Curable compositions, prepregs, resin sheets, metal foil laminates and printed circuit boards

Abstract

A curable composition comprising: an alkenylphenol (A), an epoxy-modified silicone (B), and an epoxy compound (C) other than the epoxy-modified silicone (B).

Description

Technical Field

[0001] This invention relates to curable compositions, prepregs, resin sheets, metal foil laminates, and printed circuit boards. Background Technology

[0002] In recent years, with the advancement of high functionality and miniaturization of semiconductor packages widely used in electronic devices, communication devices, and personal computers, the high integration and high-density mounting of components used in semiconductor packages have accelerated rapidly. Consequently, the characteristics required for printed circuit boards (PCBs) used in semiconductor packages have become increasingly stringent. Examples of these required characteristics include low thermal expansion coefficient, chemical resistance, and peel strength.

[0003] Patent document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, an organosilicon compound having an epoxy group in its molecular structure, and a compound having a phenolic hydroxyl group has excellent heat resistance and low thermal expansion, making it suitable for use in metal foil laminates and multilayer printed circuit boards.

[0004] Patent Document 2 discloses a manufacturing method in which polymaleimide, diglycidyl polysiloxane of Formula (I), diallyl bisphenol-based addition polymer of Formula (II), and allylated phenolic resin of Formula (III) are reacted at a predetermined ratio and under predetermined conditions to obtain a semiconductor encapsulation resin. According to this document, the semiconductor encapsulation resin obtained by the above manufacturing method exhibits good compatibility with polymaleimide and the aforementioned addition polymer, and the cured composition of the semiconductor encapsulation resin exhibits excellent properties (e.g., high glass transition temperature, moisture resistance, and thermal strength), resulting in high reliability as a semiconductor encapsulation resin composition. This document also discloses that in Formula (III), component b is an important component that reacts with maleimide groups in the resin formation reaction with polymaleimide, improving the compatibility between polymaleimide and polysiloxane.

[0005]

[0006] (where R is in the formula) 1 Indicates alkylene or phenylene, R 2 Each can independently represent an alkyl or phenyl group, where n represents an integer from 1 to 100.

[0007]

[0008] (where R is in the formula) 4 This indicates an ether bond, methylene group, propylene group, or a direct bond (single bond).

[0009]

[0010] (In the above formula, a, b, and c respectively represent the percentages of the respective components, where 0 < a, b, c < 100 and a + b + c = 100.)

[0011] Prior art documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2012 - 149154

[0014] Patent Document 2: Japanese Unexamined Patent Application Publication No. 4 - 4213 Summary of the invention

[0015] Problems to be solved by the invention

[0016] As in Patent Document 1, a resin composition containing an organosilicon compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound has excellent low thermal expansion properties. However, the inventors have found that in the above resin composition, there are problems in moldability due to insufficient compatibility between the above organosilicon compound and the thermosetting resin. Furthermore, the inventors have found that the chemical resistance of the above resin composition and the metal foil peeling strength (for example, copper foil peeling strength) when forming a metal foil - clad laminate are insufficient.

[0017] On the other hand, the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and no studies have been conducted on the low thermal expansion properties, chemical resistance, and copper foil peeling strength, which are the property requirements for printed circuit boards.

[0018] The present invention has been made in view of the above problems, and its object is to provide a curable composition, a prepreg, a resin sheet, a metal foil - clad laminate, and a printed circuit board having excellent compatibility, low thermal expansion properties, and chemical resistance.

[0019] Solutions for solving problems

[0020] The inventors have repeatedly and intensively studied to solve the above problems. As a result, it has been found that if it is a curable composition containing an alkenyl phenol, an epoxy - modified organosilicon, and an epoxy compound other than the epoxy - modified organosilicon, or a curable composition containing a polymer having them as structural units, the above problems can be solved, and thus the present invention has been completed.

[0021] That is, the present invention is as follows. [1]

[0023] A curable composition containing: an alkenyl phenol A, an epoxy - modified organosilicon B, and an epoxy compound C other than the epoxy - modified organosilicon B. [2]

[0025] According to the curable composition described in [1], the average number of phenolic groups per molecule of the aforementioned alkenylphenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the aforementioned epoxy-modified organosilicon B is 1 or more and less than 3, and the average number of epoxy groups per molecule of the aforementioned epoxy compound C is 1 or more and less than 3. [3]

[0027] According to the curable composition described in [1] or [2], wherein the aforementioned alkenylphenol A contains diallyl bisphenol and / or diallyl bisphenol. [4]

[0029] The curable composition according to any one of [1] to [3], wherein the aforementioned epoxy-modified organosilicon B comprises epoxy-modified organosilicon having an epoxy equivalent of 140 to 250 g / mol. [5]

[0031] The curable composition according to any one of [1] to [4], wherein the aforementioned epoxy-modified organosilicon B contains the epoxy-modified organosilicon shown in formula (1).

[0032]

[0033] (where R is in the formula) 1 Each can independently represent an alkylene, phenylene, or arylene group, R 2 Each can independently represent an alkyl or phenyl group having 1 to 10 carbon atoms, where n represents an integer greater than 1. [6]

[0035] The curable composition according to any one of [1] to [5], wherein the aforementioned epoxy compound C contains the epoxy compound shown in the following formula (2).

[0036]

[0037] (where R is in the formula) a Each can independently represent an alkyl group or a hydrogen atom having 1 to 10 carbon atoms. [7]

[0039] The curable composition according to any one of [1] to [6], wherein the content of the aforementioned epoxy compound C is 5 to 50% by mass relative to the total 100% mass of the aforementioned epoxy-modified silicone B and the aforementioned epoxy compound C. [8]

[0041] A curable composition comprising a polymer D, said polymer D containing: structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C. [9]

[0043] According to the curable composition described in [8], the weight-average molecular weight of the aforementioned polymer D is 3.0 × 10⁻⁶. 3 ~5.0×10 4 .

[10]

[0045] According to the curable composition described in [8] or [9], the content of the aforementioned structural units derived from epoxy-modified silicone B in the aforementioned polymer D is 20 to 60% by mass relative to the total mass of the aforementioned polymer D.

[11]

[0047] The curable composition according to any one of [8] to

[10] , wherein the alkenyl equivalent of the aforementioned polymer D is 300 to 1500 g / mol.

[12]

[0049] The curable composition according to any one of [8] to

[11] , wherein the content of the aforementioned polymer D is 5 to 50% by mass relative to 100% by mass of the resin solids.

[13]

[0051] The curable composition according to any one of [1] to

[12] further contains thermosetting resin E.

[14]

[0053] According to the curable composition described in

[13] , the aforementioned thermosetting resin E contains one or more compounds selected from the group consisting of maleimide compounds, cyanate compounds, phenolic compounds, alkenyl-substituted nadicimide compounds and epoxy compounds.

[15]

[0055] According to the curable composition of

[14] , wherein the aforementioned maleimide compound comprises one or more selected from the group consisting of bis(4-maleimide-phenyl)methane, 2,2-bis{4-(4-maleimide-phenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane and maleimide compounds represented by formula (3) below.

[0056]

[0057] (In the formula, R5 independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than or equal to 1.)

[16]

[0059] The curable composition according to

[14] or

[15] , wherein the aforementioned cyanate ester compound comprises the compound shown in formula (4) and / or the compound shown in formula (5) other than the compound shown in formula (4).

[0060]

[0061] (In the formula, R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer greater than 1.)

[0062]

[0063] (where R is in the formula) ya Each independently represents an alkenyl group having 2 to 8 carbon atoms, R yb Each independently represents an alkyl group or a hydrogen atom having 1 to 10 carbon atoms, R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optional fusion structure with benzene ring, R yc A can be either present or absent. 1a Each can independently represent an alkylene group having 1 to 6 carbon atoms, an arylene group having 7 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a fluorene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), R yc In the absence of R, any two or more R atoms can be arbitrarily selected on one benzene ring. ya and / or R yb (The group, where n represents an integer from 1 to 10.)

[17]

[0065] The curable composition according to any one of

[14] to

[16] , wherein the aforementioned epoxy compound comprises a compound represented by formula (6) or a compound represented by formula (7).

[0066]

[0067] (where R is in the formula) 13 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.

[0068]

[0069] (where R is in the formula) 14 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.

[18]

[0071] The curable composition according to any one of [1] to

[17] further contains an inorganic filler material.

[0072] The content of the aforementioned inorganic filler material is 50 to 1000 parts by weight relative to 100 parts by weight of the resin solids.

[19]

[0074] The curable composition according to any one of [1] to

[18] is used for printed circuit boards.

[20]

[0076] A prepreg comprising:

[0077] Substrate; and,

[0078] A curable composition, as described in any one of [1] to

[19] , that is impregnated or coated onto the substrate. [twenty one]

[0080] A resin sheet comprising:

[0081] Support; and

[0082] The curable composition of any one of [1] to

[19] disposed on the surface of the support. [twenty two]

[0084] A metal foil-coated laminate comprising:

[0085] A laminate formed from one or more of the prepregs described in

[20] and the resin sheets described in

[21] ; and,

[0086] Metal foil disposed on one or both sides of the laminate. [twenty three]

[0088] A printed circuit board comprising:

[0089] An insulating layer formed from one or more of the prepregs described in

[20] and the resin sheets described in

[21] ; and,

[0090] A conductor layer formed on the surface of the insulating layer.

[0091] The effects of the invention

[0092] According to the present invention, it is possible to provide: curable compositions, prepregs, resin sheets, metal foil laminates and printed circuit boards having excellent compatibility, low thermal expansion and chemical resistance. Detailed Implementation

[0093] Hereinafter, the method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from its spirit.

[0094] Unless otherwise specified, the term "solid resin component" in this specification refers to the components in the curable composition of this embodiment, excluding solvents and fillers. 100 parts by weight of solid resin component means that the total amount of components in the curable composition, excluding solvents and fillers, is 100 parts by weight.

[0095] The term "compatibility" in this specification refers to the compatibility of polymer D, which is an organosilicon component, with other thermosetting resins in the curable composition. In addition to obtaining molded articles with excellent appearance due to the suppression of polymer D separation during molding caused by excellent compatibility, the resulting molded articles also exhibit excellent isotropy in their physical properties.

[0096] [First Embodiment: Curable Composition]

[0097] The curable composition of the first embodiment contains: alkenylphenol A, epoxy-modified silicone B, and epoxy compound C (hereinafter also simply referred to as "epoxy compound C") other than epoxy-modified silicone B. For a curable composition containing these components, there is a tendency for it to exhibit better compatibility with thermosetting resins that have insufficient compatibility with epoxy-modified silicone B. Therefore, the curable composition exhibits superior compatibility. Furthermore, if a portion of each of these components is reacted (polymerized) and used in the curable composition, it exhibits superior low thermal expansion and chemical resistance.

[0098] [Alkenylphenol A]

[0099] There are no particular limitations on the type of alkenylphenol A, as long as it is a compound having one or more alkenyl groups directly bonded to a phenolic aromatic ring. Curable compositions containing alkenylphenol A can exhibit excellent compatibility.

[0100] The alkenyl group is not particularly limited, and examples include vinyl, allyl, propenyl, butenyl, and hexenyl alkenyl groups with 2 to 30 carbon atoms. From the viewpoint of more effectively and reliably utilizing the effects of the present invention, allyl and / or propenyl alkenyl groups are preferred, and allyl is more preferred. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4. From the viewpoint of more effectively and reliably utilizing the effects of the present invention, the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, and more preferably 1.

[0101] A phenolic aromatic ring refers to a ring in which one or more hydroxyl groups are directly bonded to an aromatic ring. Examples include phenolic rings and naphthol rings. The number of hydroxyl groups directly bonded to a phenolic aromatic ring is not particularly limited, but may be 1 to 2, preferably 1.

