JP2018016675A - Resin composition, prepreg, metal foil-clad laminate, resin sheet, resin composite sheet and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can achieve a printed wiring board having high peel strength and showing low weight loss at the time of heating.SOLUTION: A resin composition contains an epoxy resin (A) represented by the formula (1), an epoxy resin (B) other than epoxy resin (A) represented by the formula (1), and a cyanate compound (C).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, a resin composite sheet, and a printed wiring board.

  In recent years, higher integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, and the like have been increasingly accelerated. As a result, various characteristics required for semiconductor package laminates used for printed wiring boards have become increasingly severe. The required properties include, for example, properties such as low water absorption, moisture absorption heat resistance, flame resistance, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength. However, so far, these required properties have not always been satisfied.

  Conventionally, cyanate ester compounds have been known as resins for printed wiring boards having excellent heat resistance and electrical characteristics. Among them, resin compositions in which an epoxy resin or the like is used in combination with a cyanate ester compound have recently been used for semiconductor plastic packages. It is widely used for high-performance printed wiring board materials. In addition, due to the miniaturization and high density of multilayer printed wiring boards, multilayer printed wiring boards have multiple buildup layers, and further miniaturization and high density of wiring are required. Along with this, studies have been actively conducted to reduce the thickness of the laminate used for this build-up layer. Furthermore, since the problem of expansion of warp occurs in the multilayer printed wiring board, a high glass transition temperature is required for the resin composition used as the material of the insulating layer.

International Publication No. 2013/065694 Pamphlet International Publication No. 2014/203866 Pamphlet Japanese Patent No. 5413522

  Resin compositions comprising a cyanate ester compound and an epoxy resin that are excellent in properties such as adhesion, low water absorption, moisture absorption heat resistance, and insulation reliability have been proposed (see, for example, Patent Documents 1 and 2). However, since the resin composition is still insufficient in terms of adhesion and low water absorption, further improvement in properties is required. Among them, epoxy resins are resins that are generally excellent in adhesion, fluidity, and processability, and studies have been conducted for the purpose of imparting further characteristics using various epoxy resins having different structures. .

  Moreover, as a method for improving the peel strength and plating peel strength of a copper foil, a method of surface-treating a filler has been proposed (see Patent Document 3). However, since this method is still insufficient in terms of plating peel strength, further improvement in plating peel strength is required.

  Therefore, the present invention has been made in view of the above-described problems of the prior art, a resin composition that can realize a printed wiring board excellent in high peel strength and a low weight reduction rate during heating, and the resin composition An object of the present invention is to provide a prepreg, a metal foil-clad laminate, a resin sheet, a resin composite sheet, and a printed wiring board using the product.

  As a result of intensive studies on the above problems, the present inventors have found that the epoxy resin (A) represented by the formula (1) and the epoxy resin (B) other than the epoxy resin (A) represented by the formula (1) By using a resin composition containing a cyanate ester compound (C), a printed wiring board having high peel strength, high glass transition temperature, low water absorption and excellent weight reduction during heating is obtained. The present invention has been reached. That is, the present invention is as follows.

1. An epoxy resin (A) represented by the following formula (1), an epoxy resin (B) other than the epoxy resin (A) represented by the formula (1), and a cyanate ester compound (C) are contained. Resin composition.
2. Content of the said epoxy resin (A) is 0.1-10 mass parts with respect to 100 mass parts of resin solid content in the said resin composition. The resin composition described in 1.
3. The cyanate ester compound (C) is selected from the group consisting of a naphthol aralkyl cyanate ester compound represented by the following formula (2) and a biphenylaralkyl cyanate ester compound represented by the following formula (3). 1 or more types. Or 2. The resin composition described in 1.
(In formula, R1 shows a hydrogen atom or a methyl group each independently, and n1 shows the integer of 1-50.)
(In the formula, each R3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 to 50.)
4). Further containing a filler (D) ~ 3. The resin composition as described in any one of these.
5. Further containing at least one selected from the group consisting of a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. ~ 4. The resin composition as described in any one of these.
6). 3. Content of the said filler (D) is 50-1600 mass parts with respect to 100 mass parts of resin solid content in the said resin composition. Or 5. The resin composition described in 1.
7). A substrate and impregnated or coated on the substrate; ~ 6. A prepreg having the resin composition according to any one of the above.
8.7. A metal foil-clad laminate comprising: a layer containing at least one prepreg according to 1); and a metal foil laminated on one or both sides of the layer.
9.1. ~ 6. The resin sheet which has a resin layer containing the resin composition as described in any one of these.
10. A support and a resin layer disposed on the surface of the support. ~ 6. The resin composite sheet containing the resin composition as described in any one of these.
11. An insulating layer; and a conductor layer formed on a surface of the insulating layer. ~ 6. The printed wiring board containing the resin composition as described in any one of these.

