other represents a monovalent group represented by the above formula (2). In the reaction between the epoxy group of the epoxy-modified polydiene compound and the thiol group of the mercaptophenol compound, isomers are generated depending on the manner of cleavage of the epoxy group. For example, when cleavage of the epoxy group occurs between the carbon atom and the oxygen atom shown on the left side in formula (1), X 1 is a monovalent group represented by formula (2) and X 2 results in the structural unit (1) which is a hydroxy group, and when the cleavage of the epoxy group occurs between the carbon atom and the oxygen atom shown on the right side in formula (1), X 1 is a hydroxy group and X 2 This results in the structural unit (1), which is a monovalent group represented by formula (2) (for the structure before the epoxy group is cleaved, see structural units C and C2 described below).

[0024] In formula (1), R p1 and R p3are each independently a hydrogen atom, a methyl group, or an ethyl group depending on the epoxy-modified polydiene compound used as a raw material. For example, when an epoxy-modified polybutadiene compound is used, R p1 and R p3 For example, when an epoxy-modified poly(2-methyl-1,3-butadiene) compound, i.e., an epoxy-modified polyisoprene compound, is used, in the 1,2-bonded polydiene skeleton, R p1 and R p3 Both represent hydrogen atoms, and in the polydiene skeleton of cis-1,4-bonds or trans-1,4-bonds, R p1 is a methyl group, R p3 represents a hydrogen atom, and in the 3,4-bonded polydiene backbone, R p1 is a hydrogen atom, R p3 For example, when an epoxy-modified poly(2-ethyl-1,3-butadiene) compound is used, R p1 and R p3 Both represent hydrogen atoms, and in the polydiene skeleton of cis-1,4-bonds or trans-1,4-bonds, R p1 is an ethyl group, R p3 represents a hydrogen atom, and in the 3,4-bonded polydiene backbone, R p1 is a hydrogen atom, R p3 indicates an ethyl group.

[0025] In formula (1), R p2 represents a hydrogen atom, a methyl group, or a bond depending on the type of epoxy-modified polydiene compound used as a raw material and the form of the polydiene skeleton. For example, when an epoxy-modified polybutadiene compound or an epoxy-modified polyisoprene compound is used, R p2 represents a hydrogen atom, and in the case of a polydiene skeleton having a cis-1,4-bond or a trans-1,4-bond, R p2 When an epoxy-modified polypentadiene compound is used, Rp2 indicates a methyl group.

[0026] In formula (2), R S R indicates a substituent. S The substituent represented by the formula (I) is as described above. Among them, from the viewpoint of being able to enjoy the effects of the present invention more effectively, one or more types selected from a halogen atom, an alkyl group, and an aryl group are preferred, and one or more types selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferred.

[0027] In formula (2), n represents a number of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0028] From the viewpoint of providing a cured product exhibiting even better toughness, it is preferable that the polyhydric phenol resin (X) contains the structural unit (1) so that the phenolic hydroxyl group equivalent is preferably 200 g / eq. or more, more preferably 220 g / eq. or more, even more preferably 240 g / eq. or more, 250 g / eq. or more, 260 g / eq. or more, or 280 g / eq. or more. Furthermore, it is preferable that the structural unit (1) is contained so that the upper limit of the phenolic hydroxyl group equivalent is preferably 1000 g / eq. or less, more preferably 900 g / eq. or less, even more preferably 800 g / eq. or less, 750 g / eq. or less, 700 g / eq. or less, 680 g / eq. or less, 660 g / eq. or less, or 650 g / eq. or less. Therefore, in a preferred embodiment, the phenolic hydroxyl group equivalent of the polyhydric phenol resin (X) is in the range of 200 to 1000 g / eq. The phenolic hydroxyl group equivalent of the polyhydric phenol resin (X) is the mass of the polyhydric phenol resin (X) containing one equivalent of phenolic hydroxyl groups, and can be measured in accordance with JIS K0070.

[0029] From the viewpoint of realizing a polyhydric phenol resin (X) that provides a cured product excellent in both flexural toughness and tensile toughness, the epoxy-modified polydiene compound used as a raw material preferably contains a polydiene skeleton formed by diene polymerization of one or more conjugated diene compounds selected from the group consisting of 1,3-butadiene, isoprene (i.e., 2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 2-ethyl-1,3-butadiene, more preferably contains a polydiene skeleton formed by diene polymerization of one or more conjugated diene compounds selected from 1,3-butadiene and isoprene (2-methyl-1,3-butadiene), and even more preferably contains a polydiene skeleton formed by diene polymerization of 1,3-butadiene. That is, the polyhydric phenol resin (X) preferably contains one or more polydiene skeletons selected from a polybutadiene skeleton, a polyisoprene skeleton, a poly2,3-dimethyl-1,3-butadiene skeleton, and a poly2-ethyl-1,3-butadiene skeleton, more preferably contains one or more polydiene skeletons selected from a polybutadiene skeleton and a polyisoprene skeleton, and further preferably contains a polybutadiene skeleton as the polydiene skeleton.

[0030] Furthermore, from the viewpoint of providing a cured product excellent in both flexural toughness and tensile toughness, the polyhydric phenol resin (X) preferably contains a 1,2-bonded polydiene skeleton or a 3,4-bonded polydiene skeleton. Here, a 3,4-bonded polydiene skeleton can be contained when the epoxy-modified polydiene compound used as a raw material contains a polydiene skeleton formed by diene polymerization of a conjugated diene compound that has a substituent at the 2-position carbon atom but not at the 3-position carbon atom, or has different substituents at the 2-position carbon atom and the 3-position carbon atom, such as isoprene or 2-ethyl-1,3-butadiene. In this regard, in a polydiene skeleton formed by diene polymerization of a conjugated diene compound having no substituents on either the 2- or 3-position carbon atom, such as 1,3-butadiene, or a conjugated diene compound having the same substituents on the 2- and 3-position carbon atoms, such as 2,3-dimethyl-1,3-butadiene, the 1,2-bonded polydiene skeleton and the 3,4-bonded polydiene skeleton are the same, and both will be referred to as a 1,2-bonded polydiene skeleton.

[0031] From the viewpoint of providing a cured product having even more excellent flexural toughness and tensile toughness, when the total amount of polydiene skeletons contained in the polyhydric phenol resin (X) is taken as 100 mol%, the total content of 1,2-bonded polydiene skeletons and 3,4-bonded polydiene skeletons is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 65 mol% or more, 70 mol% or more, or more than 70 mol%. The upper limit of the total content of 1,2-bonded polydiene skeletons and 3,4-bonded polydiene skeletons may be 100 mol%, but may also be, for example, 99.9 mol% or less, 99.5 mol% or less, 99 mol% or less, or 98 mol% or less.

[0032] In the polyhydric phenol resin (X) of the present invention, the polydiene skeleton may contain, in addition to the 1,2-bonded polydiene skeleton and the 3,4-bonded polydiene skeleton, one or more polydiene skeletons selected from the group consisting of cis-1,4-bonded polydiene skeletons and trans-1,4-bonded polydiene skeletons.

[0033] In a preferred embodiment, when the total amount of polydiene skeletons contained in the polyhydric phenol resin (X) of the present invention is taken as 100 mol %, the total content of 1,2-bonded polydiene skeletons and 3,4-bonded polydiene skeletons is 70 mol % or more, and the remainder comprises one or more polydiene skeletons selected from the group consisting of cis-1,4-bonded polydiene skeletons and trans-1,4-bonded polydiene skeletons.

[0034] The polyhydric phenol resin (X) of the present invention may contain epoxy groups derived from the epoxy-modified polydiene compound used as a raw material. That is, when producing the polyhydric phenol resin (X) of the present invention, it is not necessary to convert all of the epoxy groups in the epoxy-modified polydiene compound used as a raw material into structural units (1) by reacting them with a mercaptophenol compound, and the polyhydric phenol resin (X) of the present invention may contain unreacted epoxy groups. For example, the epoxy groups are contained in the side chain portion of a 1,2-bonded or 3,4-bonded polydiene skeleton (see structural unit C described below), and in the main chain portion of a cis-1,4-bonded or trans-1,4-bonded polydiene skeleton (see structural unit C2 described below).