[0102] Phenolic aromatic rings may have substituents other than an alkenyl group. Examples of such substituents include straight-chain alkyl groups with 1 to 10 carbon atoms, branched alkyl groups with 3 to 10 carbon atoms, cyclic alkyl groups with 3 to 10 carbon atoms, straight-chain alkoxy groups with 1 to 10 carbon atoms, branched alkoxy groups with 3 to 10 carbon atoms, cyclic alkoxy groups with 3 to 10 carbon atoms, and halogen atoms. When a phenolic aromatic ring has substituents other than an alkenyl group, the number of such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2. Furthermore, the bonding position of the substituent to the phenolic aromatic ring is not particularly limited.

[0103] The alkenylphenol A may have one or more structures formed by one or more alkenyl groups directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exerting the effects of the present invention, the alkenylphenol A preferably has one or two structures formed by one or more alkenyl groups directly bonded to a phenolic aromatic ring, and more preferably two structures.

[0104] The alkenylphenol A can be, for example, a compound represented by formula (1A) or formula (1B).

[0105]

[0106] (In the formula, Rxa independently represents an alkenyl group with 2 to 8 carbon atoms, Rxb independently represents an alkyl group with 1 to 10 carbon atoms or a hydrogen atom, Rxc independently represents an aromatic ring with 4 to 12 carbon atoms, Rxc optionally forms a fused structure with the benzene ring, Rxc optionally exists or does not exist, A represents an alkylene group with 1 to 6 carbon atoms, an arylene group with 7 to 16 carbon atoms, an arylene group with 6 to 10 carbon atoms, a fluorene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), and if Rxc does not exist, a group having 2 or more Rxa and / or Rxb can optionally be placed on one benzene ring.)

[0107]

[0108] (In the formula, Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Rxf represents an aromatic ring having 4 to 12 carbon atoms, Rxf optionally forms a fused structure with the benzene ring, Rxf optionally exists or does not exist, and if Rxf does not exist, a group having 2 or more Rxd and / or Rxe can optionally be placed on one benzene ring.)

[0109] In formulas (1A) and (1B), there are no particular restrictions on the alkenyl groups with 2 to 8 carbons represented as Rxa and Rxd, for example, vinyl, allyl, propenyl, butenyl, hexenyl, etc.

[0110] In formulas (1A) and (1B), compounds in which the groups represented by Rxc and Rxf form a fused structure with the benzene ring can be cited as examples, such as compounds containing a naphthol ring as a phenolic aromatic ring. Conversely, compounds in formulas (1A) and (1B) in which the groups represented by Rxc and Rxf are absent can be cited as examples, such as compounds containing a phenolic ring as a phenolic aromatic ring.

[0111] In formulas (1A) and (1B), there are no particular restrictions on the alkyl groups with 1 to 10 carbon atoms represented as Rxb and Rxe. Examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0112] In formula (1A), there are no particular limitations on the alkylene group with 1 to 6 carbons represented by A, and examples include methylene, ethylene, trimethylene, and propylene. There are no particular limitations on the arylene group with 7 to 16 carbons represented by A, and examples include the group represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (where Ar represents phenylene, naphthylene, or biphenylene). There are no particular limitations on the arylene group with 6 to 10 carbons represented by A, and examples include phenylene rings.

[0113] For the compound shown in formula (1B), from the viewpoint of more effectively and reliably exerting the effects of the present invention, Rxf is preferably a benzene ring (a compound containing a dihydroxynaphthalene skeleton).

[0114] From the viewpoint of further improving compatibility, alkenylphenol A is preferably an alkenyl bisphenol in which one alkenyl group is bonded to each of the two phenolic aromatic rings of a bisphenol. Similarly, alkenyl bisphenol is preferably a diallyl bisphenol in which one allyl group is bonded to each of the two phenolic aromatic rings of a bisphenol, and / or a diallyl bisphenol in which one propenyl group is bonded to each of the two phenolic aromatic rings of a bisphenol.

[0115] There are no particular limitations on diallyl bisphenols; examples include o,o'-diallyl bisphenol A ("DABPA" of Daiwa Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene. Similarly, there are no particular limitations on diallyl bisphenols; examples include o,o'-diallyl bisphenol A ("PBA01" of Gunei Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene.

[0116] From the viewpoint of more effectively and reliably exerting the effects of the present invention, the average number of phenolic groups per molecule of enylphenol A is preferably 1 or more and less than 3, more preferably 1.5 or more and less than 2.5. The average number of phenolic groups is calculated according to the following formula.

[0117]

[0118] In the formula, Ai represents the number of phenolic groups in an enylphenol molecule with i phenolic groups, Xi represents the proportion of an enylphenol molecule with i phenolic groups in the total enylphenol molecule, and X1 + X2 + ... + X... n =1.

[0119] [Epoxy-modified silicone B]

[0120] There are no particular limitations on epoxy-modified silicone B, as long as it is an organosilicon compound or resin modified with epoxy-containing groups. Curable compositions containing epoxy-modified silicone B exhibit excellent low thermal expansion and chemical resistance.

[0121] There are no particular limitations on the organosilicon compound or resin, as long as it is a polysiloxane backbone with repeating siloxane bonds. The polysiloxane backbone can be a linear backbone, a cyclic backbone, or a network backbone. Among these, a linear backbone is preferred from the viewpoint of more effectively and reliably exerting the effects of the present invention.

[0122] There are no particular limitations on the group containing an epoxy group; for example, the group shown in the following formula (a1) can be cited.

[0123] -R 0 -X (a1)

[0124] (where R is in the formula) 0 The symbol represents an alkylene group (e.g., methylene, ethylene, propylene, etc., alkylene groups having 1 to 5 carbon atoms), and X represents a monovalent group as shown in formula (a2) or formula (a3) ​​below.

[0125]

[0126]

[0127] Epoxy-modified silicone B preferably comprises an epoxy-modified silicone having an epoxy equivalent of 140–250 g / mol. By comprising an epoxy-modified silicone with an epoxy equivalent within the aforementioned range, epoxy-modified silicone B tends to further improve compatibility with thermosetting resins, low thermal expansion, and chemical resistance in a balanced manner. From the same viewpoint, the aforementioned epoxy equivalent is more preferably 145–245 g / mol, and even more preferably 150–240 g / mol.

[0128] From the viewpoint of further improving the compatibility with thermosetting resins, low thermal expansion, and chemical resistance in a balanced manner, epoxy-modified organosilicon B preferably contains two or more epoxy-modified organosilicones. In the above case, the two or more epoxy-modified organosilicones preferably have different epoxy equivalents, more preferably including epoxy-modified organosilicones with an epoxy equivalent of 50 to 350 g / mol and epoxy-modified organosilicones with an epoxy equivalent of 400 to 4000 g / mol, and even more preferably including epoxy-modified organosilicones with an epoxy equivalent of 140 to 250 g / mol and epoxy-modified organosilicones with an epoxy equivalent of 450 to 3000 g / mol.

[0129] When the epoxy-modified organosilicon B contains two or more epoxy-modified organosilicones, the average epoxy equivalent of the epoxy-modified organosilicon B is preferably 140–3000 g / mol, more preferably 250–2000 g / mol, and even more preferably 300–1000 g / mol. The average epoxy equivalent is calculated according to the following formula.

[0130]

[0131] (In the formula, Ei represents the epoxy equivalent of one of the two or more epoxy-modified organosilicones, Wi represents the ratio of the above epoxy-modified organosilicones in epoxy-modified organosilicon B, W1+W2+…W) n =1.)

[0132] From the viewpoint that it can further improve the compatibility with thermosetting resins, low thermal expansion and chemical resistance in a balanced manner, epoxy-modified organosilicon B preferably contains epoxy-modified organosilicon as shown in the following formula (1).

[0133]

[0134] (where R is in the formula) 1 Each can independently represent an alkylene, phenylene, or arylene group, R 2 Each can independently represent an alkyl or phenyl group having 1 to 10 carbon atoms, where n represents an integer greater than 1.

[0135] In equation (1), R 1Each can independently represent an alkylene, phenylene, or arylene. In formula (1), R 1 The alkylene group shown can be linear, branched, or cyclic, and all are acceptable. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 4. There are no particular limitations on the alkylene group; for example, methylene, ethylene, or propylene can be used.

[0136] In equation (1), R 1 The arylene alkyl group shown preferably has 7 to 30 carbon atoms, more preferably 7 to 13. There are no particular limitations on the arylene alkyl group, and for example, the group shown in the following formula (XI) can be cited.

[0137]

[0138] (In formula (XI), * represents an atomic bond.)

[0139] In equation (1), R 1 The shown groups may further have substituents, such as straight-chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, straight-chain alkoxy groups having 1 to 10 carbon atoms, branched alkoxy groups having 3 to 10 carbon atoms, and cyclic alkoxy groups having 3 to 10 carbon atoms. Among them, R 1 Propylene is particularly preferred.

[0140] In equation (1), R 2 Each of these groups independently represents an alkyl or phenyl group having 1 to 10 carbon atoms. The alkyl and phenyl groups may have substituents. The alkyl groups having 1 to 10 carbon atoms may be straight-chain, branched, or cyclic. There are no particular limitations on the type of alkyl group; examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among these, R... 2 Methyl or phenyl is preferred.

[0141] In formula (1), n ​​represents an integer greater than or equal to 1, for example, 1 to 100. From the viewpoint that the compatibility with thermosetting resins, low thermal expansion and chemical resistance can be further improved in a balanced manner, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

[0142] From the viewpoint of further improving the compatibility with thermosetting resins, low thermal expansion, and chemical resistance in a balanced manner, epoxy-modified organosilicon B preferably contains two or more epoxy-modified organosilicones represented by formula (1). In the above case, it is preferable that the two or more epoxy-modified organosilicones each have different n values, and more preferably, it contains epoxy-modified organosilicones with n of 1 to 2 in formula (1) and epoxy-modified organosilicones with n of 5 to 20 in formula (1).

[0143] From the viewpoint of more effectively and reliably exerting the effects of the present invention, the average number of epoxy groups per molecule of epoxy-modified organosilicon B is preferably 1 or more and less than 3, more preferably 1.5 or more and less than 2.5. The average number of epoxy groups is calculated according to the following formula.

[0144]

[0145] (In the formula, Bi represents the number of epoxy groups in an epoxy-modified organosilicon with i epoxy groups in the molecule, Yi represents the proportion of epoxy-modified organosilicon with i epoxy groups in the total epoxy-modified organosilicon, Y1+Y2+…Y n =1.)

[0146] [Epoxy Compound C]

[0147] Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, and more specifically, an epoxy compound without a polysiloxane backbone. The curable composition, by containing epoxy compound C, exhibits excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability.

[0148] As for the epoxy compound C, there are no particular limitations as long as it is an epoxy compound other than epoxy-modified organosilicon B. From the viewpoint of being able to exhibit further superior compatibility, chemical resistance, copper foil adhesion, and insulation reliability, the epoxy compound is preferably a difunctional epoxy compound containing two epoxy groups in one molecule.

[0149] As a difunctional epoxy compound, there is no particular limitation, but examples include: bisphenol type epoxy resins (e.g., bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol fluorene type epoxy resin), phenolic varnish type epoxy resins (e.g., phenolic varnish type epoxy resin, bisphenol A varnish type epoxy resin, cresol varnish type epoxy resin), triphenol methane type epoxy resin, aralkyl type epoxy resin, biphenyl type epoxy resin containing a biphenyl skeleton, naphthalene type epoxy resin containing a naphthalene skeleton, anthracene type epoxy resin containing a dihydroanthracene skeleton, glycidyl ester type epoxy resin, polyol type epoxy resin, epoxy resin containing an isocyanurate ring, dicyclopentadiene type epoxy resin, fluorene type epoxy resin containing a fluorene skeleton, epoxy resins composed of bisphenol A type structural units and hydrocarbon structural units; and their halogen compounds. These epoxy compounds can be used alone or in combination of two or more.