  According to the present invention, not only has a high glass transition temperature, but also a resin composition capable of realizing a printed wiring board excellent in high peel strength, low water absorption, and a low weight loss rate upon heating, and the resin composition A prepreg, a metal foil-clad laminate, a resin sheet, a resin composite sheet, and a printed wiring board can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention to the following embodiment. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

<Resin composition>
The resin composition of this embodiment includes an epoxy resin (A) represented by the following formula (1) (hereinafter also simply referred to as “epoxy resin (A)”) and an epoxy resin other than the epoxy resin (A) ( B) (hereinafter referred to as “other epoxy resin (B)”) and a cyanate ester compound (C).
The resin composition of the present embodiment mainly contains an epoxy resin (A) together with other components, so that a high-performance print excellent in high peel strength and low weight reduction rate (that is, flame retardancy) upon heating. A wiring board can be realized. In addition to that, the resin composition of the present embodiment has a high glass transition temperature, and further provides a printed wiring board excellent in low water absorption.

  Such an epoxy resin (A) may use a commercially available thing, and may synthesize | combine by a conventional method. As an epoxy resin (A), the brand name "TEPIC-SP" (epoxy equivalent 100g / eq) by Nissan Chemical Industries Ltd. is mentioned, for example.

  In the present embodiment, the content of the epoxy resin (A) can be appropriately set according to the desired properties, and is not particularly limited. However, the content of the epoxy resin (A) is 0.1% relative to 100 parts by mass of the resin solid content in the resin composition. It is preferable that it is 1-10 mass parts, 0.5-8 mass parts is more preferable, and 0.8-6.5 mass parts is still more preferable. When this content is in the range of 0.1 to 10 parts by mass, a resin composition that is further excellent in high peel strength, high glass transition temperature, low water absorption, and low weight loss rate can be obtained. Here, unless otherwise specified, “resin solid content in the resin composition” refers to a component in the resin composition excluding components other than the resin such as a solvent and a filler (D). “Total amount of minutes” refers to the total amount of components excluding components other than resin such as solvent and filler (D) in the resin composition.

  The epoxy resin (B) in this embodiment is not represented by the formula (1), and any known epoxy resin can be used as long as it is an epoxy resin having two or more epoxy groups in one molecule. The type is not particularly limited. Specific examples of the epoxy resin (B) include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl. Ester type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, Phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphtha Type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type Examples thereof include compounds obtained by epoxidizing double bonds such as epoxy resins, phosphorus-containing epoxy resins, glycidyl amines, glycidyl esters, and butadiene, and compounds obtained by the reaction of hydroxyl group-containing silicone resins with epichlorohydrin. Among these epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable in terms of flame retardancy and heat resistance. These epoxy resins can be used alone or in combination of two or more.

  The content of the epoxy resin (B) in the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but when the resin solid content in the resin composition is 100 parts by mass, 90 mass parts is preferable, 10-80 mass parts is more preferable, 20-70 mass parts is still more preferable. By making content of an epoxy resin (B) into such a range, the effect of this invention can be show | played more effectively and reliably.

  The cyanate ester compound (C) in the present embodiment is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).

Although it does not specifically limit as a cyanate ester compound (C), For example, the compound (henceforth a "cyanato substituted aromatic compound") represented by following formula (4) is mentioned.
Here, in the formula, Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings, and when there are a plurality of them, they may be the same or different. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms and 6 to 12 carbon atoms. A group to which the aryl group is bonded. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p is a number of cyanate groups bonded to Ar _1, is an integer of 1 to 3 independently. q indicates the number of Ra bonded to Ar _1, and 4-p when Ar ₁ is a benzene ring, 6-p when Ar ₁ is a naphthalene ring, and 8-p when two benzene rings are a single bond. . t represents an average number of repetitions and is an integer of 0 to 50, and the cyanato-substituted aromatic compound may be a mixture of compounds having different t. When there are a plurality of Xs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), or a divalent group having 1 to 10 nitrogen atoms. An organic group (for example, —N—R—N— etc. (where R represents an organic group)), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group. (—OC (═O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom, or a divalent oxygen atom.

  The alkyl group in Ra of formula (4) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group). Moreover, the hydrogen atom in the alkyl group and aryl group in Ra of Formula (4) may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Good. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group. Group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group.

  Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl. Groups, methoxyphenyl groups, and o-, m- or p-tolyl groups. Furthermore, examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group. Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in the formula (4) include alkylene groups such as methylene group, ethylene group, trimethylene group and propylene group, cyclopentylene group, cyclohexylene group and trimethyl. Examples thereof include divalent organic groups having an aromatic ring such as a cycloalkylene group such as a cyclohexylene group, a biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalidodiyl group. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group.

  Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of formula (4) include a group represented by -N-R-N-, an imino group, and a polyimide group.

Moreover, as an organic group of X in Formula (4), what is a structure represented by following formula (5) or following formula (6) is mentioned, for example.
Here, in the formula, Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same as or different from each other. Rb, Rc, Rf and Rg are each independently an aryl having at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Indicates a group. Rd and Re are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a hydroxy group. u represents an integer of 0 to 5.
Here, in the formula, Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same as or different from each other. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, or An aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but may be a mixture of compounds having different v.

Furthermore, as X in Formula (4), the bivalent group represented by a following formula is mentioned.
Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of Ar _{2 in} formula (5) and Ar _{3 in} formula (6) include two carbon atoms represented by formula (5) or two oxygen atoms represented by formula (6) having 1, 4 Benzenetetrayl group bonded to the position or 1,3 position, the above two carbon atoms or two oxygen atoms are 4,4′-position, 2,4′-position, 2,2′-position, 2,3 ′ Biphenyltetrayl group bonded to the position, 3, 3 ′ position, or 3, 4 ′ position, and the above two carbon atoms or two oxygen atoms are 2, 6 position, 1, 5 position, 1, Examples thereof include naphthalenetetrayl groups bonded to the 6-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position. Rb, Rc, Rd, Re, Rf and Rg in the formula (5), and the alkyl group and aryl group in Ri and Rj in the formula (6) have the same meanings as those in the above formula (4).