[0035] When the polyhydric phenol resin (X) contains epoxy groups, the epoxy group equivalent of the polyhydric phenol resin (X) is preferably 500 g / eq. or more, more preferably 1000 g / eq. or more, 1500 g / eq. or more, 2000 g / eq. or more, or 2500 g / eq. or more, and even more preferably 3000 g / eq. or more, 3500 g / eq. or more, 4000 g / eq. or more, 4500 g / eq. or more, or 5000 g / eq. or more. When the polyhydric phenol resin (X) contains epoxy groups, the upper limit of the epoxy group equivalent of the polyhydric phenol resin (X) is not particularly limited, but may be, for example, 500,000 g / eq. or less, 400,000 g / eq. or less, or 300,000 g / eq. or less. Therefore, in one embodiment, the epoxy group equivalent of the polyhydric phenol resin (X) of the present invention is 3,000 g / eq. or more. The epoxy group equivalent of the polyhydric phenol resin (X) is the mass of the polyhydric phenol resin (X) containing one equivalent of epoxy groups, and can be measured in accordance with JIS K7236.

[0036] In the polyphenol resin (X) of the present invention, the molar ratio of epoxy groups to phenolic hydroxyl groups (epoxy groups:phenolic hydroxyl groups) is preferably in the range of 90:10 to 0:100, more preferably 80:20 to 0:100, even more preferably 70:30 to 0:100, 60:40 to 0:100, 50:50 to 0:100, 40:60 to 0:100, 30:70 to 0:100, or 20:80 to 0:100, from the viewpoint of achieving the effects of the present invention. As mentioned above, it is not necessary for all of the epoxy groups to be phenol-modified (converted to structural unit (1)) by reacting with a mercaptophenol compound. Therefore, the upper limit of the above preferred range (focusing on the phenolic hydroxyl groups) may be 0.1:99.9 or less, 0.5:99.5 or less, 1:99 or less, or 2:98 or less. Therefore, in one embodiment, the molar ratio of epoxy groups to phenolic hydroxyl groups (epoxy groups:phenolic hydroxyl groups) is in the range of 80:20 to 0:100.

[0037] As mentioned above, not all of the mercaptophenol compound used as a raw material may be subjected to the reaction, and the polyhydric phenol resin (X) of the present invention may contain unreacted mercaptophenol compound (preferable embodiments will be described later). For example, when the polyhydric phenol resin (X) of the present invention is taken as 100% by mass, the polyhydric phenol resin (X) may contain preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less or 5% by mass or less of unreacted mercaptophenol compound. The lower limit of the content of the unreacted mercaptophenol compound may be 0% by mass. Therefore, in one embodiment, the content of the unreacted mercaptophenol compound is 10% by mass or less.

[0038] A particularly preferred embodiment from the viewpoint of providing a cured product excellent in both flexural toughness and tensile toughness will be described below.

[0039] In a preferred embodiment, the polyhydric phenol resin (X) is A structural unit A represented by the following formula (A), one or more structural units B selected from a structural unit B1 represented by the following formula (B1) and a structural unit B2 represented by the following formula (B2), Includes.

[0040] [ka] (In the formula, R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group, R S and n are the same as above.)

[0041] The structural unit A is a structural unit constituting a 1,2-bonded or 3,4-bonded polydiene skeleton. For example, when the epoxy-modified polydiene compound used as a raw material has a polydiene skeleton formed by diene polymerization of 1,3-butadiene, the structural unit A is a structural unit constituting a 1,2-bonded polydiene skeleton, and R 1 and R 2 For example, when the epoxy-modified polydiene compound used as a raw material has a polydiene skeleton formed by diene polymerization of isoprene, the structural unit A is a structural unit constituting the polydiene skeleton of 1,2-bonds, and R 1 is a methyl group, R 2 is a hydrogen atom or a structural unit constituting a 3,4-bonded polydiene skeleton, and R 1 is a hydrogen atom, R 2 is a methyl group. When the epoxy-modified polydiene compound used as a raw material has a polydiene skeleton formed by diene polymerization of 2-ethyl-1,3-butadiene, the structural unit A is a structural unit constituting a 1,2-bonded polydiene skeleton, and R 1 is an ethyl group, R 2 is a hydrogen atom or a structural unit constituting a 3,4-bonded polydiene skeleton, and R 1 is a hydrogen atom, R 2 is an ethyl group.

[0042] From the viewpoint of producing a cured product with excellent flexural toughness and tensile toughness, R 1 and R 2 are each independently preferably a hydrogen atom or a methyl group.

[0043] Structural unit B is a structural unit that constitutes a 1,2-bonded or 3,4-bonded polydiene skeleton, and represents a phenol-modified moiety formed by reaction between an epoxy group of the epoxy-modified polydiene compound used as a raw material and a thiol group of the mercaptophenol compound.

[0044] As mentioned above, the polyhydric phenol resin (X) of the present invention is characterized by containing the structural unit (1), and the structural unit B, whether structural unit B1 or B2, contains the structural unit (1) in its side chain portion. The structural units B1 and B2 differ in the bonding position between the monovalent group represented by formula (2) and the hydroxy group. As mentioned above, this is due to the difference in the manner of cleavage of the epoxy group when the epoxy group of the epoxy-modified polydiene compound reacts with the mercaptophenol compound. In this regard, the structural unit B1 corresponds to a case in which cleavage occurs between the second-lowest carbon atom and the oxygen atom in the side chain portion, and the structural unit B2 corresponds to a case in which cleavage occurs between the lowest carbon atom and the oxygen atom in the side chain portion (for the structure before cleavage, see structural unit C described below).

[0045] R contained in structural unit B 1 , R 2 is as explained for the structural unit A, and depends on the type of polydiene skeleton possessed by the epoxy-modified polydiene compound used as a raw material.

[0046] R contained in structural unit B S and n are as explained for the monovalent group represented by formula (2), including their preferred embodiments and values.

[0047] From the viewpoint of providing a cured product exhibiting good toughness, the molar ratio of structural units A to structural units B (structural units A:structural units B) in the polyhydric phenol resin (X) of the present invention is preferably in the range of 15:85 to 90:10, more preferably in the range of 15:85 to 85:15, and even more preferably in the range of 15:85 to 80:20. The lower limit of this molar ratio (focusing on structural units A) is more preferably 20:80 or more, even more preferably 30:70 or more, still more preferably 40:60 or more, 50:50 or more, 60:40 or more, 65:35 or more, or 70:30 or more. Therefore, in one embodiment, the molar ratio of structural units A to structural units B (structural units A:structural units B) in the polyhydric phenol resin (X) is in the range of 15:85 to 85:15.

[0048] As described above, the polyhydric phenol resin (X) of the present invention may contain an epoxy group derived from the epoxy-modified polydiene compound used as a raw material. In one embodiment, the polyhydric phenol resin (X) of the present invention contains a structural unit C represented by the following formula (C):

[0049] [ka] (In the formula, R 1 and R 2 is the same as above.)

[0050] Structural unit C is a structural unit that constitutes a 1,2-bonded or 3,4-bonded polydiene skeleton, and represents the epoxy-modified site of the epoxy-modified polydiene compound used as a raw material, i.e., the unreacted epoxy-modified site that was not subjected to the reaction with the mercaptophenol compound.

[0051] R contained in structural unit C 1 , R 2 is as explained for the structural unit A, and depends on the type of polydiene skeleton possessed by the epoxy-modified polydiene compound used as a raw material.

[0052] From the viewpoint of providing a cured product exhibiting good toughness, the molar ratio of structural units B to structural units C in the polyhydric phenol resin (X) of the present invention (structural units B:structural units C) is preferably in the range of 10:90 to 100:0, more preferably 20:80 to 100:0, and even more preferably 30:70 to 100:0, 40:60 to 100:0, 50:50 to 100:0, 60:40 to 100:0, 70:30 to 100:0, or 80:20 to 100:0. The upper limit of this molar ratio (focusing on structural units B) may be 99.9:0.1 or less, 99.5:0.5 or less, 99:1 or less, or 98:2 or less. Therefore, in one embodiment, the molar ratio of structural units B to structural units C in the polyhydric phenol resin (X) (structural units B:structural units C) is in the range of 20:80 to 100:0.

[0053] The polyhydric phenol resin (X) of the present invention may contain other structural units in addition to the above structural units A, B, and C. Examples of other structural units include structural units that constitute a cis-1,4-bonded or trans-1,4-bonded polydiene skeleton.