[0150] There are no particular limitations on aralkyl-type epoxy resins; for example, compounds represented by the following formula (b1) can be cited.

[0151]

[0152] (where Ar) 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 R represents a benzene ring, naphthalene ring, or biphenyl ring. 3a Each ring independently represents a hydrogen atom or a methyl group, and each ring may optionally have substituents other than glycidyl etheroxy groups (e.g., alkyl or phenyl groups having 1 to 5 carbon atoms).

[0153] There are no particular limitations on the type of biphenyl epoxy resin, and for example, the compound shown in the following formula (b2) (compound b2) can be cited.

[0154]

[0155] (In the formula, Ra independently represents an alkyl group or a hydrogen atom having 1 to 10 carbon atoms.)

[0156] In formula (b2), the alkyl group having 1 to 10 carbon atoms can be straight-chain, branched, or cyclic. There are no particular limitations on the type of alkyl group; examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl.

[0157] When the biphenyl-type epoxy resin is compound b2, the biphenyl-type epoxy resin can be in the form of a mixture of compounds b2 with different numbers of Ra as alkyl groups. Specifically, a mixture of biphenyl-type epoxy resins with different numbers of Ra as alkyl groups is preferred, and a mixture of compound b2 with 0 Ra as alkyl groups and compound b2 with 4 Ra as alkyl groups is more preferred.

[0158] There are no particular limitations on naphthalene-type epoxy resins; for example, compounds shown in formula (b3) below can be cited.

[0159]

[0160] (where R is in the formula) 3b Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl or ethyl), an aralkyl group, a benzyl group, a naphthyl group, or a naphthyl group containing a glycidyl etheroxy group, where n represents an integer greater than 0 (e.g., 0 to 2).

[0161] There are no particular limitations on the dicyclopentadiene type epoxy resin, and for example, compounds shown in the following formula (b4) can be cited.

[0162]

[0163] (where R is in the formula) 3c Each can independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (e.g., methyl or ethyl).

[0164] There are no particular limitations on epoxy resins composed of bisphenol A type structural units and hydrocarbon structural units; for example, compounds shown in the following formula (b5) can be cited.

[0165]

[0166] (where R is in the formula) 1x and R 2x Each can independently represent a hydrogen atom or a methyl group, R 3x ~R 6x Each atom independently represents a hydrogen atom, a methyl atom, a chlorine atom, or a bromine atom, and X represents ethyleneoxyethyl, di(ethyleneoxy)ethyl, tri(ethyleneoxy)ethyl, propyleneoxypropyl, di(propyleneoxy)propyl, tri(propyleneoxy)propyl, or an alkylene group having 2 to 15 carbon atoms (e.g., methylene or ethylene).

[0167] From the viewpoint that it can demonstrate further superior compatibility, chemical resistance, copper foil adhesion and insulation reliability, epoxy compound C is preferably selected from one or more of the group consisting of bisphenol type epoxy resin, aralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin and dicyclopentadiene type epoxy resin, more preferably biphenyl type epoxy resin and / or naphthalene type epoxy resin.

[0168] From the viewpoint of more effectively and reliably exerting the effects of the present invention, the average number of epoxy groups per molecule of epoxy compound C is preferably 1 or more and less than 3, more preferably 1.5 or more and less than 2.5. The average number of epoxy groups is calculated according to the following formula.

[0169]

[0170] (In the formula, Ci represents the number of epoxy groups in an epoxy compound with i epoxy groups in the molecule, Zi represents the proportion of an epoxy compound with i epoxy groups in the total number of epoxy compounds, Z1+Z2+…Z n =1.)

[0171] From the viewpoint that it can further demonstrate excellent compatibility, chemical resistance, copper foil adhesion and insulation reliability, the content of epoxy compound C is preferably 5 to 95% by mass, more preferably 5 to 90% by mass, further preferably 5 to 50% by mass, and particularly preferably 20 to 50% by mass, relative to 100% by mass of the total mass of epoxy-modified silicone B and epoxy compound C.

[0172] [Phenolic compounds F other than alkenylphenol A]

[0173] From the viewpoint of achieving further superior copper foil adhesion, the curable composition of the first embodiment preferably contains a phenolic compound F other than alkenylphenol A. The phenolic compound F is not particularly limited, and examples include bisphenol-type phenolic resins (e.g., bisphenol A type resin, bisphenol E type resin, bisphenol F type resin, bisphenol S type resin, etc.), phenolic varnish resins (e.g., phenol varnish resin, naphthol varnish resin, cresol varnish resin, etc.), glycidyl ester type phenolic resins, naphthyl phenolic resins, anthracene type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic phenolic resins, polyol type phenolic resins, aralkyl type phenolic resins, phenol-modified aromatic hydrocarbon formaldehyde resins, fluorene type phenolic resins, etc. These phenolic compounds can be used alone or in combination of two or more.

[0174] Among them, from the viewpoint that it can demonstrate further superior compatibility and copper foil adhesion, phenolic compound F is preferably a difunctional phenolic compound having two phenolic hydroxyl groups in one molecule.

[0175] There are no particular limitations on the difunctional phenolic compounds, and examples include bisphenol, biscresol, bisphenols with a fluorene skeleton (e.g., bisphenol with a fluorene skeleton, biscresol with a fluorene skeleton, etc.), biphenol (e.g., p,p'-biphenol, etc.), dihydroxy diphenyl ether (e.g., 4,4'-dihydroxy diphenyl ether, etc.), dihydroxy diphenyl ketone (e.g., 4,4'-dihydroxy diphenyl ketone, etc.), dihydroxy diphenyl sulfide (e.g., 4,4'-dihydroxy diphenyl sulfide, etc.), and dihydroxy aromatic hydrocarbons (e.g., hydroquinone, etc.). These difunctional phenolic compounds can be used alone or in combination of two or more. Among them, from the viewpoint of achieving further superior copper foil adhesion, bisphenol, biscresol, and bisphenols with a fluorene skeleton are preferred difunctional phenolic compounds.

[0176] From the viewpoint that it can demonstrate further excellent compatibility, the content of alkenylphenol A is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 15 to 40 parts by mass, relative to the total amount of alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C and phenolic compound F in 100 parts by mass.

[0177] From the viewpoint that it can better balance and reflect further excellent low thermal expansion and chemical resistance, the content of epoxy-modified organosilicon B is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 40 to 50 parts by mass relative to the total amount of alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C and phenolic compound F in 100 parts by mass.

[0178] From the viewpoint that it can further demonstrate excellent compatibility, chemical resistance, copper foil adhesion and insulation reliability, the content of epoxy compound C is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to the total amount of alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C and phenolic compound F in 100 parts by mass.

[0179] From the viewpoint that it can demonstrate further superior copper foil adhesion, the content of phenolic compound F is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to the total amount of alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C and phenolic compound F in 100 parts by mass.

[0180] It should be noted that, in the case that the curable composition does not contain phenolic compound F, the contents of alkenylphenol A, epoxy-modified organosilicon B and epoxy compound C mentioned above represent the contents relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified organosilicon B and epoxy compound C.

[0181] [Second Embodiment: Curable Composition]

[0182] The curable composition of the second embodiment comprises polymer D, which contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C. The alkenylphenol A, epoxy-modified silicone B, and epoxy compound C described in the first embodiment can be used as the alkenylphenol A, epoxy-modified silicone B, and epoxy compound C.

[0183] Even when mixed with thermosetting resins that lack compatibility with silicone compounds, polymer D exhibits sufficient compatibility. Therefore, curable compositions containing polymer D and thermosetting resins can provide uniform varnishes and cured products. For cured products such as prepregs obtained using this curable composition, the components are uniformly miscible, and fluctuations in physical properties caused by component inhomogeneity are suppressed.

[0184] It should be noted that, in addition to polymer D, the curable composition of the second embodiment may also contain one or more components selected from the group consisting of alkenylphenol A, epoxy-modified organosilicon B, and epoxy compound C. In the above case, alkenylphenol A, epoxy-modified organosilicon B, or epoxy compound C contained in the curable composition of the second embodiment may be unreacted components remaining after the polymerization of polymer D, or components added back to purified polymer D.

[0185] [Polymer D]

[0186] Polymer D contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C. It may also contain structural units derived from phenolic compound F, if desired. Hereinafter, each structural unit will be referred to as structural unit A, B, C, and F, respectively. By using polymer D, the curable composition of the second embodiment exhibits further superior compatibility, thermal expansion, chemical resistance, peel strength, and insulation reliability.

[0187] The weight-average molecular weight of polymer D, converted to polystyrene in gel permeation chromatography, is preferably 3.0 × 10⁻⁶. 3 ~5.0×10 4 More preferably 3.0×10 3 ~2.0×10 4 The weight-average molecular weight is 3.0 × 10⁻⁶. 3 The above-mentioned curable compositions tend to exhibit further superior copper foil adhesion and chemical resistance. This is achieved through a weight-average molecular weight of 5.0 × 10⁻⁶. 4 The following shows a tendency to demonstrate even better compatibility.

[0188] The content of structural unit A in polymer D is preferably 5 to 50% by mass relative to the total mass of polymer D. With the content of structural unit A within the above range, the curable composition tends to exhibit further excellent compatibility. From the same viewpoint, the content of structural unit A is more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass.

[0189] The content of structural unit B in polymer D is preferably 20-60% by mass relative to the total mass of polymer D. With the content of structural unit B within the above range, the curable composition tends to exhibit further excellent low thermal expansion and chemical resistance in a well-balanced manner. From the same viewpoint, the content of structural unit B is more preferably 25-55% by mass, and even more preferably 30-50% by mass.

[0190] Structural unit B is preferably derived from epoxy-modified organosilicon with an epoxy equivalent of 50 to 350 g / mol (hereinafter also referred to as "low equivalent epoxy-modified organosilicon B1") and epoxy-modified organosilicon with an epoxy equivalent of 400 to 4000 g / mol (hereinafter also referred to as "high equivalent epoxy-modified organosilicon B2").

[0191] The content of structural unit B1 derived from low-equivalent epoxy-modified organosilicon B1 in polymer D is preferably 5 to 22.5% by mass, more preferably 10 to 20% by mass, and even more preferably 10 to 17% by mass relative to the total mass of polymer D.

[0192] The content of structural unit B2 derived from high-equivalent epoxy-modified organosilicon B2 in polymer D is preferably 15-55% by mass, more preferably 20-52.5% by mass, and even more preferably 25-50% by mass relative to the total mass of polymer D.

[0193] The mass ratio of structural unit B2 to structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and even more preferably 1.9 to 3.1. With the above-mentioned relationship between the contents of structural unit B1 and structural unit B2, there is a tendency for further improvement in the copper foil adhesion and chemical resistance.

[0194] The content of structural unit C in polymer D is preferably 5 to 30% by mass relative to the total mass of polymer D. If the content of structural unit C is within the above range, the curable composition tends to exhibit further excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability. From the same viewpoint, the content of structural unit C is preferably 10 to 25% by mass, more preferably 15 to 20% by mass.

[0195] Furthermore, the content of structural unit C relative to the total mass of structural unit B and structural unit C is preferably 5 to 95% by mass, more preferably 5 to 90% by mass, even more preferably 5 to 50% by mass, and particularly preferably 20 to 50% by mass. With the above-mentioned relationship between the contents of structural unit B and structural unit C, there is a tendency for further improvements in compatibility, chemical resistance, copper foil adhesion, and insulation reliability.

[0196] The content of structural unit F in polymer D is preferably 5 to 30% by mass relative to the total mass of polymer D. With the content of structural unit F within the above range, the curable composition tends to exhibit further excellent copper foil adhesion. From the same viewpoint, the content of structural unit F is preferably 10 to 25% by mass, more preferably 15 to 20% by mass.