Specific examples of the cyanato-substituted aromatic compound represented by the above formula (4) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1- Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1 -Cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- ( 4-cyanatophenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro- 2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1 -Cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-si Anatobenzophenone, 1-cyanato-2,6-di-tert- Butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4- Dimethylbenzene, 1,4-dicyanato-2,3,4-trimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2- Cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatonaphthalene, 2,2'- or 4,4'-dicyanatobi Phenyl, 4,4′-dicyanatooctafluorobiphenyl, 2,4′- or 4,4′-dicyanatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis (4 -Cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) Propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5-dimethyl) Phenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) pen 1,1-bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) -2-methylbutane, 1,1-bis (4-cyanatophenyl) -2 , 2-dimethylpropane, 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2, 2-bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanatophenyl) -3,3- Dimethylbutane, 3,3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3-bis (4-cyanatophenyl 2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4-bis ( 4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis (4- Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1-phenylethane, Bis (4-Cyanatov Enyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropylphenyl) propane 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1,3-bis [ 2- (4-Cyanatophenyl) -2-propyl] benzene, 1,4-bis [2- (4-cyanatophenyl) -2-propyl] benzene, 1,1-bis (4-cyanatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanatobenzophenone 1,3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanatophenyl) Adamantane, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthalein) 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (she of o-cresolphthalein) ), 9,9′-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) ) Fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) propane, α, α, α '-Tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2, 4,6-tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl-4-cyanatoanilino) -6- (N-methylanilino) -1,3 5 Triazine, bis (N-4-cyanato-2-methylphenyl) -4,4′-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4,4′-oxydiphthalimide, bis ( N-4-cyanatophenyl) -4,4′-oxydiphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4 ′-(hexafluoroisopropylidene) diphthalimide, tris (3 5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3,3-bis (4-cyanato) Phenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanatof) ) Indoline-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one. In addition, as other specific examples of the cyanato-substituted aromatic compound represented by the above formula (4), phenol novolak resin and cresol novolak resin (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, A product obtained by reacting a formaldehyde compound such as paraformaldehyde in an acidic solution), a trisphenol novolak resin (a product obtained by reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), a fluorene novolac resin (9 , 9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), furan ring-containing phenol novolak resin (furfural and phenol reacted in the presence of a basic catalyst), phenol Ara Kill resin, cresol aralkyl resin, naphthol aralkyl resin, a binaphthol aralkyl resin and a biphenyl aralkyl resin (a known _{method, Ar 2 -. (CH 2} Y) 2 (Ar 2 represents a phenyl group, Y represents a halogen atom or less The same as in this paragraph) and a bishalogenomethyl compound and a phenol compound reacted with an acidic catalyst or non-catalyst, or bis (alkoxy) represented by Ar ₂ — (CH ₂ OR) _2. Methyl) compound and phenol compound reacted in the presence of an acidic catalyst, or bis (hydroxymethyl) compound and phenol compound as represented by Ar ₂ — (CH ₂ OH) ₂ Reacted in the presence, or aromatic aldehyde compound, aralkyl compound and phenol compound ), Phenol-modified xylene formaldehyde resin (reacted xylene formaldehyde resin and phenol compound in the presence of an acidic catalyst by a known method), modified naphthalene formaldehyde resin (naphthalene by a known method) A product obtained by reacting a formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthylene ether structure. A polyhydric hydroxynaphthalene compound having two or more in the molecule obtained by dehydrating and condensing a phenolic resin in the presence of a basic catalyst) and the like, and these prepolymers Can be mentioned. These are not particularly limited. These cyanate ester compounds can be used alone or in combination of two or more.

  Among them, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, biphenyl aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, and adamantane skeleton type cyanate One or more selected from the group consisting of ester compounds are preferred, and naphthol aralkyl type cyanate ester compounds are particularly preferred.

The cyanate ester compound (C) is selected from the group consisting of a naphthol aralkyl cyanate ester compound represented by the following formula (2) and a biphenylaralkyl cyanate ester compound represented by the following formula (3). It is preferable that it is 1 or more types. By using these cyanate ester compounds, the effect of the cyanate ester compound (C) can be exhibited more reliably and reliably.
Here, in formula, R1 shows a hydrogen atom or a methyl group each independently, and n1 shows the integer of 1-50.
Here, in formula, R3 shows a hydrogen atom or a methyl group each independently, and n3 shows the integer of 1-50.

  By using these cyanate ester compounds (C) together with other components contained in the resin composition of the present embodiment, a resin composition having excellent properties such as glass transition temperature, low thermal expansibility, and plating adhesion Things can be given.

  The content of the cyanate ester compound (C) in the resin composition of the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but the resin solid content in the resin composition is 100 parts by mass. 1 to 90 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 70 parts by mass. By making content of a cyanate ester compound (C) into such a range, the effect of this invention can be show | played more effectively and reliably.