[0054] For example, the polyhydric phenol resin (X) of the present invention may further include A structural unit A2 represented by the following formula (A2), one or more structural units B2 selected from a structural unit B2-1 represented by the following formula (B2-1) and a structural unit B2-2 represented by the following formula (B2-2); may include:

[0055] [ka] (In the formula, R 1 , R 2 , R S and n are the same as above.)

[0056] The structural units A2 and B2 are structural units that constitute a polydiene skeleton having a cis-1,4-bond or a trans-1,4-bond. Note that the above formulas (A2), (B2-1), and (B2-2) are shown without distinction between cis and trans geometric isomers.

[0057] R contained in structural units A2 and B2 1 , R 2 is as explained for the structural unit A, and depends on the type of polydiene skeleton possessed by the epoxy-modified polydiene compound used as a raw material.

[0058] For example, when the epoxy-modified polydiene compound used as a raw material has a polydiene skeleton formed by diene polymerization of 1,3-butadiene, the structural unit A2 is a structural unit constituting a polydiene skeleton of cis-1,4-bond or trans-1,4-bond, and R 1 and R 2 For example, when the epoxy-modified polydiene compound used as a raw material has a polydiene skeleton formed by diene polymerization of isoprene, the structural unit A2 is a structural unit constituting a polydiene skeleton of cis-1,4-bonds or trans-1,4-bonds, and R 1 is a methyl group, R 2 is a hydrogen atom.

[0059] Furthermore, structural unit B2 represents a phenol-modified moiety resulting from the reaction between the epoxy group of the epoxy-modified polydiene compound and the thiol group of the mercaptophenol compound used as a raw material. As mentioned above, the polyhydric phenol resin (X) of the present invention is characterized by containing structural unit (1), and structural unit B2, regardless of whether it is structural unit B2-1 or B2-2, contains structural unit (1) in the main chain portion. Structural units B2-1 and B2-2 differ in the bonding position between the monovalent group represented by formula (2) and the hydroxy group. As mentioned above, this is due to the difference in the manner of cleavage of the epoxy group when the epoxy group of the epoxy-modified polydiene compound reacts with the mercaptophenol compound. In this regard, structural unit B2-1 corresponds to a case in which cleavage occurs between the carbon atom and the oxygen atom shown second from the left in the main chain portion, and structural unit B2-2 corresponds to a case in which cleavage occurs between the carbon atom and the oxygen atom shown third from the left in the main chain portion (for the structure before cleavage, see structural unit C2 described below).

[0060] The polyhydric phenol resin (X) of the present invention may further contain a structural unit C2 represented by the following formula (C2).

[0061] [ka] (In the formula, R 1 and R 2 is the same as above.)

[0062] Structural unit C2 represents the epoxy-modified site of an epoxy-modified polydiene compound having a cis-1,4-bonded or trans-1,4-bonded polydiene skeleton when the epoxy-modified polydiene compound is used as a raw material, i.e., the unreacted epoxy-modified site that has not been subjected to the reaction with the mercaptophenol compound.

[0063] R contained in structural unit C2 1 , R 2 is as explained for the structural unit A, and depends on the type of polydiene skeleton possessed by the epoxy-modified polydiene compound used as a raw material.

[0064] From the viewpoint of providing a cured product excellent in both flexural toughness and tensile toughness, when the total amount of polydiene skeletons contained in the polyhydric phenol resin (X) of the present invention is taken as 100 mol%, the total content of the structural units A, B, and C is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 65 mol% or more, 70 mol% or more, or more than 70 mol%. The upper limit of the total content of the structural units A, B, and C may be 100 mol%, but may also be, for example, 99.9 mol% or less, 99.5 mol% or less, 99 mol% or less, or 98 mol% or less.

[0065] In a preferred embodiment, when the total amount of polydiene skeletons contained in the polyhydric phenol resin (X) of the present invention is taken as 100 mol %, the total content of the structural units A, B, and C is 70 mol % or more, and the remainder comprises one or more structural units selected from the group consisting of structural units A2, B2, and C2.

[0066] From the viewpoint of providing a cured product excellent in both flexural toughness and tensile toughness, the average total number of structural units A, B, and C contained per molecule of the polyhydric phenol resin (X) of the present invention is preferably 10 or more, more preferably 12 or more, and even more preferably 14 or more or 15 or more. The upper limit of the average total number of structural units A, B, and C is preferably 100 or less, more preferably 80 or less, and even more preferably 70 or less, 60 or less, 50 or less, or 45 or less. Therefore, in one embodiment, the average total number of structural units A, B, and C contained per molecule of the polyhydric phenol resin (X) of the present invention is in the range of 10 to 100.

[0067] -Synthesis of polyphenol resin (X)- The polyhydric phenol resin (X) of the present invention is synthesized by reacting the epoxy group of an epoxy-modified polydiene compound with the thiol group of a mercaptophenol compound.

[0068] Thus, in one embodiment, the polyhydric phenol resin (X) is Epoxy modified polydiene compound (x1) and Mercaptophenol compounds (x2) and is the reactant of

[0069] -Epoxy-modified polydiene compound (x1)- The component (x1) is an epoxy-modified polydiene compound.

[0070] As described above, the epoxy-modified polydiene compound preferably contains a 1,2-bonded or 3,4-bonded polydiene skeleton from the viewpoint of providing a cured product excellent in both flexural toughness and tensile toughness. The preferred range of the total content of the 1,2-bonded polydiene skeleton and the 3,4-bonded polydiene skeleton when the total amount of polydiene skeletons contained in the epoxy-modified polydiene compound is taken as 100 mol % is as described above for the polyhydric phenol resin (X).

[0071] In a preferred embodiment, the epoxy-modified polydiene compound (x1) comprises a structure represented by the following formula (x1):

[0072] [ka] (In the formula, R 1 and R 2 is the same as above, a and c represent the average number of each structural unit.

[0073] As the epoxy-modified polydiene compound represented by formula (x1), any epoxy-modified polydiene compound containing a 1,2-bonded or 3,4-bonded polydiene skeleton may be used depending on the structure of the desired polyhydric phenol resin (X). 1 or R 2 Suitable examples of R in the desired polyhydric phenol resin (X) are as described above. 1 and R 2 When both R and R are hydrogen atoms, an epoxy-modified polydiene compound having a polydiene skeleton formed by diene polymerization (1,2-bond) of a conjugated diene compound such as 1,3-butadiene having no substituents on either the 2- or 3-position carbon atom may be used. 1 is a methyl group or an ethyl group, R 2 When R is a hydrogen atom, an epoxy-modified polydiene compound having a polydiene skeleton formed by diene polymerization (1,2-bond) of a conjugated diene compound such as isoprene or 2-ethyl-1,3-butadiene having a methyl group or an ethyl group as a substituent at the 2-position carbon atom and no substituent at the 3-position carbon atom may be used. 1 is a hydrogen atom, R 2 When is a methyl group or an ethyl group, an epoxy-modified polydiene compound having a polydiene skeleton formed by diene polymerization (3,4-bond) of a conjugated diene compound such as isoprene or 2-ethyl-1,3-butadiene having a methyl group or an ethyl group as a substituent on the 2-position carbon atom and no substituent on the 3-position carbon atom may be used.

[0074] In formula (x1), a and c represent the average number of each structural unit. For example, when the average total number of structural units A, B, and C contained per molecule of the target polyhydric phenol resin (X) is in the range of 10 to 100, an epoxy-modified polydiene compound in which the sum of a and c is in the range of 10 to 100 may be used. The average number of structural units A contained per molecule of the polyhydric phenol resin (X) can be adjusted by adjusting the value of c in formula (x1). The average numbers of structural units B and C contained per molecule of the polyhydric phenol resin (X) can be adjusted by adjusting the value of a in formula (x1). Furthermore, the molar ratio of structural units B and C contained in the polyhydric phenol resin (X) can be adjusted by adjusting the degree of reaction between the epoxy groups of the epoxy-modified polydiene compound (x1) and the thiol groups of the mercaptophenol compound (x2) described below. From the viewpoint of easily realizing a suitable molar ratio of the structural units A, B, and C described above for the polyhydric phenol resin (X), it is preferable that a and c in formula (x1) satisfy the relationship 0.1≦a / (a+c)≦0.5.