[0197] The alkenyl equivalent of polymer D is preferably 300 to 1500 g / mol. When the alkenyl equivalent is 300 g / mol or higher, the cured product of the curable composition tends to have a further decrease in elastic modulus, resulting in a tendency to further reduce the thermal expansion of substrates and the like obtained using the cured product. When the alkenyl equivalent is 1500 g / mol or lower, the compatibility, chemical resistance, and reliability of the curable composition tend to be further improved. From the same viewpoint, the alkenyl equivalent is preferably 350 to 1200 g / mol, and more preferably 400 to 1000 g / mol.

[0198] Polymer D can be obtained, for example, by reacting alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C, and a desired phenolic compound F in the presence of polymerization catalyst G. This reaction can be carried out in the presence of an organic solvent. More specifically, in the above steps, polymer D can be obtained by performing addition reactions of the epoxy groups of epoxy-modified organosilicon B and epoxy compound C with the hydroxyl groups of alkenylphenol A, and by performing addition reactions of the hydroxyl groups of the resulting addition product with the epoxy groups of epoxy-modified organosilicon B and epoxy compound C.

[0199] There are no particular limitations on the polymerization catalyst G; for example, imidazole catalysts and phosphorus-based catalysts can be cited. These catalysts can be used alone or in combination of two or more. Among them, imidazole catalysts are preferred.

[0200] There are no particular limitations on the imidazole catalysts used, and examples include 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (TBZ, manufactured by Shikoku Chemical Industry Co., Ltd.), and 2,4,5-triphenylimidazolium (TPIZ, manufactured by Tokyo Chemical Industry Co., Ltd.). From the viewpoint of preventing homopolymerization of the epoxy component, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and / or 2,4,5-triphenylimidazolium (TPIZ, manufactured by Tokyo Chemical Industry Co., Ltd.) are preferred.

[0201] The amount of polymerization catalyst G (preferably imidazole catalyst) is not particularly limited, for example, it is 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C and phenolic compound F. From the viewpoint of increasing the weight-average molecular weight of polymer D, the amount of polymerization catalyst G is preferably 1.0 parts by mass or more, more preferably 4.0 parts by mass or less.

[0202] As organic solvents, there are no particular limitations; for example, polar or non-polar solvents can be used. As polar solvents, there are no particular restrictions; examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide. As non-polar solvents, there are no particular limitations; examples include aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0203] There is no particular limitation on the amount of organic solvent used, for example, it is 50 to 150 parts by mass relative to the total amount of alkenylphenol A, epoxy-modified organosilicon B, epoxy compound C and phenolic compound F, 100 parts by mass.

[0204] There is no particular limitation on the heating temperature; for example, it can be 100–170°C. There is also no particular limitation on the heating time; for example, it can be 3–8 hours.

[0205] After the reaction in this process is completed, polymer D can be separated and purified from the reaction mixture using common methods.

[0206] [Thermosetting Resin E]

[0207] The curable compositions of the first and second embodiments preferably contain a thermosetting resin E. The polymer D, having an organosilicon backbone, exhibits excellent compatibility with thermosetting resins lacking compatibility with organosilicon compounds. Therefore, even when polymer D is combined with thermosetting resin E, the components do not separate within the curable composition, demonstrating excellent compatibility. Furthermore, the curable composition of the second embodiment, containing both polymer D and thermosetting resin E, exhibits further superior low thermal expansion and chemical resistance.

[0208] For thermosetting resin E, from the viewpoint of further improving low thermal expansion, chemical resistance and copper foil adhesion, it is preferable to contain one or more compounds selected from the group consisting of maleimide compounds, cyanate compounds, phenolic compounds, alkenyl-substituted nadicimide compounds and epoxy compounds, and more preferably, it contains one or more compounds selected from the group consisting of maleimide compounds, cyanate compounds, phenolic compounds and epoxy compounds.

[0209] The content of thermosetting resin E relative to 100% by mass of the resin solids is preferably 10-90% by mass, more preferably 20-80% by mass, and even more preferably 30-75% by mass.

[0210] [Maleimide compounds]

[0211] From the viewpoint of further improving low thermal expansion and chemical resistance, thermosetting resin E preferably contains a maleimide compound. As a maleimide compound, there is no particular limitation as long as it is a compound having one or more maleimide groups in one molecule. Examples include: monomaleimide compounds having one maleimide group in one molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), and polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleiminophenyl)methane, 2,2-bis{4-(4-maleiminophenoxy)-phenyl}). Propane, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, bis(3,5-dimethyl-4-maleimide-phenyl)methane, bis(3,5-diethyl-4-maleimide-phenyl)methane, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, maleimide compounds represented by formula (3) below, prepolymers of these maleimide compounds and amine compounds, etc.

[0212]

[0213] (where R is in the formula) 5 Each atom can be independently represented by a hydrogen atom or a methyl group, and n1 represents an integer greater than or equal to 1.

[0214] n1 is 1 or more, preferably 1 to 100, and more preferably 1 to 10.

[0215] These maleimide compounds can be used alone or in combination of two or more. From the viewpoint of further improving low thermal expansion and chemical resistance, the maleimide compounds preferably include at least one selected from the group consisting of bis(4-maleiminophenyl)methane, 2,2-bis{4-(4-maleiminophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane and the maleimide compound shown in formula (3).

[0216] Maleimide compounds can be commercially available or prepared by known methods. Examples of commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" manufactured by K·I Chemical Industry Co., Ltd.; "BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300" manufactured by Yamato Chemical Industry Co., Ltd.; and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

[0217] Regarding the content of maleimide compounds, from the viewpoint of further improving low thermal expansion and chemical resistance, it is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and even more preferably 10 to 40 parts by weight, relative to 100 parts by weight of the resin solids.

[0218] [Cyanate ester compounds]

[0219] From the viewpoint of further improving low thermal expansion and chemical resistance, thermosetting resin E preferably contains a cyanate ester compound. As a cyanate ester compound, there is no particular limitation as long as it is a compound having two or more cyanoxy (cyanate ester groups) in one molecule. Examples include compounds shown in formula (4) below, compounds shown in formula (5) below other than those shown in formula (4), biphenyl aralkyl cyanate esters, bis(3,3-dimethyl-4-cyanoxyphenyl)methane, bis(4-cyanoxyphenyl)methane, 1,3-dicyanoxyphenyl, 1,4-dicyanoxyphenyl, 1,3,5-tricyanoxyphenyl, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene, 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4'-dicyanoxybiphenyl, bis(4-cyanoxyphenyl) ether, bis(4-cyanoxyphenyl) sulfide, bis(4-cyanoxyphenyl) sulfone, and 2,2-bis(4-cyanoxyphenyl)propane. These cyanate compounds can be used alone or in combination of two or more.

[0220]

[0221] (where R is in the formula) 6 Each can independently represent a hydrogen atom or a methyl group, and n2 represents an integer greater than or equal to 1.

[0222]

[0223] (In the formula, Rya independently represents an alkenyl group with 2 to 8 carbon atoms, Ryb independently represents an alkyl group with 1 to 10 carbon atoms or a hydrogen atom, Ryc independently represents an aromatic ring with 4 to 12 carbon atoms, Ryc optionally forms a fused structure with a benzene ring, Ryc optionally exists or does not exist, A) 1a The group can be an alkylene group having 1 to 6 carbon atoms, an arylene group having 7 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a fluorene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a directly bonded (single bond). In the absence of Ryc, it can be a group optionally having two or more Rya and / or Ryb groups on one benzene ring. n represents an integer from 1 to 10.

[0224] For cyanate ester compounds, from the viewpoint of further improving low thermal expansion and chemical resistance, compounds containing formula (4) and / or formula (5) are preferred.

[0225] In equation (4), n2 represents an integer greater than or equal to 1, preferably an integer from 1 to 20, and more preferably an integer from 1 to 10.

[0226] In formula (5), there are no particular restrictions on the alkenyl groups with 2 to 8 carbon atoms represented as Rya. Examples include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0227] In formula (5), there are no particular restrictions on the alkyl groups with 1 to 10 carbon atoms represented as Ryb. Examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0228] In equation (5), for A 1a The alkylene group representing 1 to 6 carbon atoms is not particularly limited, and examples include methylene, ethylene, trimethylene, and propylene. Additionally, in formula (5), for A... 1a The arylene alkyl group representing 7 to 16 carbon atoms is not particularly limited, and examples include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (where Ar represents phenylene, naphthylene, or biphenylene). Furthermore, for groups represented as A... 1a The arylene group represented has 6 to 10 carbon atoms and is not particularly limited; for example, a phenylene ring can be used.

[0229] In equation (5), n represents an integer from 1 to 10, preferably an integer from 1 to 20, and more preferably an integer from 1 to 10.

[0230] The compound represented by formula (5) is preferably the compound represented by formula (c1) below.

[0231]

[0232] (In the formula, Rx independently represents a hydrogen atom or a methyl group, R independently represents an alkenyl group with 2 to 8 carbon atoms, an alkyl group with 1 to 10 carbon atoms, or a hydrogen atom, and n represents an integer from 1 to 10.)

[0233] These cyanate compounds can be manufactured using known methods. Specific manufacturing methods include those described in Japanese Patent Application Publication No. 2017-195334 (particularly paragraphs 0052-0057).

[0234] Regarding the content of the cyanate compound in thermosetting resin E, from the viewpoint of further improving low thermal expansion and chemical resistance, it is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass relative to 100 parts by mass of the resin solids.

[0235] [Phenolic compounds]

[0236] From the viewpoint of further improving the adhesion of copper foil, thermosetting resin E preferably contains a phenolic compound. As a phenolic compound, there is no particular limitation as long as it is a compound having two or more phenolic hydroxyl groups per molecule. Examples include phenols, bisphenols (e.g., bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (e.g., diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.), phenolic varnish resins (e.g., phenolic varnish resin, naphthol varnish resin, cresol varnish resin, etc.), naphthyl-type phenolic resins, dihydroanthracene-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, and aralkyl-type phenolic resins. These phenolic compounds can be used alone or in combination of two or more. Among them, from the viewpoint of further improving the adhesion of copper foil, the phenolic compound preferably contains an aralkyl-type phenolic resin.

[0237] (Aryl phenolic resin)

[0238] Examples of aralkyl-type phenolic resins include compounds represented by the following formula (c2).

[0239]

[0240] (where Ar) 1 Each independently represents a benzene ring or a naphthalene ring, Ar 2 R represents a benzene ring, naphthalene ring, or biphenyl ring. 2a Each ring independently represents a hydrogen atom or a methyl group, m represents an integer from 1 to 50, and each ring may optionally have substituents other than a hydroxyl group (e.g., alkyl groups with 1 to 5 carbon atoms or phenyl groups).

[0241] From the viewpoint of further improving the adhesion of copper foil, the compound represented by formula (c2) is preferably the one containing Ar in formula (c2). 1 Naphthalene ring, Ar 2 Compounds containing a benzene ring (hereinafter also referred to as "naphthol aralkyl phenolic resins"), and in formula (c2), Ar 1 It is a benzene ring, Ar 2 It is a compound of biphenyl ring (hereinafter also referred to as "biphenyl aralkyl type phenolic resin").

[0242] Naphthol aralkyl phenolic resin is preferably a compound represented by the following formula (2b).

[0243]

[0244] (where R is in the formula) 2a Each element independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), and m represents an integer from 1 to 10 (preferably an integer from 1 to 6).

[0245] The preferred compound is the one shown in formula (2c).

[0246]

[0247] (where R is in the formula) 2b Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group (preferably a hydrogen atom); m1 represents an integer from 1 to 20 (preferably an integer from 1 to 6).

[0248] Aryl alkyl phenolic resins can be commercially available or synthesized using known methods. Examples of commercially available aryl alkyl phenolic resins include "KAYAHARD GPH-65", "KAYAHARD GPH-78", and "KAYAHARD GPH-103" (biphenyl aryl phenolic resin) from Nippon Chemical Co., Ltd., and "SN-495" (naphthol aryl phenolic resin) from Nippon Steel Chemical Co., Ltd.