The resin composition of this embodiment can further contain a filler. As a filler (D), a well-known thing can be used suitably, The kind is not specifically limited. In particular, a filler generally used in laminate applications can be suitably used as the filler (D). Specific examples of the filler (D) include silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil and hollow silica, oxides such as white carbon, titanium white, zinc oxide, magnesium oxide and zirconium oxide. , Boron nitride, Aggregated boron nitride, Silicon nitride, Aluminum nitride, Barium sulfate, Aluminum hydroxide, Aluminum hydroxide heat-treated product (Aluminum hydroxide is heat-treated and part of crystal water is reduced), boehmite, water Metal hydrates such as magnesium oxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass , A-glass, NE-glass, C-glass, L-glass, D-gas S, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass, and other inorganic fillers In addition to the material, rubber powders such as styrene type, butadiene type, and acrylic type, core shell type rubber powder, and organic fillers such as silicone resin powder, silicone rubber powder, and silicone composite powder can be used. These fillers can be used alone or in combination of two or more.
Among these, inorganic fillers are preferable, and one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide are more preferable. By using such a filler, characteristics such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.

  The content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but the resin solid content in the resin composition is 100 parts by mass. In this case, 50 to 1600 parts by mass is preferable, 60 to 1200 parts by mass is more preferable, and 70 to 1000 parts by mass is still more preferable. By making content of a filler (D) into such a range, the moldability of a resin composition becomes still more favorable.

  Here, when the filler (D) is contained in the resin composition, it is preferable to use a silane coupling agent or a wetting and dispersing agent in combination. As a silane coupling agent, what is generally used for the surface treatment of an inorganic substance can be used suitably, and the kind is not specifically limited. Specific examples of silane coupling agents include γ-aminopropyltriethoxysilane, aminosilanes such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Epoxysilanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N-β- (N- Cationic silanes such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, and phenylsilanes. A silane coupling agent can be used individually by 1 type or in combination of 2 or more types. Moreover, as a wet dispersing agent, what is generally used for coating materials can be used suitably, The kind is not specifically limited. As the wetting and dispersing agent, a copolymer-based wetting and dispersing agent is preferably used, and may be a commercially available product. Specific examples of commercially available products include Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, and BYK-W940 (trade names) manufactured by Big Chemie Japan Co., Ltd. . Wet dispersants can be used alone or in combination of two or more.

  Furthermore, the resin composition of the present embodiment contains a maleimide compound, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group as long as the desired characteristics are not impaired. Also good. By using these in combination, desired properties such as flame retardancy and low dielectric property of a cured product obtained by curing the resin composition can be improved.

  As the maleimide compound, generally known compounds can be used as long as they have one or more maleimide groups in one molecule. Examples of maleimide compounds include 4,4-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, and 3,3-dimethyl-5. , 5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, polyphenylmethane maleimide, novolac maleimide, biphenylaralkyl maleimide, And these males Prepolymers of bromide compound, or although prepolymer of the maleimide compound and amine compound, but is not particularly limited. These maleimide compounds can be used singly or in combination of two or more. Among these maleimide compounds, novolac maleimide compounds and biphenylaralkyl maleimide compounds are particularly preferable.

  As the phenol resin, generally known resins can be used as long as they are phenol resins having two or more hydroxy groups in one molecule. Examples of the phenol resin include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, and aralkyl novolak type. Phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin , Naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, bif Sulfonyl type phenolic resins, alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, and a hydroxyl group-containing silicone resins and the like, but is not particularly limited. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in terms of flame retardancy. These phenol resins can be used individually by 1 type or in combination of 2 or more types.

  As the oxetane resin, generally known oxetane resins can be used. Examples of the oxetane resin include alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3- Examples include di (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, and biphenyl type oxetane. OXT-101 (trade name of Toagosei Co., Ltd.), OXT-121 ( Toagosei product name) may be used, and is not particularly limited. These oxetane resins can be used singly or in combination of two or more.

  As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule. Examples of the benzoxazine compound include bisphenol A type benzoxazine (for example, BA-BXZ (trade name, manufactured by Konishi Chemical)), bisphenol F type benzoxazine (for example, BF-BXZ (trade name, manufactured by Konishi Chemical)), bisphenol S type Examples include benzoxazine (for example, BS-BXZ (trade name, manufactured by Konishi Chemical), Pd-type benzoxazine (trade name, manufactured by Shikoku Chemicals), and Fa type benzoxazine (trade name, manufactured by Shikoku Chemicals). However, it is not particularly limited. These benzoxazine compounds can be used alone or in combination of two or more.

  As the compound having a polymerizable unsaturated group, generally known compounds can be used. Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meta). ) Acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or the like Epoxy (meth) acrylates such as (meth) acrylates of polyhydric alcohols, bisphenol A type epoxy (meth) acrylates, bisphenol F type epoxy (meth) acrylates And include benzocyclobutene resin, but is not particularly limited. These compounds having an unsaturated group can be used singly or in combination of two or more. The “(meth) acrylate” is a concept including acrylate and methacrylate corresponding to the acrylate.