[0075] As described above, the epoxy-modified polydiene compound may further contain a cis-1,4-bonded or trans-1,4-bonded polydiene skeleton, so long as it contains the structure represented by formula (x1).

[0076] To achieve a polyphenol resin (X) that provides a cured product exhibiting good toughness, the epoxy group equivalent of the epoxy-modified polydiene compound (x1) is preferably 150 g / eq or more, more preferably 160 g / eq or more, even more preferably 170 g / eq or more, or 180 g / eq or more, and its upper limit is preferably 500 g / eq or less, more preferably 450 g / eq or less, even more preferably 400 g / eq or less, 350 g / eq or less, 300 g / eq or less, 280 g / eq or less, 260 g / eq or less, or 250 g / eq or less. Accordingly, in one embodiment, the epoxy group equivalent of the epoxy-modified polydiene compound (x1) is in the range of 150 to 500 g / eq.

[0077] The epoxy-modified polydiene compound (x1) can be synthesized by modifying at least a portion of the carbon-carbon double bonds of a polydiene compound to an epoxide structure. Such epoxidation can be carried out according to a conventionally known method, such as oxidation of the carbon-carbon double bonds using a peracid such as hydrogen peroxide. The ratio of a to c in formula (x1) can be adjusted by adjusting the degree of epoxidation.

[0078] The epoxy-modified polydiene compound (x1) may be a commercially available product. Examples of commercially available epoxy-modified polydiene compounds (x1) include "JP-100" (epoxy group equivalent: 200 g / eq., in formula (x1), a = 4 to 7, a + c = 16 to 25, R 1 and R 2 are both hydrogen atoms, the content of 1,2-bonded polydiene skeleton is more than 70 mol%, "JP-200" (epoxy group equivalent 215 g / eq., in formula (x1), a = 8 to 11, a + c = 35 to 43, R 1 and R 2 is a hydrogen atom, and the content of 1,2-bonded polydiene skeleton is more than 70 mol %.

[0079] -Mercaptophenol compound (x2)- The component (x2) is a mercaptophenol compound.

[0080] Depending on the structure of the desired polyhydric phenol resin (X), any mercaptophenol compound represented by the following formula (x2) may be used.

[0081] [ka] (In the formula, R S and n are the same as above.)

[0082] R SSuitable examples and values ​​of R and n are as described above. For example, when n in the target polyhydric phenol resin (X) is 0, mercaptophenol (p-mercaptophenol, m-mercaptophenol, o-mercaptophenol) may be used. S When is a methyl group, 4-hydroxy-3-methyl-benzenethiol, 4-hydroxy-2-methyl-benzenethiol, 4-methyl-3-hydroxy-benzenethiol, etc. may be used.

[0083] In the reaction between the epoxy-modified polydiene compound (x1) and the mercaptophenol compound (x2), the epoxy group of the (x1) component reacts with the thiol group of the (x2) component. During this reaction, depending on the cleavage reaction of the epoxy group of the (x1) component, the aforementioned structural units B1 and B2 are produced in the 1,2- or 3,4-bonded polydiene skeleton, and the aforementioned structural units B2-1 and B2-2 are produced in the cis-1,4- or trans-1,4-bonded polydiene skeleton. Furthermore, if not all of the epoxy groups in the (x1) component react and unreacted epoxy groups remain in the resulting polyhydric phenol resin (X), the aforementioned structural unit C remains in the 1,2- or 3,4-bonded polydiene skeleton, and the aforementioned structural unit C2 remains in the cis-1,4- or trans-1,4-bonded polydiene skeleton.

[0084] To facilitate the production of a polyhydric phenol resin (X) that provides a cured product exhibiting good toughness, the reaction molar ratio (epoxy group:mercaptophenol compound) of the epoxy groups in the epoxy-modified polydiene compound (x1) to the mercaptophenol compound (x2) is preferably in the range of 100:10 to 100:100, more preferably 100:30 to 100:100, and even more preferably 100:50 to 100:100, 100:60 to 100:100, 100:70 to 100:100, 100:80 to 100:100, or 100:90 to 100:100. Thus, in one embodiment, the reaction molar ratio (epoxy group:mercaptophenol compound) of the epoxy groups in the epoxy-modified polydiene compound (x1) to the mercaptophenol compound (x2) is in the range of 100:10 to 100:100.

[0085] The present invention also provides a method for producing such a polyhydric phenol resin (X) (hereinafter, also simply referred to as "the production method of the present invention").

[0086] That is, the production method of the present invention is characterized by reacting an epoxy-modified polydiene compound (x1) with a mercaptophenol compound (x2).

[0087] The reaction between component (x1) and component (x2), i.e., the reaction between the epoxy group of component (x1) and the thiol group of component (x2), can be carried out in a solvent-free system, or in an organic solvent system. Examples of organic solvents used in the condensation reaction include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate-based solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol-based solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. The organic solvents may be used alone or in combination.

[0088] The reaction between component (x1) and component (x2) may involve the use of a reaction catalyst such as a base catalyst, or may involve substantially no reaction catalyst. The reaction between a thiol compound and an epoxy compound has long been known, and a base catalyst such as a tertiary amine is often used to facilitate the reaction (for example, the reaction between an alkanethiol and an epoxy compound typically involves the use of a base catalyst to facilitate the reaction). In this regard, we have confirmed that the reaction between the epoxy group in component (x1) and the thiol group in component (x2) proceeds smoothly without the substantial use of a reaction catalyst. Therefore, in one embodiment, the production method of the present invention involves the reaction between component (x1) and component (x2) without the substantial use of a reaction catalyst. In this specification, "without the substantial use of a reaction catalyst" refers to the amount of the reaction catalyst being 0.01 parts by mass or less, preferably 0.005 parts by mass or less, or 0.0001 parts by mass or less, when the total amount of component (x1) and component (x2) is 100 parts by mass.

[0089] The reaction temperature between components (x1) and (x2) is not particularly limited as long as the reaction proceeds, and may be, for example, in the range of 30 to 150°C. In the production method of the present invention, the reaction can be carried out at a lower temperature even when a reaction catalyst is not substantially used. For example, in the production method of the present invention, the reaction temperature between components (x1) and (x2) may be 140°C or lower, 120°C or lower, or 100°C or lower.

[0090] The reaction time between the (x1) and (x2) components is not particularly limited as long as the desired structure of the polyhydric phenol resin (X) is achieved, and may be, for example, in the range of 30 minutes to 30 hours. In the production method of the present invention, the reaction between the (x1) and (x2) components can proceed smoothly even without the substantial use of a reaction catalyst. For example, the reaction time between the (x1) and (x2) components may be 20 hours or less, 15 hours or less, 14 hours or less, or 12 hours or less.

[0091] The production method of the present invention may be carried out in a solvent-free system, substantially without using a reaction catalyst. The reaction of components (x1) and (x2) produces very few by-products (theoretically no by-products are produced). Therefore, the reaction of components (x1) and (x2) can produce the desired polyhydric phenol resin (X) with high purity. As mentioned above, the resulting polyhydric phenol resin (X) may contain unreacted mercaptophenol compounds, and the preferred range of the mercaptophenol compound content in such cases is also as mentioned above.

[0092] [Resin composition] The polyhydric phenol resin (X) of the present invention can be used to produce a resin composition, and the present invention also provides such a resin composition.

[0093] The resin composition of the present invention is characterized by containing the polyhydric phenol resin (X) of the present invention. From the viewpoint of producing a cured product exhibiting good toughness, the content of the polyhydric phenol resin (X) in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit of the content is not particularly limited and may be determined depending on the properties required of the resin composition, but may be, for example, 99.8% by mass or less, 99.6% by mass or less, 99.5% by mass or less, 99.4% by mass or less, or 99.2% by mass or less. In the present invention, the "resin component" in the resin composition refers to the non-volatile components constituting the resin composition, excluding the inorganic filler described below.

[0094] -Crosslinkable resin (Y)- The resin composition of the present invention may contain a crosslinkable resin as component (Y) in addition to the polyhydric phenol resin (X) of the present invention. The crosslinkable resin of component (Y) refers to a crosslinkable resin other than the polyhydric phenol resin (X).