[0249] Regarding the content of phenolic compounds in thermosetting resin E, from the viewpoint of further improving the adhesion of copper foil, it is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, and even more preferably 20 to 30 parts by mass relative to 100 parts by mass of resin solids.

[0250] [Alkenyl-substituted nadicimide compounds]

[0251] From the viewpoint of further improving heat resistance, thermosetting resin E preferably contains an alkenyl-substituted nadicimide compound. The alkenyl-substituted nadicimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadicimide groups in one molecule, and examples include compounds shown in the following formula (2d).

[0252]

[0253] (In the formula, R1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl or ethyl), and R2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by formula (6) or formula (7) below.)

[0254]

[0255] (In formula (6), R3 represents methylene, isopropylidene, CO, O, S or SO2.)

[0256]

[0257] (In formula (7), R4 independently represents an alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.)

[0258] The alkenyl-substituted nadicimide compounds shown in formula (6) or formula (7) can be commercially available products or manufactured products produced according to known methods. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

[0259] The content of the alkenyl-substituted nadicimide compound as thermosetting resin E is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass relative to 100 parts by mass of the resin solids.

[0260] [Epoxy Compounds]

[0261] From the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, thermosetting resin E preferably contains an epoxy compound. It should be noted that this epoxy compound refers to an epoxy compound different from the epoxy-modified silicone B and epoxy compound C that constitute polymer D.

[0262] As for epoxy compounds, there are no particular limitations as long as they are compounds having two or more epoxy groups in one molecule. Examples include bisphenol type epoxy resins (such as bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin), diallyl bisphenol type epoxy resins (such as diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol S type epoxy resin, etc.), and phenolic varnish type epoxy resins. Epoxy resins (e.g., phenolic varnish epoxy resins, bisphenol A phenolic varnish epoxy resins, cresol phenolic varnish epoxy resins), aralkyl epoxy resins, biphenyl-type epoxy resins containing a biphenyl skeleton, naphthalene-type epoxy resins containing a naphthalene skeleton, anthracene-type epoxy resins containing a dihydroanthracene skeleton, glycidyl esters, polyol-type epoxy resins, epoxy resins containing isocyanurate rings, dicyclopentadiene-type epoxy resins, epoxy resins composed of bisphenol A type structural units and hydrocarbon structural units, and their halogenated compounds. These epoxy compounds can be used alone or in combination of two or more.

[0263] Of the epoxy compounds, from the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, one or more are preferably selected from the group consisting of aryl alkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins and epoxy resins composed of bisphenol A structural units and hydrocarbon structural units, and more preferably contain naphthalene epoxy resins.

[0264] (Aryl alkyl type epoxy resin)

[0265] There are no particular limitations on aralkyl-type epoxy resins; for example, compounds represented by the following formula (3a) can be cited.

[0266]

[0267] (where Ar) 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 R represents a benzene ring, naphthalene ring, or biphenyl ring. 3a Each ring independently represents a hydrogen atom or a methyl group, k represents an integer from 1 to 50, and each ring may optionally have substituents other than glycidyl etheroxy groups (e.g., alkyl or phenyl groups having 1 to 5 carbon atoms).

[0268] The compound shown in formula (3a) is preferably Ar 3 Naphthalene ring, Ar 4 Compounds consisting of benzene rings (also known as "naphthalene alkyl alkyl type epoxy resins") and Ar 3 It is a benzene ring, Ar 4 It is a compound of biphenyl ring (also known as "biphenyl aralkyl type epoxy resin"), more preferably a biphenyl aralkyl type epoxy resin.

[0269] Biphenyl aryl epoxy resins are preferably compounds represented by the following formula (3b).

[0270]

[0271] (In the formula, ka represents an integer greater than or equal to 1, preferably 1 to 20, and more preferably 1 to 6.)

[0272] Alternatively, aralkyl epoxy resins can be compounds represented by the following formula (3c).

[0273]

[0274] (In the formula, ky represents an integer from 1 to 10.)

[0275] Aryl alkyl type epoxy resins can be commercially available products or products prepared by known methods. Examples of commercially available naphthalene alkyl type epoxy resins include Nippon Steel & Sumitomo Chemical Co., Ltd.'s "Epototo (registered trademark) ESN-155", "Epototo (registered trademark) ESN-355", "Epototo (registered trademark) ESN-375", "Epototo (registered trademark) ESN-475V", "Epototo (registered trademark) ESN-485", and "Epototo (registered trademark) ESN-175", Nippon Kayaku Co., Ltd.'s "NC-7000", "NC-7300", and "NC-7300L", and DIC Co., Ltd.'s "HP-5000" and "HP-9900". Commercially available products of biphenyl aralkyl type epoxy resins include, for example, “NC-3000”, “NC-3000L”, and “NC-3000FH” manufactured by Nippon Kayaku Co., Ltd.

[0276] (Naphthalene-type epoxy resin)

[0277] There are no particular limitations on the naphthalene-type epoxy resin. For example, it can be any epoxy resin other than the naphthalene aralkyl-type epoxy resin described above. Examples include multifunctional epoxy resins containing a naphthalene skeleton with the naphthalene skeleton shown in formula (3-1) below, and epoxy resins having a naphthalene skeleton. As specific examples of naphthalene-type epoxy resins, examples include naphthalene ether-type epoxy resins. From the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, naphthalene ether-type epoxy resins are preferred.

[0278]

[0279] (where Ar) 31 Each independently represents a benzene ring or a naphthalene ring, Ar 41 R represents a benzene ring, naphthalene ring, or biphenyl ring. 31a Each ring independently represents a hydrogen atom or a methyl group, p is an integer from 0 to 2, preferably 0 or 1, kz is an integer from 1 to 50, and each ring may optionally have substituents other than glycidyl etheroxy groups (e.g., alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, or phenyl groups), Ar 31 and Ar 41 (At least one of them represents a naphthalene ring.)

[0280] As a compound represented by formula (3-1), a compound represented by formula (3-2) can be cited.

[0281]

[0282] (In the formula, R represents methyl, and kz has the same meaning as kz in the above formula (3-1).)

[0283] Multifunctional epoxy resins containing a naphthalene skeleton can be commercially available products or products prepared by known methods. Examples of commercially available multifunctional epoxy resins containing a naphthalene skeleton include "HP-9540" and "HP-9500" manufactured by DIC Corporation.

[0284] From the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, naphthalene ether type epoxy resin is preferably a compound shown in formula (3-3) or a compound shown in formula (3-4).

[0285]

[0286] (where R is in the formula) 13 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0287]

[0288] (where R is in the formula) 14 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0289] Naphthalene ether type epoxy resins can be commercially available products or products prepared by known methods. Examples of commercially available naphthalene ether type epoxy resins include products from DIC Corporation such as "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", and "EXA-7311G5".

[0290] (Dicyclopentadiene type epoxy resin)

[0291] There are no particular limitations on dicyclopentadiene-type epoxy resins; for example, compounds shown in formulas (3-5) below can be cited.

[0292]

[0293] (where R is in the formula) 3c Each can independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer from 0 to 10.

[0294] Dicyclopentadiene-type epoxy resins can be commercially available or prepared products made using known methods. Examples of commercially available dicyclopentadiene-type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", and "EPICRON HP-7000HH" manufactured by Dai Nippon Ink & Chemical Co., Ltd.

[0295] (Epoxy resin composed of bisphenol A structural units and hydrocarbon structural units)

[0296] Epoxy resins composed of bisphenol A type structural units and hydrocarbon structural units (also referred to as "specific epoxy resins") have one or more bisphenol A type structural units and one or more hydrocarbon structural units in their molecules. Examples of such specific epoxy resins include compounds represented by the following formula (3e).

[0297]

[0298] (where R is in the formula) 1x and R 2x Each can independently represent a hydrogen atom or a methyl group, R 3x ~R 6x Each atom independently represents a hydrogen atom, a methyl atom, a chlorine atom, or a bromine atom; X represents ethyleneoxyethyl, di(ethyleneoxy)ethyl, tri(ethyleneoxy)ethyl, propyleneoxypropyl, di(propyleneoxy)propyl, tri(propyleneoxy)propyl, or an alkylene group having 2 to 15 carbon atoms; and k3 represents a natural number.

[0299] k3 represents a natural number, preferably 1 to 100, and more preferably 1 to 10.

[0300] Specific epoxy resins can be commercially available products or products prepared by known methods. Examples of commercially available specific epoxy resins include "EPICLON EXA-4850-150" and "EPICLON EXA-4816" manufactured by DIC Corporation.

[0301] Regarding the content of the epoxy compound in thermosetting resin E, from the viewpoint of further improving chemical resistance, copper foil adhesion and insulation reliability, it is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass relative to 100 parts by mass of the resin solids.

[0302] The thermosetting resin E may also contain other resins, as long as it does not interfere with the effects of the curable compositions of the first and second embodiments. Examples of other resins include oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins may be used alone or in combination of two or more.

[0303] Examples of oxetane resins include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3'-di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, and "OXT-101" and "OXT-121" manufactured by Toa Synthetic Co., Ltd.

[0304] The term "benzoxazine compound" as used in this specification refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of benzoxazine compounds include "bisphenol F type benzoxazine BF-BXZ" and "bisphenol S type benzoxazine BS-BXZ" manufactured by Konishi Chemical Co., Ltd.

[0305] Examples of compounds containing polymerizable unsaturated groups include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; monohydric or polyhydric alcohols such as methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polypropylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol hexamethacrylate; epoxy methacrylates such as bisphenol A epoxy methacrylate and bisphenol F epoxy methacrylate; and benzocyclobutene resins.

[0306] The content of polymer D relative to 100% by mass of the resin solids is preferably 5-50% by mass, more preferably 10-45% by mass, and even more preferably 10-30% by mass. If the content is within the above range, the curable composition tends to exhibit evenly excellent compatibility, low thermal expansion, and chemical resistance.

[0307] Furthermore, the content of polymer D relative to the total mass of polymer D and thermosetting resin E is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 30% by mass. If the content is within the above range, the curable composition tends to exhibit evenly excellent compatibility, low thermal expansion, and chemical resistance.

[0308] [Inorganic filler materials]

[0309] From the viewpoint of further improving low thermal expansion, the curable compositions of the first and second embodiments preferably also contain inorganic filler materials. As an inorganic filler material, there are no particular limitations. Examples include silica, silicon compounds (such as white carbon), metal oxides (such as aluminum oxide, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides (such as boron nitride, polyboron nitride, silicon nitride, aluminum nitride, etc.), metal sulfates (such as barium sulfate, etc.), metal hydroxides (such as aluminum hydroxide, heat-treated aluminum hydroxide (e.g., aluminum hydroxide that has undergone heat treatment to reduce some of its water of crystallization), boehmite, magnesium hydroxide, etc.), molybdenum compounds (such as molybdenum oxide, zinc molybdate, etc.), zinc compounds (such as zinc borate, zinc stannate, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass micropowders of E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), insulated glass, spherical glass, etc. These inorganic filler materials can be used alone or in combination of two or more. Among them, for inorganic filler materials, from the viewpoint of further improving low thermal expansion, it is preferable to select at least one from the group consisting of metal hydroxides and metal oxides, more preferably to include at least one from the group consisting of silica, boehmite and alumina, and even more preferably silica.

[0310] Examples of silica types include natural silica, fused silica, synthetic silica, Aerosil, and hollow silica. These silica types can be used individually or in combination of two or more. From a dispersibility perspective, fused silica is preferred; from a filling and flowability perspective, two or more types of fused silica with different particle sizes are more preferred.