  Moreover, the resin composition of this embodiment may contain the hardening accelerator for adjusting a hardening rate suitably as needed. As this hardening accelerator, what is generally used as hardening accelerators, such as a cyanate ester compound and an epoxy resin, can be used suitably, The kind is not specifically limited. Specific examples of the curing accelerator include zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, phenol, xylenol, cresol, resorcin, and catechol. Phenol compounds such as octylphenol and nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and Derivatives of imidazoles such as carboxylic acids or anhydrides thereof, dicyandiamide, benzyldimethylamine, amines such as 4-methyl-N, N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, Phosphorium salt compounds, phosphorus compounds such as diphosphine compounds, epoxy-imidazole adduct compounds, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl Examples thereof include peroxides such as peroxycarbonate, and azo compounds such as azobisisobutyronitrile. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

  The usage-amount of a hardening accelerator can be suitably adjusted in consideration of the hardening degree of resin, the viscosity of a resin composition, etc., and is not specifically limited. 0.005-10 mass parts may be sufficient as the usage-amount of a hardening accelerator with respect to 100 mass parts of resin solid content in a resin composition.

  Furthermore, the resin composition of the present embodiment includes various thermosetting resins such as other thermosetting resins, thermoplastic resins and oligomers thereof, elastomers and the like within a range in which desired characteristics are not impaired. In addition, various additives can be used in combination. These are not particularly limited as long as they are generally used. For example, specific examples of flame retardant compounds include bromine compounds such as 4,4′-dibromobiphenyl, phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, In addition, a silicone compound may be mentioned. Examples of various additives include, for example, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents. , Dispersants, leveling agents, brighteners, polymerization inhibitors and the like. These may be used alone or in combination of two or more as desired.

  In addition, the resin composition of this embodiment can contain an organic solvent as needed. In this case, the resin composition of the present embodiment can be used as an aspect (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible with an organic solvent. Any known organic solvent can be used as long as it dissolves or is compatible with at least a part, preferably all of the above-mentioned various resin components, and the kind thereof is not particularly limited. . Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, and acetic acid. Examples thereof include ester solvents such as isoamyl, methyl methoxypropionate and methyl hydroxyisobutyrate, polar solvents such as amides such as dimethylacetamide and dimethylformamide, and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. These can be used alone or in combination of two or more.

  The resin composition of the present embodiment can be prepared according to a conventional method, and includes an epoxy resin (A), another epoxy resin (B), a cyanate ester compound (C), and the above-described other components as necessary. The method for preparing the resin composition is not particularly limited as long as the resin composition containing the optional component uniformly can be obtained. For example, the resin composition of this embodiment can be prepared by blending the epoxy resin (A), the other epoxy resin (B), and the cyanate ester compound (C) sequentially in an organic solvent and stirring sufficiently. .

  In preparing the resin composition, a known process (such as stirring, mixing, and kneading process) for uniformly dissolving or dispersing each component can be performed. For example, in order to disperse the filler (D) more uniformly in the resin composition, the stirring and dispersing treatment can be performed using a stirring tank provided with a stirrer having an appropriate stirring ability. Thereby, the dispersibility of the filler (D) with respect to a resin composition is improved. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill and a bead mill for mixing, or a revolution / spinning mixing device.

The resin composition of the present embodiment can be used as a constituent material for prepregs, metal foil-clad laminates, printed wiring boards, and semiconductor packages. For example, a prepreg can be obtained by impregnating or applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a base material and drying.
Also, a peelable plastic film is used as a substrate, and a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to the plastic film and dried to obtain a build-up film or a dry film solder resist. be able to. Here, the solvent can be dried by drying at a temperature of 20 ° C. to 150 ° C. for 1 to 90 minutes. Moreover, the resin composition of this embodiment can also be used in the uncured state which dried the solvent, and can also be used in the semi-cured (B-stage) state as needed.

  Hereinafter, the prepreg of this embodiment will be described in detail. The prepreg of this embodiment has a base material and the resin composition impregnated or coated on the base material. The manufacturing method of the prepreg of this embodiment will not be specifically limited if it is a method of manufacturing a prepreg combining the resin composition of this embodiment, and a base material. Specifically, after impregnating or coating the base material with the resin composition of the present embodiment, it is semi-cured by, for example, a method of drying for about 2 to 15 minutes in a dryer at 120 to 220 ° C. Thus, the prepreg of the present embodiment can be manufactured. At this time, the amount of the resin composition attached to the substrate, that is, the content of the resin composition (including the filler (D)) with respect to the total amount of the prepreg after semi-curing is in the range of 20 to 99% by mass. Is preferred.

  As a base material used when manufacturing the prepreg of this embodiment, the well-known thing used for various printed wiring board materials may be used. Examples of such a substrate include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass, and inorganic fibers other than glass such as quartz, Examples thereof include organic fibers such as polyimide, polyamide, and polyester, and woven fabrics such as liquid crystal polyester, but are not particularly limited thereto. As the shape of the substrate, woven fabric, non-woven fabric, roving, chopped strand mat, surfacing mat, and the like are known, and any of these may be used. A base material can be used individually by 1 type or in combination of 2 or more types as appropriate. Among the woven fabrics, a woven fabric that has been subjected to ultra-opening treatment or plugging treatment is particularly preferable from the viewpoint of dimensional stability. Furthermore, a glass woven fabric surface-treated with a silane coupling agent such as an epoxy silane treatment or an amino silane treatment is preferable from the viewpoint of moisture absorption heat resistance. A liquid crystal polyester woven fabric is preferable from the viewpoint of electrical characteristics. Furthermore, the thickness of the substrate is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for use in a laminated board.