[0095] The type of crosslinkable resin (Y) is not particularly limited as long as it can be crosslinked in the presence of the polyhydric phenol resin (X). From the viewpoint of providing a cured product exhibiting good toughness in combination with the polyhydric phenol resin (X) and further exhibiting good insulating properties, the crosslinkable resin (Y) is preferably at least one selected from the group consisting of thermosetting resins and radically polymerizable resins.

[0096] As the thermosetting resin and radical polymerizable resin, known resins used for forming insulating layers of printed wiring boards and semiconductor chip packages may be used. Hereinafter, thermosetting resins and radical polymerizable resins that can be used as the crosslinkable resin will be described.

[0097] Examples of thermosetting resins include epoxy resins, benzocyclobutene resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, silicone resins, and phenoxy resins. One type of thermosetting resin may be used alone, or two or more types may be used in combination. Among these, the crosslinkable resin preferably contains an epoxy resin, since a cured product having exceptionally excellent flexural toughness and tensile toughness can be obtained in combination with the polyhydric phenol resin (X).

[0098] The type of epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups per molecule. Examples of epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, phenol novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthol epoxy resins, naphthalene epoxy resins, naphthylene ether epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, cresol novolac epoxy resins, biphenyl epoxy resins, phenol aralkyl epoxy resins, biphenyl aralkyl epoxy resins, fluorene skeleton epoxy resins, dicyclopentadiene epoxy resins, anthracene epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol epoxy resins, trimethylol epoxy resins, and halogenated epoxy resins. The resin composition of the present invention containing the polyhydric phenol resin (X) can provide a cured product exhibiting good toughness, regardless of the type of epoxy resin.

[0099] Epoxy resins can be classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition of the present invention may contain only a liquid epoxy resin as the crosslinkable resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. When a combination of a liquid epoxy resin and a solid epoxy resin is contained, the blending ratio (liquid:solid) may be in the range of 20:1 to 1:20 (preferably 10:1 to 1:10, more preferably 3:1 to 1:3) by mass.

[0100] The epoxy group equivalent of the epoxy resin is preferably 50 g / eq. to 2000 g / eq., more preferably 60 g / eq. to 1000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. As mentioned above, the epoxy group equivalent can be measured in accordance with JIS K7236.

[0101] 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 1500. The Mw of the epoxy resin can be measured as a polystyrene-equivalent value by the GPC method.

[0102] The type of radically polymerizable resin is not particularly limited, as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule. Examples of the radically polymerizable resin include resins having one or more radically polymerizable unsaturated groups selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, and maleoyl groups. In particular, from the viewpoint of being able to provide a cured product exhibiting good toughness in combination with the polyhydric phenol resin (X), it is preferred that the crosslinkable resin contains one or more selected from maleimide resins, (meth)acrylic resins, and styryl resins.

[0103] The type of maleimide resin is not particularly limited as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of maleimide resins include maleimide resins containing an aliphatic skeleton with 36 carbon atoms derived from dimer diamine, such as "BMI-3000J," "BMI-5000," "BMI-1400," "BMI-1500," "BMI-1700," and "BMI-689" (all manufactured by DigiCner Molecules, Inc.); maleimide resins containing an indane skeleton, as described in the Japan Institute of Invention and Innovation's Disclosure Technical Bulletin No. 2020-500211; and maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by Keiai Kasei Co., Ltd.).

[0104] The (meth)acrylic resin may be a monomer or an oligomer, and may be any type of (meth)acrylic resin, as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule. Here, the term "(meth)acryloyl group" is a general term for acryloyl groups and methacryloyl groups. Examples of methacrylic resins include (meth)acrylate monomers, as well as (meth)acrylic resins such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA," "FM-400," "R-687," "THE-330," "PET-30," and "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0105] The styryl resin is not particularly limited in type, and may be a monomer or oligomer, as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule. Examples of the styryl resin include styrene monomers and styryl resins such as "OPE-2St," "OPE-2St 1200," and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0106] The resin composition of the present invention may contain only a thermosetting resin as the crosslinkable resin (Y), may contain only a radical polymerizable resin, or may contain a combination of a thermosetting resin and a radical polymerizable resin. In one embodiment, the resin composition of the present invention contains a thermosetting resin in addition to the polyhydric phenol resin (X).

[0107] When the resin composition of the present invention contains a crosslinkable resin (Y), in combination with the polyhydric phenol resin (X), in order to obtain a cured product exhibiting good toughness, the content of the crosslinkable resin (Y) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 12% by mass or more, 14% by mass or more, or 15% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit of the content is not particularly limited and may be determined depending on the properties required of the resin composition, but may be, for example, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0108] In the resin composition of the present invention, the mass ratio ((Y) / (X)) of the polyhydric phenol resin (X) to the crosslinkable resin (Y) is preferably 4 or less, more preferably 3 or less, 2 or less, 1.5 or less, or 1 or less, and even more preferably 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less, from the viewpoint of further enjoying the effects of the present invention. The lower limit of the mass ratio ((Y) / (X)) may be 0, but may also be, for example, 0.01 or more, 0.05 or more, 0.1 or more, etc. Accordingly, in one embodiment, the mass ratio ((Y) / (X)) of the polyhydric phenol resin (X) to the crosslinkable resin (Y) is in the range of 0 to 4.

[0109] -Inorganic filler- The resin composition of the present invention may further contain an inorganic filler, which can reduce the linear thermal expansion coefficient and the dielectric loss tangent.

[0110] Examples of inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica is preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred. The inorganic fillers may be used alone or in combination of two or more. Commercially available inorganic fillers include, for example, "UFP-30" (manufactured by Denka); "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," "SO-C1," and "SC-C2" (all manufactured by Admatechs); and "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" (manufactured by Tokuyama Corporation).

[0111] The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less, from the viewpoint of achieving low surface roughness of the cured product (insulating layer) and facilitating the formation of fine wiring. The lower limit of the average particle size is not particularly limited and may be, for example, 0.01 μm or more, 0.02 μm or more, or 0.03 μm or more. The average particle size of the 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 preferably used is one in which the inorganic filler is dispersed in water using ultrasonic waves. Examples of laser diffraction / scattering particle size distribution analyzers that can be used include the LA-950 manufactured by Horiba, Ltd.

[0112] The inorganic filler is preferably one that has been surface-treated with a surface treatment agent such as an aminosilane coupling agent, a ureidosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a vinylsilane coupling agent, a styrylsilane coupling agent, an acrylatesilane coupling agent, an isocyanatesilane coupling agent, a sulfidesilane coupling agent, an organosilazane compound, or a titanate coupling agent to improve its moisture resistance and dispersibility.

[0113] When the resin composition of the present invention contains an inorganic filler, the content of the inorganic filler in the resin composition may be determined depending on the properties required of the resin composition, but when the nonvolatile components in the resin composition are taken as 100% by mass, it is, for example, 5% by mass or more, 10% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit of the content of the inorganic filler is not particularly limited, but can be, for example, 90% by mass or less, 80% by mass or less, etc.

[0114] -Resin crosslinking agent- The resin composition of the present invention may further contain a resin crosslinking agent (resin curing agent).

[0115] Resin crosslinking agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8500-65T", "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", and "HPC Active ester crosslinkers such as "HPB-8150-62T", "HPB-8151-62T" (manufactured by DIC Corporation), "PC1300-02-65T" (manufactured by Air Water Inc.), "DC808", "YLH1026", "DC808", "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "TD2090", "TD2131" (manufactured by DIC Corporation), "MEH-7600", and "MEH-7851" "," MEH-8000H" (manufactured by Meiwa Kasei Co., Ltd.), "NHN", "CBN", "GPH-65", "GPH-103" (manufactured by Nippon Kayaku Co., Ltd.), "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (manufactured by Nippon Steel Chemical & Material Co., Ltd.), "LA7052", "LA7054", "LA3018", "LA1356" (manufactured by DIC Corporation) and other phenolic curing agents; "Fa", "Pd" (manufactured by Shikoku Kasei Co., Ltd.), "HFB2006M" (manufactured by Showa Polymer Co., Ltd.) and other benzoxazine-based crosslinking agents; acid anhydride-based crosslinking agents such as methylhexahydrophthalic anhydride, methyl nadic anhydride, and hydrogenated methyl nadic anhydride; cyanate ester-based crosslinking agents such as PT30, PT60, and BA230S75 (manufactured by Lonza Japan); and benzoxazine-based crosslinking agents.