[0311] Regarding the content of inorganic filler material, from the viewpoint of further improving low thermal expansion, it is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, and even more preferably 100 to 300 parts by mass relative to 100 parts by mass of resin solids.

[0312] [Silane coupling agent]

[0313] The curable compositions of the first and second embodiments may further contain a silane coupling agent. By containing a silane coupling agent, the curable compositions of the first and second embodiments tend to further improve the dispersibility of inorganic filler materials or the adhesion strength between the components of the curable compositions of the first and second embodiments and the substrate described later.

[0314] As a silane coupling agent, there is no particular limitation. Examples of silane coupling agents commonly used for surface treatment of inorganic materials include aminosilane compounds (such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (such as γ-glycidyl etheroxypropyltrimethoxysilane, etc.), acrylic silane compounds (such as γ-acryloyloxypropyltrimethoxysilane, etc.), cationic silane compounds (such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds, and phenylsilane compounds. A single silane coupling agent can be used alone, or in combination of two or more. Among these, epoxysilane compounds are preferred. Examples of epoxy silane compounds include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

[0315] The content of the silane coupling agent is not particularly limited, but can be 0.1 to 5.0 parts by weight relative to 100 parts by weight of the resin solids.

[0316] [Wetting and dispersing agents]

[0317] The curable compositions of the first and second embodiments may further contain a wetting and dispersing agent. The curable compositions of the first and second embodiments, by containing a wetting and dispersing agent, tend to further improve the dispersibility of the filler material.

[0318] As a wetting and dispersing agent, any known dispersant (dispersion stabilizer) used to disperse filler materials can be used, such as DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, W903, etc. manufactured by BYK CHEMIE Japan Ltd.

[0319] The content of the wetting and dispersing agent is not particularly limited, but it is preferably 0.5 parts by weight or more and 5.0 parts by weight or less relative to 100 parts by weight of the resin solids.

[0320] [Solvent]

[0321] The curable compositions of the first and second embodiments may further contain a solvent. By including a solvent, the curable compositions of the first and second embodiments tend to have a tendency to reduce viscosity during the preparation of the curable composition, further improve workability (processability), or further improve the penetration into the substrate.

[0322] As a solvent, there are no particular limitations as long as it can dissolve some or all of the components in the curable composition. Examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g., toluene, xylene, etc.), amides (e.g., dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetates, etc. These solvents can be used alone or in combination of two or more.

[0323] As a method for manufacturing the curable composition of the first and second embodiments, one example is the method of simultaneously or sequentially mixing each component with a solvent and stirring. In this case, known processes such as stirring, mixing, and kneading can be used to ensure that each component is uniformly dissolved or dispersed.

[0324] [use]

[0325] The curable composition of this embodiment exhibits excellent compatibility, low thermal expansion, and chemical resistance, as described above. Therefore, the curable composition of this embodiment is suitable for use in metal foil laminates and printed circuit boards.

[0326] [Prepreg]

[0327] The prepreg of this embodiment comprises: a substrate; and a curable composition of this embodiment impregnated or coated onto the substrate. As described above, the prepreg can be a prepreg obtained by a known method, specifically, by impregnating or coating the curable composition of this embodiment onto the substrate and then heating and drying it at 100 to 200°C to semi-cur it (B-stage curing).

[0328] The prepreg in this embodiment also includes the form of a cured product obtained by heat curing a semi-cured prepreg at a heating temperature of 180 to 230°C and a heating time of 60 to 180 minutes.

[0329] The content of the curable composition in the prepreg, relative to the total amount of the prepreg, is preferably 30-90% by volume, more preferably 35-85% by volume, and even more preferably 40-80% by volume, calculated as the solids content of the prepreg. A content of the curable composition within the above range tends to further improve moldability. It should be noted that the solids content of the prepreg referred to here means the components from which the solvent has been removed, such as filler materials included in the solids content of the prepreg.

[0330] There are no particular limitations on the substrate material; for example, known substrates used in various printed circuit boards can be cited. Specific examples of substrate materials include glass substrates, inorganic substrates other than glass (e.g., inorganic substrates composed of inorganic fibers other than quartz glass), and organic substrates (e.g., organic substrates composed of organic fibers such as fully aromatic polyamides, polyesters, poly(p-phenylenebenzoxazole), and polyimide). These substrates can be used alone or in combination of two or more. Among them, glass substrates are preferred from the viewpoint of further improving dimensional stability under heat.

[0331] Examples of fibers constituting a glass substrate include E-glass, D-glass, S-glass, T-glass, Q-glass, L-glass, NE-glass, and HME-glass fibers. From the viewpoint of further improving strength and low water absorption, the fibers constituting the glass substrate are preferably selected from one or more fibers in the group consisting of E-glass, D-glass, S-glass, T-glass, Q-glass, L-glass, NE-glass, and HME-glass.

[0332] The form of the substrate is not particularly limited; examples include woven fabric, nonwoven fabric, roving, chopped strand mat, and cushioning mat. The weaving method is also not particularly limited; known methods include plain weave, square plain weave, and twill weave. These well-known methods can be selected and used appropriately based on the intended use and performance. Additionally, glass fabrics that have undergone fiber opening treatment or surface treatment with silane coupling agents are suitable. The thickness and weight of the substrate are not particularly limited; a thickness of approximately 0.01–0.1 mm is generally suitable.

[0333] The resin sheet of this embodiment includes: a support; and a curable composition of this embodiment disposed on the surface of the support. The resin sheet of this embodiment can be formed, for example, by coating one or both sides of the support with the curable composition of this embodiment. The resin sheet of this embodiment can also be manufactured, for example, by directly coating a support such as a metal foil or film with a curable composition used in prepregs and then drying it.

[0334] There are no particular limitations on the support material; for example, various known supports used in printed circuit board materials can be used, with resin sheets or metal foils being preferred. Examples of resin sheets and metal foils include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, and other resin sheets, as well as metal foils such as aluminum foil, copper foil, and gold foil. Among these, electrolytic copper foil and PET film are preferred as supports.

[0335] The resin sheet of this embodiment is obtained, for example, by applying the curable composition of this embodiment to a support and then performing semi-curing (B-stage curing). The manufacturing method of the resin sheet of this embodiment is generally preferably a method for manufacturing a composite of B-stage resin and a support. Specifically, examples include methods such as semi-curing by applying the above-mentioned curable composition to a support such as copper foil, and then heating it in a dryer at 100-200°C for 1-60 minutes, and then manufacturing the resin sheet. The amount of curable composition adhering to the support is preferably in the range of 1.0 μm or more and 300 μm or less, based on the resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a lamination material for printed circuit boards.

[0336] [Metal Foil-Clad Laminate]

[0337] The metal-coated laminate of this embodiment comprises: a laminate formed from one or more prepregs and resin sheets selected from the group consisting of the prepregs and resin sheets of this embodiment; and a metal foil disposed on one or both sides of the laminate. The laminate may be formed from one prepreg or resin sheet, or from multiple prepregs and / or resin sheets.

[0338] As the metal foil (conductor layer), any metal foil used in various printed circuit board materials can be used, such as copper or aluminum foil. For copper foil, rolled copper foil, electrolytic copper foil, and other copper foils can be used. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

[0339] There are no particular limitations on the forming methods and conditions for metal-clad laminates; the methods and conditions used for general printed circuit board laminates and multilayer boards can be applied. For example, multi-stage presses, multi-stage vacuum presses, continuous forming machines, and autoclave forming machines can be used in the forming of laminates or metal-clad laminates. Furthermore, in the forming (laminar forming) of laminates or metal-clad laminates, the temperature is typically 100–300°C, and the pressure is a surface pressure of 2–100 kgf / cm². 2 The heating time ranges from 0.05 to 5 hours. Furthermore, post-curing can be performed at temperatures between 150 and 300°C, depending on the requirements. Especially when using a multi-stage press, from the viewpoint of fully promoting the curing of the prepreg, a temperature of 200°C to 250°C and a pressure of 10 to 40 kgf / cm² are preferred. 2 Heating time: 80-130 minutes, preferably 215-235℃, pressure: 25-35 kgf / cm² 2 Heating time: 90-120 minutes. Alternatively, the above-mentioned prepreg can be laminated with a separately manufactured inner layer circuit board to form a multilayer board.

[0340] Printed Circuit Board

[0341] The printed circuit board of this embodiment has: an insulating layer formed from one or more materials selected from the group consisting of prepreg and resin sheet of this embodiment; and a conductor layer formed on the surface of the insulating layer. For example, the printed circuit board of this embodiment can be formed by etching the metal foil of the metal foil laminate of this embodiment into a predetermined wiring pattern to form the conductor layer.

[0342] Specifically, the printed circuit board of this embodiment can be manufactured, for example, by the following method. First, a metal-clad laminate of this embodiment is prepared. The metal foil of the metal-clad laminate is etched into a predetermined wiring pattern to form an inner layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of insulating layers and metal foils for the outer layer circuit are sequentially laminated on the surface of the conductor layer (internal circuit) of the inner layer substrate, and integrally formed by heating and pressing (laminarization) to obtain a laminate. It should be noted that the lamination method and its forming conditions are the same as those for the lamination of the laminate and the metal-clad laminate described above. Next, through-hole and via hole opening processing is performed on the laminate, and a metal-plated coating film for conducting between the conductor layer (internal circuit) and the metal foil for the outer layer circuit is formed on the wall surface of the hole formed therefrom. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to form an outer layer substrate having a conductor layer (outer layer circuit). The printed circuit board is thus manufactured.

[0343] Alternatively, without using a metal foil laminate, a conductor layer that forms the circuit can be formed on the aforementioned insulating layer to fabricate a printed circuit board. In this case, chemical plating can also be used to form the conductor layer.

[0344] Example

[0345] The present invention will be further described in detail below with reference to embodiments, but the present invention is not limited to these embodiments.

[0346] (Synthetic Example 1) The synthesis of 1-naphthol aryl cyanate compound (SN495V-CN) makes R in the above formula (2b) 2a300g of α-naphthol aralkyl phenolic resin (SN495V, OH group equivalent: 236g / eq., manufactured by Nippon Steel Chemical Co., Ltd.) consisting entirely of hydrogen atoms (OH group equivalent: 1.28mol) and 194.6g (1.92mol) of triethylamine (1.5mol relative to 1mol of hydroxyl group) were dissolved in 1800g of dichloromethane to form solution 1. While stirring, 125.9g (2.05mol) of cyanogen chloride (1.6mol relative to 1mol of hydroxyl group), 293.8g of dichloromethane, 194.5g (1.92mol) of 36% hydrochloric acid (1.5mol relative to 1mol of hydroxyl group), and 1205.9g of water were added to solution 1 over 30 minutes while maintaining the solution temperature at -2 to -0.5°C. After the injection of Solution 1 was completed, the mixture was stirred at the same temperature for 30 minutes. Then, a solution containing 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl group) dissolved in 65 g of dichloromethane was injected over 10 minutes (Solution 2). After the injection of Solution 2 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction. The reaction mixture was then allowed to stand, and the organic and aqueous phases were separated. The obtained organic phase was washed five times with 1300 g of water. The conductivity of the wastewater from the fifth wash was 5 μS / cm, confirming that the ionic compounds were effectively removed by water washing. The washed organic phase was concentrated under reduced pressure and finally concentrated and dried at 90 °C for 1 hour to obtain 331 g of the target naphthol aralkyl cyanate compound (SN495V-CN, cyanate equivalent: 261 g / eq.) (orange viscous substance). The infrared absorption spectrum of the obtained SN495V-CN showed a wavelength of 2250 cm⁻¹. -1 It exhibits absorption of (cyanate ester group) but does not show absorption of hydroxyl group.