The metal foil-clad laminate of this embodiment has a layer containing at least one prepreg as described above and a metal foil laminated on one or both sides of the layer. Specifically, it is produced by laminating and forming a metal foil such as copper or aluminum on one side or both sides of one prepreg or a plurality of prepregs stacked. be able to. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Copper foil, such as a rolled copper foil and an electrolytic copper foil, is preferable. Moreover, although the thickness of metal foil is not specifically limited, It is preferable in it being 2-70 micrometers, and it is more preferable in it being 3-35 micrometers. As a molding condition, a technique used when producing a normal laminated board for a printed wiring board and a multilayer board can be employed. For example, using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, or an autoclave molding machine, lamination molding is performed under conditions of a temperature of 180 to 350 ° C., a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm ^2. Thus, the metal foil-clad laminate of this embodiment can be manufactured. Moreover, a multilayer board can also be produced by laminating and molding the above prepreg and a separately produced wiring board for the inner layer. As a manufacturing method of a multilayer board, for example, first, 35 μm copper foil is arranged on both surfaces of one prepreg described above, and is laminated and formed under the above conditions. Thereafter, an inner layer circuit is formed, and the blackening process is performed on this circuit to form an inner layer circuit board. Further, this inner layer circuit board and the above prepreg are alternately disposed one by one, and a copper foil is further disposed on the outermost layer, and lamination molding is performed under the above conditions, preferably under vacuum. In this way, a multilayer board can be produced.

  The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board by further forming a predetermined wiring pattern. The printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of the manufacturing method of a printed wiring board is shown. First, the metal foil-clad laminate described above is prepared. Next, an inner layer substrate is manufactured by performing an etching process on the surface of the metal foil-clad laminate to form an inner layer circuit. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment for increasing the adhesive strength as necessary, and then the required number of the prepregs described above are stacked on the inner layer circuit surface. Further, a metal foil for an outer layer circuit is laminated on the outside, and is integrally formed by heating and pressing. In this way, a multilayer laminate is produced in which an insulating layer made of a cured product of the base material and the resin composition is formed between the inner layer circuit and the outer layer circuit metal foil. Next, after drilling a through hole or a via hole in the multilayer laminate, a plated metal film is formed on the wall surface of the hole to electrically connect the inner layer circuit and the outer layer metal foil. Furthermore, the printed circuit board is manufactured by performing an etching process on the metal foil for the outer layer circuit to form the outer layer circuit.

  The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the above-described resin composition of the present embodiment. That is, the prepreg of the present embodiment described above (the base material and the resin composition of the present embodiment impregnated or applied thereto), the layer of the resin composition of the metal foil-clad laminate of the present embodiment described above (the present embodiment). The layer made of the resin composition) is composed of an insulating layer containing the resin composition of the present embodiment.

  On the other hand, the resin composite sheet of the present embodiment has a support and a resin layer disposed on the surface of the support, and the resin layer includes the above-described resin composition. Such a resin composite sheet can be obtained by applying a solution obtained by dissolving the above resin composition in a solvent to a support and drying it. Although it does not specifically limit as a support body used here, For example, the mold release agent was apply | coated to the surface of a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and these films. Examples thereof include organic film base materials such as release films and polyimide films, conductive foils such as copper foil and aluminum foil, and plate-like inorganic films such as glass plates, SUS plates, and FRP. Examples of the coating method include a method in which a solution obtained by dissolving the above resin composition in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Moreover, a single layer sheet (resin sheet | seat) can also be obtained by peeling or etching a support body from the resin composite sheet obtained by drying further after application | coating.

  Moreover, the resin sheet of this embodiment has a resin layer containing the said resin composition. Such a resin sheet is formed into a sheet shape by supplying a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-like cavity and drying it. It can be obtained as a single layer sheet without using a support.

  In addition, in preparation of the resin sheet or resin composite sheet (single layer or laminated sheet) of this embodiment, the drying conditions at the time of removing a solvent are not specifically limited, However, It is 1 to 90 minutes at the temperature of 20 to 200 degreeC. It is preferable to dry. When the temperature is 20 ° C. or higher, the solvent can be prevented from remaining in the resin composition, and when the temperature is 200 ° C. or lower, the progress of curing of the resin composition can be further suppressed. In addition, the thickness of the resin layer in the resin sheet or resin composite sheet (single layer or laminated sheet) of the present embodiment can be adjusted by the concentration of the resin composition solution and the coating thickness of the present embodiment. It is not limited. However, the thickness is preferably 0.1 to 500 μm. When the thickness of the resin layer is 500 μm or less, the solvent is less likely to remain during drying.

  According to the present embodiment, a resin composition capable of realizing a printed wiring board excellent in high peel strength and a low weight reduction rate (that is, flame retardancy) upon heating, and a prepreg and a metal using the resin composition A foil-clad laminate, a resin sheet, a resin composite sheet, a printed wiring board, and the like can be provided. In addition, the resin composition of the present embodiment has a high glass transition temperature in addition to it, and is also excellent in low water absorption.

  Hereinafter, although a synthesis example, an Example, and a comparative example are shown and embodiment of this invention is described further in detail, this invention is not limited to these.