[0116] When the resin composition of the present invention contains a resin crosslinking agent, the content of the resin crosslinking agent in the resin composition may be determined depending on the properties required of the resin composition, but when the resin component in the resin composition is taken as 100% by mass, the content is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, and the lower limit may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, etc.

[0117] -Crosslinking accelerator- The resin composition of the present invention may further contain a crosslinking accelerator (curing accelerator), which makes it possible to efficiently adjust the crosslinking time and crosslinking temperature.

[0118] Examples of crosslinking accelerators include organic phosphine compounds such as "TPP," "TPP-K," "TPP-S," and "TPTP-S" (manufactured by Hokko Chemical Industry Co., Ltd.); imidazole compounds such as "Curezol 2MZ," "2E4MZ," "Cl1Z," "Cl1Z-CN," "Cl1Z-CNS," "Cl1Z-A," "2MZ-OK," "2MA-OK," and "2PHZ" (manufactured by Shikoku Chemical Industry Co., Ltd.); amine adduct compounds such as Novacure (manufactured by Asahi Chemical Industry Co., Ltd.) and Fujicure (manufactured by Fuji Chemical Industry Co., Ltd.); amine compounds such as 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 4-dimethylaminopyridine; and organometallic complexes or organometallic salts of cobalt, copper, zinc, iron, nickel, manganese, tin, and the like.

[0119] When the resin composition of the present invention contains a crosslinking accelerator, the content of the crosslinking accelerator in the resin composition may be determined depending on the properties required of the resin composition, but when the resin component in the resin composition is taken as 100% by mass, it is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, and the lower limit may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, etc.

[0120] -Other additives- The resin composition of the present invention may further contain other additives. Examples of such additives include organic fillers such as rubber particles; photocationic polymerization initiators and photoacid generators such as sulfonium salts, iodonium salts, and nonionic types; photosensitizers such as naphthoquinone diazide compounds; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; silicone defoamers and acrylic defoamers. Antifoaming agents such as foaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silanes; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphine Examples of suitable additives include flame retardants such as acid compounds, red phosphorus, nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. The content of such additives may be determined depending on the properties required of the resin composition.

[0121] The resin composition of the present invention may further contain an organic solvent as a volatile component. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of suitable organic solvents include ether ester solvents such as ethanol; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. These organic solvents may be used singly or in combination of two or more.

[0122] When the resin composition of the present invention contains an organic solvent, the content of the organic solvent in the resin composition may be determined depending on the properties required of the resin composition, and may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, when all components in the resin composition are taken as 100% by mass.

[0123] The resin composition of the present invention can be prepared by appropriately mixing the necessary components among the above-mentioned components, and kneading or mixing them as needed using a kneading means such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer or a planetary mixer.

[0124] The resin composition of the present invention can be prepared as a thermosetting resin composition or a photocurable resin composition by using an appropriate combination of the above-mentioned components in addition to the polyhydric phenol resin (X). For example, a thermosetting resin composition may be prepared by using the polyhydric phenol resin (X) in combination with one or more components selected from the group consisting of a crosslinkable resin (Y), an inorganic filler, a resin crosslinking agent, a crosslinking accelerator, and the other additives described above. Alternatively, a photocurable resin composition may be prepared by using the polyhydric phenol resin (X) in combination with one or more components selected from the group consisting of a photocationic polymerization initiator, a photoacid generator, and a photosensitizer in combination with one or more components selected from the group consisting of a crosslinkable resin (Y), an inorganic filler, a resin crosslinking agent, a crosslinking accelerator, and the other additives described above. Therefore, in one embodiment, the resin composition of the present invention is a thermosetting resin composition or a photocurable resin composition.

[0125] The resin composition of the present invention containing the polyhydric phenol resin (X) can provide a cured product exhibiting good toughness.

[0126] In one embodiment, the cured product of the resin composition of the present invention is characterized by high flexural toughness. For example, as described in the "Flexural toughness" section below, the flexural toughness of the cured product of the resin composition of the present invention may be preferably 4.5 MPa or more, 5.0 MPa or more, 5.2 MPa or more, 5.4 MPa or more, or 5.5 MPa or more, when measured according to JIS K7171.

[0127] In one embodiment, the cured product of the resin composition of the present invention is characterized by high tensile toughness. For example, as described in the "Tensile toughness" section below, the tensile toughness of the cured product of the resin composition of the present invention may be preferably 1.0 MPa or more, 1.2 MPa or more, 1.4 MPa or more, 1.5 MPa or more, or 1.6 MPa or more, when measured according to JIS K7161.

[0128] As described above, the resin composition of the present invention can provide a cured product exhibiting good toughness. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming automobile parts such as brakes (resin composition for automobile parts). The resin composition of the present invention can also provide a cured product exhibiting good toughness and can suppress crack defects even when the product is thinned. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for an insulating interlayer of a printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a circuit board with built-in components. The resin composition of the present invention can also be suitably used as a resin composition for encapsulating semiconductor chips (resin composition for semiconductor encapsulation), and can be suitably used as a resin composition for a rewiring formation layer (resin composition for a rewiring formation layer) as an insulating layer for forming a rewiring layer. The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, hole filling resins, and component embedding resins.

[0129] [Sheet-type laminated materials (resin sheets, prepregs)] The resin composition of the present invention can be used as it is, but may also be used in the form of a sheet-like laminate material containing the resin composition.

[0130] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0131] In one embodiment, the resin sheet includes a support and a layer of a resin composition (hereinafter simply referred to as a "resin composition layer") provided on the support, and is characterized in that the resin composition layer is formed from the resin composition of the present invention.

[0132] The thickness of the resin composition layer varies depending on the application, and may be appropriately determined depending on the application. For example, from the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, or 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 5 μm or more, etc.

[0133] Examples of the support include a thermoplastic resin film, a metal foil, and a release paper, and a thermoplastic resin film or a metal foil is preferred. Therefore, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0134] When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and 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.

[0135] 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.).

[0136] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment. Alternatively, a support having a release layer on the surface to be bonded to the resin composition layer may be used as the support. Examples of the release agent used in the release layer of the support having 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 be used as the support having a release layer, such as "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.

[0137] 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.

[0138] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0139] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, but examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. Furthermore, the release layer is not particularly limited as long as it allows the metal foil to be released from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0140] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0141] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. The thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0142] In one embodiment, the resin sheet may further include an optional layer, if necessary. Examples of such optional layers include a protective film 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.

[0143] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0144] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0145] 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 composition or resin varnish, for example, when a resin composition or 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.

[0146] 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.

[0147] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0148] The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular lower limit to the thickness of the sheet-like fiber substrate. It is usually 10 μm or more.

[0149] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0150] The thickness of the prepreg may be in the same range as that of the resin composition layer in the resin sheet described above.

[0151] The sheet-like laminate material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and more suitably used for forming an interlayer insulating layer of a printed wiring board (for an insulating interlayer of a printed wiring board). The sheet-like laminate material of the present invention can also be suitably used for encapsulating a semiconductor chip (for semiconductor encapsulation), and can be suitably used for a rewiring formation layer as an insulating layer for forming a rewiring layer.

[0152] [Printed wiring board] The printed wiring board of the present invention includes an insulating layer made of a cured product of the resin composition of the present invention.

[0153] 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) A step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer.

[0154] 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 (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." Furthermore, the "inner layer substrate" of the present invention also includes 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. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0155] 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 end plate) or a metal roll (SUS roll). The thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed 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.

[0156] 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.

[0157] 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.

[0158] After lamination, the laminated resin sheets may be smoothed under normal pressure (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 lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0159] The support may be removed between step (I) and step (II), or after step (II). When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. When a metal foil with a supporting substrate is used as the support, the supporting substrate (and the release layer) may be peeled off. Then, the conductor layer can be formed using the metal foil.

[0160] In step (II), the resin composition layer is cured (for example, by heat curing) 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 conditions typically employed for forming insulating layers for printed wiring boards may be used.

[0161] 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 250° C., more preferably 150° C. to 240° C., and even more preferably 180° C. to 230° C. The curing time is preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0162] 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.

[0163] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0164] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as when a resin sheet is used.

[0165] 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.