[0347] (Example 1)

[0348] In a three-necked flask equipped with a thermometer and a serpentine condenser, add 5.3 parts by weight of diallyl bisphenol A (DABPA, Yamato Chemical Co., Ltd.), 5.8 parts by weight of bis(cresol)fluorene (BCF, Osaka Gas Chemicals Co., Ltd.), 4.4 parts by weight of epoxy-modified organosilicon b1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol), 8.7 parts by weight of epoxy-modified organosilicon b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 490 g / mol), 5.8 parts by weight of biphenyl-type epoxy compound c1 (YL-6121H, Mitsubishi Chemical Co., Ltd.), and 30 parts by weight of propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) as a solvent. Heat to 120°C in an oil bath and stir. After confirming that the raw material is dissolved in the solvent, 0.3 parts by weight of imidazole catalyst g1 (TBZ, Shikoku Kasei Corporation) were added, the temperature was raised to 140°C, and the mixture was stirred for 5 hours. After cooling, a phenoxy polymer solution (50% by weight of solid content) was obtained (polymer generation process).

[0349] It should be noted that diallylbisphenol A is equivalent to "alkenylphenol A", epoxy-modified organosilicon b1 and epoxy-modified organosilicon b2 are equivalent to "epoxy-modified organosilicon B", and biphenyl-type epoxy compound c1 is equivalent to "epoxy compound C". Additionally, the phenoxy polymer solution contains polymer D, which contains structural units derived from alkenylphenol A, structural units derived from epoxy-modified organosilicon B, and structural units derived from epoxy compound C. Hereinafter, polymer D will also be referred to as the phenoxy polymer.

[0350] In 30 parts by mass of the phenoxy polymer solution (converted to solid components), 26 parts by mass of the α-naphthol aralkyl cyanate compound obtained from Synthesis Example 1, 17 parts by mass of the phenolic varnish-type maleimide compound (BMI-2300, Yamato Kasei Corporation), 27 parts by mass of the naphthalene ether-type epoxy compound (HP-6000, DIC Corporation), 100 parts by mass of spherical silica (SFP-130MC, Denka Co., Ltd.), 40 parts by mass of spherical silica (SC-4500SQ, Admatex Co., Ltd.), 1 part by mass of wetting and dispersing agent (DISPERBYK-161, BYK Chemie Japan Co., Ltd.), and 5 parts by mass of silane coupling agent (KMB-403, Shin-Etsu Chemical Industry Co., Ltd.) were mixed to obtain a varnish (varnish production process). The varnish was impregnated and coated onto S-glass fabric (100 μm thick), and then heated and dried at 150°C for 3 minutes to obtain a prepreg with a resin composition solid content (including filler material) of 46% by mass (prepreg generation process).

[0351] (Example 2)

[0352] In the polymer generation process, the amount of the imidazole catalyst g1 added was 1.2 parts by mass instead of 0.3 parts by mass. Otherwise, a prepreg with a content of 46% by mass of solid components (including filler material) of resin composition was obtained in the same manner as in Example 1.

[0353] (Example 3)

[0354] In the polymer generation process, the amount of diallyl bisphenol A added was 5.0 parts by mass instead of 5.3 parts by mass, the amount of biscresol fluorene added was 5.5 parts by mass instead of 5.8 parts by mass, the amount of epoxy-modified organosilicon b1 added was 3.7 parts by mass instead of 4.4 parts by mass, the amount of epoxy-modified organosilicon b2 added was 11 parts by mass instead of 8.7 parts by mass, the amount of biphenyl-type epoxy compound c1 added was 4.9 parts by mass instead of 5.8 parts by mass, and the amount of imidazole catalyst g1 added was 1.2 parts by mass instead of 0.30 parts by mass. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass was obtained in the same manner as in Example 1.

[0355] (Example 4)

[0356] In the polymer generation process, 1.2 parts by weight of imidazole catalyst g2 (TPIZ, Tokyo Chemical Industry Co., Ltd.) was added instead of 0.3 parts by weight of imidazole catalyst g1. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by weight was obtained in the same manner as in Example 1.

[0357] (Example 5)

[0358] In the polymer formation process, 5.8 parts by weight of biphenyl-type epoxy compound C2 (YX-4000, Mitsubishi Chemical Corporation) were added instead of 5.8 parts by weight of biphenyl-type epoxy compound C1. Otherwise, a prepreg with a resin composition solids content (including filler material) of 46% by weight was obtained in the same manner as in Example 1. It should be noted that biphenyl-type epoxy compound C2 is equivalent to "epoxy compound C".

[0359] (Example 6)

[0360] In the polymer generation process, the amount of diallyl bisphenol A added is 10 parts by mass instead of 5.3 parts by mass, biscresol fluorene is not added, the amount of epoxy-modified organosilicon b1 added is 4.5 parts by mass instead of 4.4 parts by mass, the amount of epoxy-modified organosilicon b2 added is 9.1 parts by mass instead of 8.7 parts by mass, the amount of biphenyl-type epoxy compound c1 added is 6.0 parts by mass instead of 5.8 parts by mass, and the amount of imidazole catalyst g1 added is 1.2 parts by mass instead of 0.3 parts by mass. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass is obtained in the same manner as in Example 1.

[0361] (Example 7)

[0362] In the polymer formation process, 7.0 parts by weight of epoxy-modified organosilicon b2 were added instead of 11 parts by weight, and 4.0 parts by weight of epoxy-modified organosilicon b3 (X-22-163A, Shin-Etsu Chemical Co., Ltd., functional group equivalent 1000 g / mol) were added. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by weight was obtained in the same manner as in Example 3. It should be noted that epoxy-modified organosilicon b3 is equivalent to "epoxy-modified organosilicon B".

[0363] (Example 8)

[0364] In the polymer generation process, the amount of diallyl bisphenol A added was 1.7 parts by mass instead of 5.3 parts by mass, the amount of bis(cresol)fluorene added was 1.8 parts by mass instead of 5.8 parts by mass, the amount of epoxy-modified organosilicon b1 added was 1.2 parts by mass instead of 4.4 parts by mass, the amount of epoxy-modified organosilicon b2 added was 3.7 parts by mass instead of 8.7 parts by mass, the amount of biphenyl-type epoxy compound c1 added was 1.6 parts by mass instead of 5.8 parts by mass, the amount of solvent added was 10 parts by mass instead of 30 parts by mass, and the amount of imidazole catalyst g1 added was 0.4 parts by mass instead of 0.3 parts by mass. Otherwise, a phenoxy polymer solution (50% by mass solids) was obtained in the same manner as in Example 1. In the varnish production process and the prepreg production process, the amount of α-naphthol aralkyl cyanate compound added is 33 parts by mass instead of 26 parts by mass, the amount of phenolic varnish maleimide compound added is 22 parts by mass instead of 17 parts by mass, and the amount of naphthalene ether epoxy compound added is 35 parts by mass instead of 27 parts by mass. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass is obtained in the same manner as in Example 1.

[0365] (Example 9)

[0366] In the varnish production process, 50 parts by weight of α-naphthol aralkyl cyanate compound were added instead of 26 parts by weight, no phenolic varnish maleimide compound was added, and 50 parts by weight of naphthalene ether epoxy compound were added instead of 27 parts by weight. Otherwise, a prepreg with a resin composition solids content (including filler material) of 46% by weight was obtained in the same manner as in Example 3.

[0367] (Example 10)

[0368] In the varnish production process, no α-naphthol aralkyl cyanate compound is added, and 40 parts by weight of phenolic varnish-type maleimide compound are added instead of 17 parts by weight. No naphthalene ether-type epoxy compound is added, and 30 parts by weight of alkenyl-substituted nadicimide (BANI-M, Maruzen Petrochemical Co., Ltd.) are added. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by weight is obtained in the same manner as in Example 3.

[0369] (Example 11)

[0370] In the varnish production process, no α-naphthol aralkyl cyanate compound is added. Instead, 18 parts by mass of phenolic varnish-type maleimide compound are added, replacing 17 parts by mass. Instead, 26 parts by mass of naphthalene ether-type epoxy compound are added, replacing 27 parts by mass. 26 parts by mass of phenolic compound (GPH-103, Nippon Kayaku Co., Ltd.) are added. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass is obtained in the same manner as in Example 3.

[0371] (Comparative Example 1)

[0372] A varnish was prepared by mixing 37 parts by mass of the α-naphthol aralkyl cyanate compound obtained from Synthesis Example 1, 24 parts by mass of the phenolic varnish-type maleimide compound (BMI-2300, Yamato Kasei Corporation), 39 parts by mass of the naphthalene ether-type epoxy compound (HP-6000, DIC Corporation), 100 parts by mass of spherical silica (SFP-130MC, Denka Co., Ltd.), 40 parts by mass of spherical silica (SC-4500SQ, Admatex Co., Ltd.), 1 part by mass of wetting and dispersing agent (DISPERBYK-161, BYK Chemie Japan Co., Ltd.), and 5 parts by mass of silane coupling agent (KMB-403, Shin-Etsu Chemical Industry Co., Ltd.). The varnish was impregnated and coated onto S-glass fabric (100 μm thick), and then heated and dried at 150°C for 3 minutes to obtain a prepreg with a resin composition solid content (including filler material) of 46% by mass.

[0373] (Comparative Example 2)

[0374] In the polymer generation process, 10 parts by mass of diallyl bisphenol A were added instead of 5.3 parts by mass, biscresol fluorene and epoxy-modified organosilicon b1 were not added, 20 parts by mass of epoxy-modified organosilicon b2 were added instead of 8.7 parts by mass, biphenyl-type epoxy compound c1 was not added, and 1.2 parts by mass of imidazole catalyst g1 were added instead of 0.3 parts by mass. Otherwise, a prepreg with a resin composition solids content (including filler material) of 46% by mass was obtained in the same manner as in Example 1.

[0375] (Comparative Example 3)

[0376] In the polymer generation process, the amount of diallyl bisphenol A added is 17 parts by mass instead of 5.3 parts by mass, biscresol fluorene is not added, the amount of epoxy-modified organosilicon b1 added is 4.5 parts by mass instead of 4.4 parts by mass, the amount of epoxy-modified organosilicon b2 added is 9.0 parts by mass instead of 8.7 parts by mass, biphenyl-type epoxy compound c1 is not added, and the amount of imidazole catalyst g1 added is 1.2 parts by mass instead of 0.3 parts by mass. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass is obtained in the same manner as in Example 1.

[0377] (Comparative Example 4)

[0378] In the polymer generation process, 5.8 parts by weight of maleimide compound (BMI-70, K·I Chemical Industry Co.,LTD.) were added instead of 5.8 parts by weight of biphenyl-type epoxy compound C1. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by weight was obtained in the same manner as in Example 4.

[0379] (Comparative Example 5)

[0380] In the polymer generation process, the amount of diallyl bisphenol A added is 15 parts by mass instead of 5.3 parts by mass, biscresol fluorene, epoxy-modified organosilicon b1 and epoxy-modified organosilicon b2 are not added, the amount of biphenyl-type epoxy compound c1 added is 15 parts by mass instead of 5.8 parts by mass, and the amount of imidazole catalyst g1 added is 1.2 parts by mass instead of 0.3 parts by mass. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass is obtained in the same manner as in Example 1.

[0381] (Comparative Example 6)

[0382] A varnish was prepared by mixing 30 parts by weight of epoxy-modified organosilicon b1, 26 parts by weight of α-naphthol aralkyl cyanate compound obtained from Synthesis Example 1, 17 parts by weight of phenolic varnish-type maleimide compound (BMI-2300, Yamato Kasei Corporation), 27 parts by weight of naphthalene ether-type epoxy compound (HP-6000, DIC Corporation), 100 parts by weight of spherical silica (SFP-130MC, Denka Co., Ltd.), 40 parts by weight of spherical silica (SC-4500SQ, Admatex Co., Ltd.), 1 part by weight of wetting and dispersing agent (DISPERBYK-161, BYK Chemie Japan Co., Ltd.), and 5 parts by weight of silane coupling agent (KMB-403, Shin-Etsu Chemical Industry Co., Ltd.). The varnish was impregnated and coated onto S-glass fabric (100 μm thick), and then heated and dried at 150°C for 3 minutes to obtain a prepreg with a resin composition solid content (including filler material) of 46% by mass.