(Synthesis Example 1) Synthesis of cyanate ester compound 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 300 g (1.28 mol in terms of OH group) and triethylamine 194.6 g (1.92 mol, 1-naphthol aralkyl resin) 1.5 mol) was dissolved in 1800 g of dichloromethane to obtain a solution 1.

  Next, 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group of 1-naphthol aralkyl resin), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1-naphthol) While stirring a mixture of 1205.9 g of water and 1205.9 g of water with respect to 1 mol of the hydroxy group of the aralkyl resin while maintaining the liquid temperature at −2 to −0.5 ° C., Solution 1 was poured into the mixture over 30 minutes. did. After completion of the pouring of solution 1, after stirring at the same temperature for 30 minutes, 65 g (0.64 mol) of triethylamine (0.5 mol based on 1 mol of hydroxy group of 1-naphthol aralkyl resin) was dissolved in 65 g of dichloromethane. The solution (solution 2) was poured over 10 minutes. After completion of the pouring of the solution 2, the reaction was completed by stirring at the same temperature for 30 minutes.

  Thereafter, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The organic phase obtained was washed 5 times with 1300 g of water. The electric conductivity of the waste water in the fifth washing with water was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed by washing with water were sufficiently removed.

The organic phase after washing with water is concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour. The target naphthol aralkyl-type cyanate ester compound (SNCN) represented by the following formula (7) ( 331 g of an orange viscous product was obtained. The obtained SNCN had a mass average molecular weight Mw of 600. Further, the IR spectrum of SNCN showed absorption of 2250 cm ⁻¹ (cyanate group) and did not show absorption of a hydroxy group.
The cyanate ester compound SNCN was a mixture of n in the formula (7) in the range of 1-5.

Example 1
50 parts by mass of SNCN obtained by Synthesis Example 1, 1 part by mass of an epoxy resin (trade name “TEPIC-SP”, manufactured by Nissan Chemical Industries, Ltd.) represented by the following formula (1), represented by the following formula (8) 49 parts by mass of a biphenyl aralkyl type epoxy resin (trade name “NC-3000FH”, manufactured by Nippon Kayaku Co., Ltd.), 100 parts by mass of fused silica (trade name “SC2050MB”, manufactured by Admatex), and zinc octylate Varnish was obtained by mixing 0.12 parts by mass (manufactured by Nippon Chemical Industry Co., Ltd.). This varnish is diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm thick E glass woven fabric, dried by heating at 150 ° C. for 5 minutes, and the total amount of resin solids and fused silica is 100 parts by mass. A prepreg containing 50 parts by mass of resin solids was obtained.
(In formula (8), n represents an integer of 1 to 10)

Eight prepregs obtained were stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) was placed on both sides in the stacking direction at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. Lamination molding was performed for 120 minutes to obtain a metal foil-clad laminate with an insulating layer thickness of 0.8 mm. Using the obtained metal foil-clad laminate, glass transition temperature, copper foil peel strength, plating peel strength, water absorption rate, and weight loss rate during heating were evaluated. The results are shown in Table 1.

(Example 2)
As an epoxy resin, 3 parts by mass of the epoxy resin represented by the above formula (1) and a biphenylaralkyl type epoxy resin represented by the above formula (8) (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) 47 A metal foil-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1 except that the parts by mass were used. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Example 3)
As the epoxy resin, 5 parts by mass of the epoxy resin represented by the above formula (1) and the biphenylaralkyl type epoxy resin represented by the above formula (8) (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) 45 A metal foil-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1 except that the parts by mass were used. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

Example 4
As a cyanate ester compound, 50 parts by mass of a novolak-type cyanate ester compound represented by the following formula (9) (product name “Primaset PT-30”, manufactured by Lonza Japan Co., Ltd., weight average molecular weight of about 700) was used. A metal foil-clad laminate with a thickness of 0.8 mm was obtained in the same manner as Example 2 except for the above. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.
(In formula (9), n represents an integer of 1 to 10)

(Comparative Example 1)
Without using the epoxy resin represented by the formula (1), 50 parts by mass of the biphenyl aralkyl type epoxy resin represented by the above formula (8) (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) was used. Except for the above, a metal foil-clad laminate having a thickness of 0.8 mm was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Comparative Example 2)
Without using the epoxy resin represented by the formula (1), 50 parts by mass of the biphenyl aralkyl type epoxy resin represented by the above formula (8) (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.) was used. Otherwise, a metal foil-clad laminate with a thickness of 0.8 mm was obtained in the same manner as Example 4. Table 1 shows the evaluation results of the obtained metal foil-clad laminate.

(Measurement method and evaluation method)
1) Glass transition temperature About the obtained metal foil tension laminated board, the glass transition temperature was measured by DMA method with the dynamic viscoelasticity analyzer (made by TA Instruments) based on JISC6481.
2) Copper foil peel strength For the obtained metal foil-clad laminate, using a test piece (30 mm x 150 mm x 0.8 mm) cut to a predetermined size according to JIS C6481, the copper foil was pulled with a test number of 3. The peel strength was measured, and the average of the lower limit values was taken as the measured value.