[0166] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal (desmear) is also performed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be adopted. 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.

[0167] The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be carried out by, for example, immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes. To keep the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0168] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof 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.

[0169] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

[0170] 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, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] In one embodiment, the conductor layer may be 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 conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0175] First, a plating seed layer is formed on the surface of an 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. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, 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.

[0176] In another embodiment, the conductor layer may be formed using a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0177] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0178] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[0179] [Semiconductor chip package] The semiconductor chip package of the present invention includes a sealing layer made of a cured product of the resin composition of the present invention. As described above, the semiconductor chip package of the present invention may also include an insulating layer (rewiring formation layer) for forming a rewiring layer made of a cured product of the resin composition of the present invention.

[0180] A semiconductor chip package can be produced, for example, by a method including the following steps (1) to (6) using the resin composition and resin sheet of the present invention. The resin composition and resin sheet of the present invention can be used to form the encapsulating layer in step (3) or the rewiring formation layer in step (5). An example of forming an encapsulating layer or a rewiring formation layer using a resin composition or a resin sheet will be shown below. However, techniques for forming encapsulating layers and rewiring formation layers for semiconductor chip packages are known, and a person skilled in the art can produce a semiconductor package using the resin composition and resin sheet of the present invention according to known techniques. (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.

[0181] -Process (1)- The material used for the substrate is not particularly limited. Examples of the substrate include a silicon wafer, a glass wafer, a glass substrate, a metal substrate such as copper, titanium, stainless steel, or cold-rolled steel sheet (SPCC), a substrate made of glass fiber impregnated with epoxy resin or the like and subjected to a thermosetting treatment (e.g., an FR-4 substrate), and a substrate made of bismaleimide triazine resin (BT resin).

[0182] The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. Commercially available products can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

[0183] -Process (2)- The semiconductor chips can be temporarily fixed using known devices such as a flip chip bonder, a die bonder, etc. The layout and number of semiconductor chips to be arranged can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc., and for example, the semiconductor chips can be temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0184] -Process (3)- The resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied to a semiconductor chip and cured (for example, thermally cured) to form a sealing layer.

[0185] For example, lamination of a semiconductor chip and a resin sheet can be performed by removing the protective film from the resin sheet and then thermocompressing the resin sheet to the semiconductor chip from the support side. Examples of a member for thermocompressing the resin sheet to the semiconductor chip (hereinafter also referred to as a "thermocompression member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber, so that the resin sheet can adequately conform to the surface irregularities of the semiconductor chip. The semiconductor chip and resin sheet can also be laminated by a vacuum lamination method, and the lamination conditions and preferred ranges are the same as those described in relation to the method for manufacturing a printed wiring board.

[0186] After lamination, the resin composition is thermally cured to form the sealing layer under the same conditions as those described in relation to the method for producing a printed wiring board.

[0187] The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

[0188] When forming a sealing layer by applying the resin composition of the present invention, the application conditions are the same as the application conditions when forming the resin composition layer described in relation to the resin sheet of the present invention, and the preferred ranges are also the same.

[0189] -Process (4)- The method for peeling off the substrate and the temporary fixing film can be changed as appropriate depending on the material of the temporary fixing film, etc., and examples include a method in which the temporary fixing film is heated and foamed (or expanded) to peel it off, and a method in which ultraviolet light is irradiated from the substrate side to reduce the adhesive strength of the temporary fixing film and peel it off.

[0190] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100 to 250°C for 1 to 90 seconds or 5 to 15 minutes. In the method of irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film to peel it off, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 is.

[0191] -Process (5)- The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring formation layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing a semiconductor chip package, ultraviolet-curable resins and thermosetting resins are preferred. The rewiring formation layer may be formed using the resin composition or resin sheet of the present invention.

[0192] After forming the redistribution layer, via holes may be formed in the redistribution layer to connect the semiconductor chip to a conductor layer (described later). The via holes may be formed by a known method depending on the material of the redistribution layer.

[0193] -Process (6)- The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as in step (V) described in relation to the method for producing a printed wiring board. Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0194] The manufacturing of the semiconductor chip package may further include the steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing the plurality of semiconductor chip packages into individual semiconductor chip packages. These steps may be performed according to various methods known to those skilled in the art for use in manufacturing semiconductor chip packages.

[0195] By forming an encapsulating layer and a rewiring formation layer using the resin composition and resin sheet of the present invention, which provide a cured product exhibiting good toughness, a semiconductor chip package can be realized regardless of whether the semiconductor package is a fan-in package or a fan-out package. In one embodiment, the semiconductor chip package of the present invention is a fan-out package. The resin composition and resin sheet of the present invention can be applied to both a fan-out panel level package (FOPLP) and a fan-out wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a fan-out panel level package (FOPLP). In another embodiment, the semiconductor package of the present invention is a fan-out wafer level package (FOWLP).

[0196] [Semiconductor Devices] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition layer of the present invention. The semiconductor device of the present invention can be produced using the printed wiring board or semiconductor chip package of the present invention.

[0197] 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]

[0198] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0199] Example 1: Synthesis of polyphenol resin (1) [ka]

[0200] In a 200 mL flask equipped with a stirrer and a thermometer, the ratio of the structural units was (A):[(B1)+(B2)]:(C)=71:28:1 (molar ratio), and R 1 and R 2 The types and ratios of raw materials in which both are hydrogen atoms and n = 0 are epoxidized polybutadiene resin (JP-100 manufactured by Nippon Soda Co., Ltd., epoxy equivalent 200 g / eq., a = 4 to 7, a + c = 16 to 25 in the above formula (x1), R 1 and R 2 400 g (epoxy group 2.0 mol) of (where n is a hydrogen atom) and 239 g (1.9 mol) of p-mercaptophenol (manufactured by Sankyo Chemical Co., Ltd., n = 0 in the above formula (x2)) were added, and the temperature was raised to 90°C with stirring. Stirring was continued at that temperature for 10 hours, yielding 601 g of a pale yellow resin.

[0201] The resin obtained was subjected to the following measurement methods. 1 The H-NMR spectrum is shown in Figure 1a. 13 The C-NMR spectrum is shown in Figure 1b, the GPC chart in Figure 1c, and the IR chart in Figure 1d. These results confirmed that the resulting resin had the desired molecular structure. Furthermore, the hydroxyl equivalent of the resin, measured according to the following method, was 352 g / eq. (theoretical value: 337 g / eq.), and the epoxy equivalent was 6020 g / eq. (theoretical value: 6394 g / eq.).

[0202] (NMR measurement conditions) Measurement equipment: AVANCE NEO 500 nuclear magnetic resonance spectrometer (Bruker BioSpin) Measurement nuclei: 1H, 13C Measurement mode: 1H = single pulse, 13C = single pulse proton broadband decoupling Solvent: deuterated DMSO Pulse angle: 1H=45°, 13C=30° Sample concentration: 27 wt% (300 mg / 0.75 mL) Accumulation count: 1H=8 times, 13C=256 times

[0203] (GPC measurement conditions) Measuring device: Tosoh Corporation "HLC-8420GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL SuperHZ2000" + Tosoh Corporation "TSK-GEL SuperHZ2000" + Tosoh Corporation "TSK-GEL SuperHZ3000" + Tosoh Corporation "TSK-GEL SuperHZ4000" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation) Sample: 0.2% by mass of tetrahydrofuran solution (equivalent to resin solids) filtered through a microfilter (10 μl)

[0204] (IR measurement conditions) Measuring device: JASCO Corporation "FT / IR-4600"

[0205] (Method for measuring hydroxyl equivalent) According to JIS K0070, the hydroxyl groups in the phenolic resin were acetylated with acetic anhydride-pyridine, followed by hydrolysis, and the hydroxyl equivalent was measured by back titration of the remaining acetic acid.

[0206] (Method for measuring epoxy group equivalent) The epoxy group equivalent was measured by potentiometric titration according to JIS K7236.

[0207] Example 2: Synthesis of polyphenol resin (2) The ratio of the structural units present is (A):[(B1)+(B2)]:(C)=71:28:1 (molar ratio), and R 1 and R 2 The types and ratios of raw materials in which both are hydrogen atoms and n = 0 are used. The epoxy polybutadiene resin is a high molecular weight epoxy polybutadiene resin (JP-200 manufactured by Nippon Soda Co., Ltd., epoxy equivalent 215 g / eq., a = 8 to 11, a + c = 35 to 43 in the above formula (x1), R 1 and R 2 is a hydrogen atom) and the amount of p-mercaptophenol was changed to 120 g (1.9 mol), and the same procedure as in Example 1 was repeated to obtain 612 g of a pale yellow resin.