[0383] (Comparative Example 7)

[0384] In addition to replacing 30 parts by mass of epoxy-modified organosilicon b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 490 g / mol), 30 parts by mass of epoxy-modified organosilicon b1 were added. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass was obtained in the same manner as in Comparative Example 6.

[0385] (Comparative Example 8)

[0386] In addition to replacing 30 parts by mass of epoxy-modified organosilicon b3 (X-22-163A, Shin-Etsu Chemical Co., Ltd., functional group equivalent 1000 g / mol), 30 parts by mass of epoxy-modified organosilicon b1 were added. Otherwise, a prepreg with a resin composition solid content (including filler material) of 46% by mass was obtained in the same manner as in Comparative Example 6.

[0387] The various physical properties of the phenoxy polymers obtained in the examples and comparative examples are shown in Table 1. The weight-average molecular weights shown in Table 1 were determined by using polystyrene as a standard substance via GPC.

[0388] [Appearance Evaluation of Phenoxy Polymer Solutions]

[0389] The phenoxy polymer solutions obtained in Examples 1-11 and Comparative Examples 1-5 were visually confirmed. The results showed that the phenoxy polymer solutions in Examples 1-11 and Comparative Examples 1 and 5 were homogeneous, but the phenoxy polymer solutions in Comparative Examples 2 and 3 were two-phase, and the phenoxy polymer solution in Comparative Example 4 was gelled.

[0390] [Appearance evaluation of varnish and prepreg]

[0391] The appearance of the varnishes and prepregs of Examples 1-11 and Comparative Examples 1-8 was evaluated visually according to the following evaluation criteria.

[0392] ○: It has a uniform appearance.

[0393] ×: It has an uneven appearance.

[0394] [Fabrication of metal foil-coated laminates]

[0395] Two or eight sheets of the prepreg obtained in Examples 1-11 and Comparative Examples 1-8 were overlapped, and an electrolytic copper foil (3EC-M2S-VLP, manufactured by Mitsui Metals & Minerals Co., Ltd.) with a thickness of 12 μm was placed on top and bottom, and the mixture was subjected to a pressure of 30 kgf / cm². 2 A metal foil laminate was formed by lamination at 220°C for 120 minutes, resulting in a copper-clad laminate containing an insulating layer with a thickness of 0.2 mm or 0.8 mm. It should be noted that copper-clad laminates could not be fabricated for Comparative Examples 4 and 6-8. The characteristics of the obtained copper-clad laminates were evaluated according to the methods shown below. The evaluation results are shown in Table 1.

[0396] Coefficient of thermal expansion

[0397] The longitudinal linear thermal expansion coefficient of the glass cloth in the insulating layer of the laminate was determined according to the TMA (Thermo-mechanical analysis) method specified in JIS C 6481. Specifically, after etching away the copper foil on both sides of the copper-clad laminate (5mm × 5mm × 0.8mm) obtained above, it was heated in a constant temperature bath at 220°C for 2 hours to remove the stress generated during molding. Then, the linear thermal expansion coefficient (CTE) (ppm / °C) was measured at 60°C to 260°C using a thermomechanical analysis apparatus (manufactured by TA Instruments) at a rate of 10°C per minute from 40°C to 320°C.

[0398] [Copper foil peel strength (copper foil adhesion)]

[0399] The copper-clad laminate (30mm × 150mm × 0.8mm) obtained by the above method was tested for copper foil peel strength (copper foil adhesion) according to JIS C6481. It should be noted that peeling occurred during the test for Comparative Example 2, therefore, the test could not be performed.

[0400] [Stain Removal Resistance]

[0401] After removing the copper foil from both sides of the copper-clad laminate (50mm × 50mm × 0.2mm) obtained by the above method through etching, the laminate was immersed in Atotech Japan KK's Swelling Dip Securiganth P as a swelling solution for 10 minutes at 80°C. Then, it was immersed in Atotech Japan KK's Concentrate Compact CP as a roughening solution for 5 minutes at 80°C. Finally, it was immersed in Atotech Japan KK's Reduction Solution Securiganth P500 as a neutralizing solution for 10 minutes at 45°C. This treatment was repeated three times. The mass of the copper-clad laminate before and after treatment was measured, and the mass reduction was calculated. The smaller the absolute value of the mass reduction, the better the staining resistance and removability.

[0402] [Insulation Reliability]

[0403] Insulation reliability was evaluated using a line-to-line insulation reliability test based on HAST (Highly Accelerated Life Test). First, a printed circuit board (line width / spacing (L / S = 100 / 100μm)) was formed from the copper-clad laminate (insulation layer thickness 0.2mm) obtained above using a subtraction method. Next, a power supply was connected to the wiring, and the continuous wet insulation resistance was evaluated under conditions of 130°C, 85% humidity, and an applied voltage of 5VDC. It should be noted that a resistance value of 1.0 × 10⁻⁶ was used. 8 A reading below Ω is considered a fault. The evaluation criteria are as follows.

[0404] ○: More than 500 hours is considered trouble-free.

[0405] ×: Fault occurred within 500 hours.

[0406] [Table 1]

[0407]

[0408] ※In the table, “epoxy group number / phenolic group number” refers to the total number of epoxy groups used in the preparation of polymer D, relative to the number of phenolic groups in alkenylphenol A, and the total number of epoxy groups in epoxy-modified organosilicon B and epoxy compound C.

[0409] ※In the table, “B / D” refers to the content (mass%) of structural units derived from epoxy-modified organosilicon B in the phenoxy polymer solution relative to polymer D. Polymer D does not contain imidazole catalyst and solvent.

[0410] ※In the table, “C / (B+C)” refers to the content (mass%) of structural units derived from epoxy compound C relative to the total amount of structural units derived from epoxy-modified organosilicon B and structural units derived from epoxy compound C.

[0411] [Table 2]

[0412]

[0413] ※In the table, “cannot be produced” means that the phenoxy polymer solution is two-phase or gelled (Comparative Examples 2-4), or the epoxy-modified silicone B used is incompatible with other thermosetting resins, thus making it impossible to produce a prepreg for evaluation.

[0414] This application is based on Japanese Patent Application No. 2018-140494, filed with the Japan Patent Office on July 26, 2018, the contents of which are incorporated herein by reference.

[0415] Industrial availability

[0416] This invention is industrially available as a curable composition for use as a material such as prepreg, resin sheet, metal foil laminate, and printed circuit board.

Claims

1. A curable composition comprising: an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B, wherein, The alkenylphenol A has an average of 1 or more phenolic groups per molecule and less than 3; the epoxy-modified organosilicon B has an average of 1 or more epoxy groups per molecule and less than 3; and the epoxy compound C has an average of 1 or more epoxy groups per molecule and less than 3. The epoxy-modified organosilicon B contains two or more epoxy-modified organosilicones represented by formula (1) below, and the two or more epoxy-modified organosilicones each have different n values. In equation (1), R 1 Each can independently represent an alkylene, phenylene, or arylene group, R 2 Each can independently represent an alkyl or phenyl group having 1 to 10 carbon atoms, where n represents an integer greater than 1. The content of the epoxy compound C is 5 to 50% by mass relative to the total mass percentage of the epoxy-modified organosilicon B and the epoxy compound C (100% by mass).

2. The curable composition according to claim 1, wherein, The alkenylphenol A contains diallyl bisphenol and / or diallyl bisphenol.

3. The curable composition according to claim 1 or 2, wherein, The epoxy-modified organosilicon B comprises epoxy-modified organosilicon with an epoxy equivalent of 140–250 g / mol.

4. The curable composition according to claim 1 or 2, wherein, The epoxy compound C contains the epoxy compound shown in formula (2) below. In equation (2), R a Each can independently represent an alkyl group or a hydrogen atom having 1 to 10 carbon atoms.

5. A curable composition comprising a polymer D, said polymer D containing: structural units derived from alkenylphenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C, wherein, The alkenylphenol A has an average of 1 or more phenolic groups per molecule and less than 3; the epoxy-modified organosilicon B has an average of 1 or more epoxy groups per molecule and less than 3; and the epoxy compound C has an average of 1 or more epoxy groups per molecule and less than 3. The epoxy-modified organosilicon B contains two or more epoxy-modified organosilicones represented by formula (1) below, and the two or more epoxy-modified organosilicones each have different n values. In equation (1), R 1 Each can independently represent an alkylene, phenylene, or arylene group, R 2 Each can independently represent an alkyl or phenyl group having 1 to 10 carbon atoms, where n represents an integer greater than 1. The content of the structural unit derived from epoxy compound C is 5 to 50% by mass relative to the total mass of the structural units derived from epoxy-modified organosilicon B and the structural units derived from epoxy compound C.

6. The curable composition according to claim 5, wherein, The weight-average molecular weight of polymer D is 3.0 × 10⁻⁶. 3 ~5.0×10 4 .

7. The curable composition according to claim 5 or 6, wherein, The content of the structural units derived from epoxy-modified organosilicon B in polymer D is 20-60% by mass relative to the total mass of polymer D.

8. The curable composition according to claim 5 or 6, wherein, The alkenyl equivalent of polymer D is 300–1500 g / mol.

9. The curable composition according to claim 5 or 6, wherein, The content of polymer D is 5 to 50% by mass relative to 100% by mass of the resin solids.

10. The curable composition according to claim 1 or 5, further comprising thermosetting resin E.

11. The curable composition according to claim 10, wherein, The thermosetting resin E contains one or more compounds selected from the group consisting of maleimide compounds, cyanate compounds, phenolic compounds, alkenyl-substituted nadicimide compounds, and epoxy compounds.

12. The curable composition according to claim 11, wherein, The maleimide compound comprises one or more selected from the group consisting of bis(4-maleiminophenyl)methane, 2,2-bis{4-(4-maleiminophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane, and maleimide compounds represented by formula (3) below. In equation (3), R5 independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than or equal to 1.

13. The curable composition according to claim 11 or 12, wherein, The cyanate ester compound comprises the compound shown in formula (4) below and / or the compound shown in formula (5) below, other than the compound shown in formula (4) below. In equation (4), R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer greater than or equal to 1. In equation (5), R ya Each independently represents an alkenyl group having 2 to 8 carbon atoms, R yb Each independently represents an alkyl group or a hydrogen atom having 1 to 10 carbon atoms, R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optional fusion structure with benzene ring, R yc A can be either present or absent. 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an arylene group having 7 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a fluorene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a single bond, R yc In the absence of R, any two or more R atoms can be arbitrarily selected on one benzene ring. ya and / or R yb The group, n represents an integer from 1 to 10.

14. The curable composition according to claim 11 or 12, wherein, The epoxy compound comprises a compound represented by formula (6) or a compound represented by formula (7). In equation (6), R 13 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. In equation (7), R 14 Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.

15. The curable composition according to claim 1 or 5, further comprising an inorganic filler. The content of the inorganic filler material is 50 to 1000 parts by weight relative to 100 parts by weight of the resin solids.

16. The curable composition according to claim 1 or 5, used in a printed circuit board.

17. A prepreg comprising: Substrate; and, The curable composition of any one of claims 1 to 16 that is impregnated or coated onto the substrate.

18. A resin sheet comprising: Support; and The curable composition of any one of claims 1 to 16 disposed on the surface of the support.

19. A metal foil-clad laminate, comprising: A laminate formed from one or more of the prepreg of claim 17 and the resin sheet of claim 18; and, Metal foil disposed on one or both sides of the laminate.

20. A printed circuit board comprising: An insulating layer formed from one or more of the prepreg of claim 17 and the resin sheet of claim 18; and, A conductor layer formed on the surface of the insulating layer.

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