3) Peeling peel strength After removing the copper foil on both sides of the obtained metal foil-clad laminate by etching, the sheet was subjected to a swelling treatment solution (trade name “OPC-B103 pre-etch” 400 ml / L manufactured by Okuno Pharmaceutical Co., Ltd.) and water. Sodium oxide 13 g / L) was immersed at 65 ° C. for 5 minutes. Next, it was immersed for 8 minutes at 80 ° C. in a roughening treatment solution (trade name “OPC-1540MN” manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / L and trade name “OPC-1200 Epochet” manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / L). Finally, it was immersed in a neutralization treatment solution (trade name “OPC-1300 Neutrizer” 200 ml / L) manufactured by Okuno Pharmaceutical Co., Ltd. for 5 minutes at 45 ° C. to perform desmear treatment. Then, electroless copper plating process (OPC-370 Condy Clean M, OPC-SAL M, OPC-80 Catalyst, OPC-555 Accelerator M, and ATS Ad Copper IW (Our product) Name)), electroless copper plating of about 0.5 μm was applied and dried at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was performed so that the thickness of the plated copper was 18 μm (30 mm × 150 mm × 0.8 mm), and drying was performed at 180 ° C. for 1 hour. Thus, a circuit wiring board test piece having a conductor layer (plated copper) having a thickness of 18 μm formed on the insulating layer was produced. Using the circuit wiring board test piece, the peel strength was measured with the number of tests 3 in accordance with JIS C6481, and the average value of the lower limit values was taken as the measured value.

4) Water absorption rate About the test piece which cut | disconnected the obtained metal foil tension laminated board to the predetermined dimension (30mmx30mmx0.8mm), based on JISC6481, a pressure cooker test machine (the Hirayama Seisakusho make, PC- Type 3) was measured for water absorption after treatment at 121 ° C. and 2 atm for 1, 3, and 5 hours.
5) Weight reduction rate during heating (%)
About the sheet | seat after removing the copper foil of the obtained metal foil tension laminated board by an etching, based on JIS-K7120-1987, a differential thermo-thermogravimetric simultaneous measuring apparatus (product name "TG nanotechnology Co., Ltd. product name" TG / DTA6200 "), sheet test piece dimensions: 3 mm x 3 mm x 0.8 mm, start temperature: 30 ° C, end temperature: 500 ° C, rate of temperature rise: 10 ° C / min, and weight measurement under nitrogen atmosphere The weight loss rate at 450 ° C. was calculated based on the following formula.
Weight reduction rate (%) = (I−J) / I × 100
Here, I represents the test piece weight at the starting temperature, and J represents the test piece weight at 450 ° C.
Here, the flame retardancy in the present invention is defined as a large amount of residue during pyrolysis, that is, a low weight loss rate during heating.

  As is apparent from Table 1, by using the resin composition of the present invention, a prepreg having a high peel strength and a low weight reduction rate upon heating, a high glass transition temperature, and a low water absorption rate, and It was confirmed that a printed wiring board can be realized.

  The resin composition of the present invention is used in various applications such as electrical / electronic materials, machine tool materials, and aviation materials, for example, electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminate materials, resists, build-up laminates. It can be used widely and effectively as a plate material. In particular, the resin composition of the present invention can be used particularly effectively as a printed wiring board material capable of high integration and high density in recent information terminal equipment and communication equipment. In addition, the metal foil-clad laminate of the present invention has a high peel strength and glass transition temperature, and has a low water absorption rate and a weight reduction rate during heating, so its industrial practicality is extremely high. It becomes.

Claims (11)

An epoxy resin (A) represented by the following formula (1), an epoxy resin (B) other than the epoxy resin (A) represented by the formula (1), and a cyanate ester compound (C) are contained. Resin composition.
  The resin composition of Claim 1 whose content of the said epoxy resin (A) is 0.1-10 mass parts with respect to 100 mass parts of resin solid content in the said resin composition. The cyanate ester compound (C) is selected from the group consisting of a naphthol aralkyl cyanate ester compound represented by the following formula (2) and a biphenylaralkyl cyanate ester compound represented by the following formula (3). The resin composition of Claim 1 or 2 which is 1 or more types.
(In formula, R1 shows a hydrogen atom or a methyl group each independently, and n1 shows the integer of 1-50.)
(In the formula, each R3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 to 50.)   The resin composition according to any one of claims 1 to 3, further comprising a filler (D).   The maleimide compound, the phenol resin, the oxetane resin, the benzoxazine compound, and at least one selected from the group consisting of compounds having a polymerizable unsaturated group, further containing at least one selected from Claims 1-4. Resin composition.   The resin composition of Claim 4 or 5 whose content of the said filler (D) is 50-1600 mass parts with respect to 100 mass parts of resin solid content in the said resin composition.   The prepreg which has a base material and the resin composition as described in any one of Claims 1-6 impregnated or apply | coated to this base material.   A metal foil-clad laminate comprising a layer containing at least one prepreg according to claim 7 and a metal foil laminated on one or both sides of the layer.   The resin sheet which has a resin layer containing the resin composition as described in any one of Claims 1-6. A support, and a resin layer disposed on the surface of the support,
The resin composite sheet in which the said resin layer contains the resin composition as described in any one of Claims 1-6. An insulating layer, and a conductor layer formed on the surface of the insulating layer,
The printed wiring board in which the said insulating layer contains the resin composition as described in any one of Claims 1-6.