[0208] The resulting resin was subjected to GPC and IR measurements in the same manner as in Example 1. The GPC chart and IR chart of the resulting resin are shown in Figure 2a and Figure 2b, respectively. These results confirmed that the resulting resin had the desired molecular structure. Furthermore, the hydroxyl equivalent of the resin, measured in the same manner as in Example 1, was 299 g / eq. (theoretical value: 289 g / eq.), and the epoxy equivalent was 5790 g / eq. (theoretical value: 6000 g / eq.).

[0209] Example 3: Synthesis of polyphenol resin (3) The molar ratio of the structural units is (A):[(B1)+(B2)]:(C)=70:15:15, and R 1 and R 2The raw material ratio was set so that both were hydrogen atoms and n=0, and 524 g of a pale yellow resin was obtained in the same manner as in Example 1, except that the amount of p-mercaptophenol was changed to 126 g (1.0 mol).

[0210] The resulting resin was subjected to GPC and IR measurements in the same manner as in Example 1. The GPC chart and IR chart of the resulting resin are shown in Figure 3a and Figure 3b, respectively. These results confirmed that the resulting resin had the desired molecular structure. Furthermore, the hydroxyl equivalent of the resin, measured in the same manner as in Example 1, was 567 g / eq. (theoretical value: 556 g / eq.), and the epoxy equivalent was 539 g / eq. (theoretical value: 556 g / eq.). This confirmed that approximately 50 mol% of the epoxy groups in the starting epoxidized polybutadiene resin had been modified with phenol.

[0211] <Examples 4 to 7 and Comparative Example 1> (1) Preparation of resin composition The synthesized polyhydric phenol resins (1) to (3) were used to prepare resin compositions having the formulations shown in Table 1 below. When preparing the resin compositions, the raw materials were heated to 100°C and mixed uniformly.

[0212] (2) Manufacturing of hardened products The prepared resin composition was poured into a casting frame with a gap of approximately 2 mm, which was created by sandwiching a spacer between two glass plates coated with a release agent, and heated at 150°C for 2 hours and then at 190°C for 3 hours to produce a sheet-like cured product.

[0213] The cured product was subjected to evaluation tests as follows, and the results are shown in Table 2.

[0214] [Flexural toughness] A bending test was carried out in accordance with JIS K7171 using Shimadzu Corporation's "AUTOGRAPH AG-X / R," and the energy per unit area calculated from the integral value of the SS curve was taken as the bending toughness.

[0215] [Tensile toughness] A tensile test was carried out in accordance with JIS K7161 using Shimadzu Corporation's "AUTOGRAPH AG-Xplus," and the energy per unit area calculated from the integral value of the SS curve was taken as the tensile toughness.

[0216] [Table 1]

[0217] [Table 2]

[0218] As shown in Table 2, it was confirmed that the polyhydric phenol resin of the present invention provides a cured product excellent in both flexural toughness and tensile toughness. Furthermore, it was confirmed that even when the resin composition further contains an inorganic filler (e.g., 30 to 90% by mass, when the non-volatile components of the resin composition are taken as 100% by mass) or a crosslinkable resin such as another thermosetting resin or a radically polymerizable resin (e.g., 10 to 60% by mass, when the resin components of the resin composition are taken as 100% by mass), a resin composition containing the polyhydric phenol resin of the present invention provides a cured product exhibiting good toughness (flexural toughness more than 10% higher, and tensile toughness more than 50% higher, compared to a resin composition not containing the polyhydric phenol resin of the present invention).

Claims

1. A polyhydric phenol resin (X) containing a polydiene skeleton, A structural unit A represented by the following formula (A), one or more structural units B selected from a structural unit B1 represented by the following formula (B1) and a structural unit B2 represented by the following formula (B2); The polyhydric phenol resin (X) comprises: 【Chemistry 1】 (In the formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group, Each R S independently represents a substituent; n represents a number from 0 to 4.

2. The polyhydric phenol resin (X) according to claim 1, further comprising a structural unit C represented by the following formula (C): 【Chemistry 2】 (In the formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

3. The polyhydric phenol resin (X) according to claim 1, wherein the molar ratio of the structural unit A to the structural unit B (structural unit A:structural unit B) is in the range of 15:85 to 85:

15.

4. Further, the compound may or may not contain a structural unit C represented by the following formula (C): The polyhydric phenol resin (X) according to claim 1, wherein the molar ratio of the structural unit B to the structural unit C (structural unit B:structural unit C) is in the range of 20:80 to 100:

0. 【Transformation 3】 (In the formula, R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group.)

5. The polyhydric phenol resin (X) according to claim 1, wherein the polydiene skeleton is a polybutadiene skeleton.

6. The polyhydric phenol resin (X) according to claim 1, wherein the phenolic hydroxyl group equivalent is in the range of 200 to 1000 g / eq.

7. The polyhydric phenol resin (X) according to claim 2, having an epoxy group equivalent of 3000 g / eq. or more.

8. Further, the compound may or may not contain a structural unit C represented by the following formula (C): The polyhydric phenol resin (X) according to claim 1, wherein the molar ratio of epoxy groups to phenolic hydroxyl groups (epoxy groups:phenolic hydroxyl groups) is in the range of 80:20 to 0:

100. 【Chemistry 4】 (In the formula, R 1 and R 2 each independently represent a hydrogen atom, a methyl group, or an ethyl group.)

9. The polyhydric phenol resin (X) according to claim 1, which is a reaction product of an epoxy-modified polydiene compound (x1) and a mercaptophenol compound (x2).

10. The polyhydric phenol resin (X) according to claim 9, wherein the epoxy-modified polydiene compound (x1) comprises a structure represented by the following formula (x1): 【Transformation 5】 (In the formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group, a and c represent the average number of each structural unit.

11. The polyhydric phenol resin (X) according to claim 9, wherein the epoxy group equivalent of the epoxy-modified polydiene compound (x1) is in the range of 150 to 500 g / eq.

12. The polyhydric phenol resin (X) according to claim 9, wherein the reaction molar ratio of the epoxy groups in the epoxy-modified polydiene compound (x1) to the mercaptophenol compound (x2) (epoxy groups:mercaptophenol compound) is in the range of 100:10 to 100:

100.

13. The polyhydric phenol resin (X) according to claim 9, wherein the content of the unreacted mercaptophenol compound (x2) is 10 mass% or less.

14. The method for producing the polyhydric phenol resin (X) according to any one of claims 1 to 13, comprising reacting an epoxy-modified polydiene compound (x1) with a mercaptophenol compound (x2).

15. The method for producing the polyhydric phenol resin (X) according to claim 14, wherein the reaction temperature is in the range of 30 to 150°C.

16. The method for producing the polyhydric phenol resin (X) according to claim 14, wherein a reaction catalyst is not substantially used.

17. A resin composition comprising the polyhydric phenol resin (X) according to any one of claims 1 to 13.

18. The resin composition according to claim 17, which is a thermosetting resin composition or a photocurable resin composition.

19. The resin composition according to claim 17, further comprising a thermosetting resin.

20. The resin composition according to claim 17, further comprising an inorganic filler.

21. The resin composition according to claim 17, which is used for an insulating layer of a printed wiring board.

22. The resin composition according to claim 17, which is used for semiconductor encapsulation.

23. A resin sheet comprising a support and a layer of the resin composition according to claim 17 provided on the support.

24. The resin sheet according to claim 23, wherein the support is a thermoplastic resin film or a metal foil.

25. A prepreg obtained by impregnating a sheet-like fiber substrate with the resin composition according to claim 17.

26. A cured product of the resin composition according to claim 17.

27. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to claim 17.

28. A semiconductor chip package comprising an encapsulating layer made of a cured product of the resin composition according to claim 17.

29. 30. The semiconductor chip package of claim 28, which is a fan-out type package.

30. A semiconductor device comprising the printed wiring board according to claim 27.

31. 30. A semiconductor device comprising the semiconductor chip package of claim 28.

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