JP2019014859A - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

To provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet and a printed wiring board that express a good balance of physical properties in peel strength and dielectric properties.SOLUTION: A resin composition contains (A) a silicon-containing polymer having constitutional units, where its polymerization terminals independently represent a thiol group, a glycidyl group, a hydroxy group or an alkoxy group, and its epoxy equivalent is 100 g/eq inclusive to 500 g/eq exclusive, and (B) a cyanate ester compound and (C) a maleimide compound.SELECTED DRAWING: None

Description

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

  In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, and the like have been 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 retardancy, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength.

Conventionally, cyanate ester compounds have been known as resins for printed wiring boards that have excellent heat resistance and electrical characteristics. In recent years, resin compositions in which cyanate ester compounds are used in combination with epoxy resins, bismaleimide compounds, etc. are used in semiconductor plastic packages. Widely used for high-performance printed wiring board materials.
For example, Patent Document 1 describes that a resin composition comprising a cyanate ester compound having a specific structure and other components is excellent in properties such as low water absorption and low thermal expansion coefficient.

International Publication No. 2012/105547

  Although it can be said that the resin composition described in Patent Document 1 has good physical properties such as low water absorption and low coefficient of thermal expansion, there is still room for improvement from the viewpoint of balance between peel strength and dielectric properties. It is what has.

  The present invention has been made in view of the above problems, and provides a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that exhibit excellent physical property balance in peel strength and dielectric properties. The purpose is to do.

  The present inventors diligently studied to solve the above problems. As a result, it has been found that the above problems can be achieved by using a silicon-containing polymer having a specific structure together with a cyanate ester compound and a maleimide compound, and the present invention has been completed.

That is, the present invention includes the following aspects.
[1]
A silicon-containing polymer having a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), wherein the polymerization terminals are each independently R ₁ , a hydroxyl group or an alkoxy group. A silicon-containing polymer (A) having an epoxy equivalent of 100 g / eq or more and less than 500 g / eq;
A cyanate ester compound (B);
A maleimide compound (C);
Containing a resin composition.
(In the formulas (a) and (b), each R ₁ independently represents a thiol group or a glycidyl group, and X represents a thiol group, a glycidyl group, a hydroxyl group, or a methoxy group, At least one of R ₁ and X is a glycidyl group, and at least one is a thiol group, and a plurality of R ₁ present in the silicon-containing polymer (A) may be the same or different. In addition, a plurality of Xs that may exist in the silicon-containing polymer (A) may be the same or different.
[2]
The resin composition according to claim 1, wherein the silicon-containing polymer (A) has a random structure.
[3]
The resin composition of Claim 1 or 2 whose content in the resin composition of the said silicon-containing polymer (A) is 1-25 mass parts with respect to 100 mass parts of resin solid content.
[4]
Furthermore, the resin composition as described in any one of Claims 1-3 containing a filler (D).
[5]
The resin composition according to claim 4, wherein the filler (D) is fused silica or aluminum oxide.
[6]
The resin composition of Claim 4 or 5 whose content in the resin composition of the said filler (D) is 50-1600 mass parts with respect to 100 mass parts of resin solid content.
[7]
A substrate;
The resin composition according to any one of claims 1 to 6, impregnated or coated on the base material,
Having a prepreg.
[8]
The prepreg according to claim 7, wherein at least one sheet is laminated,
A metal foil disposed on one or both sides of the prepreg;
A metal foil-clad laminate.
[9]
The resin sheet which has the resin composition as described in any one of Claims 1-6.
[10]
An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The printed wiring board in which the said insulating layer contains the resin composition as described in any one of Claims 1-6.

  According to the present invention, it is possible to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that exhibit excellent physical property balance in peel strength and dielectric properties.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[Resin composition]
The resin composition of the present embodiment is a silicon-containing polymer having a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), each having a polymerization terminal independently of each other. , R ₁ , a hydroxyl group or an alkoxy group, and an epoxy equivalent of 100 g / eq or more and less than 500 g / eq, a silicon-containing polymer (A), a cyanate ester compound (B), and a maleimide compound (C) , Containing. Since it is comprised in this way, the resin composition of this embodiment can express the outstanding physical property balance in peel strength and a dielectric property.

(In the formulas (a) and (b), each R ₁ independently represents a thiol group or a glycidyl group, and X represents a thiol group, a glycidyl group, a hydroxyl group, or a methoxy group, At least one of R ₁ and X is a glycidyl group, and at least one is a thiol group, and a plurality of R ₁ present in the silicon-containing polymer (A) may be the same or different. In addition, a plurality of Xs that may exist in the silicon-containing polymer (A) may be the same or different.

(Silicon-containing polymer (A))
The silicon-containing polymer (A) in the present embodiment is a silicon-containing polymer having structural units represented by the above formulas (a) and (b), and each polymerization terminal is independently R _1. , A hydroxyl group or an alkoxy group, and an epoxy equivalent is 100 g / eq or more and less than 500 g / eq. As long as such a configuration is satisfied, the silicon-containing polymer (A) is not particularly limited, but preferred embodiments will be described below.

When at least one of R ₁ and X in the above formulas (a) and (b) is a thiol group, the resin composition of the present embodiment can exhibit excellent peel strength. From the same viewpoint, R ₁ is preferably a thiol group, and X is preferably a glycidyl group.
Further, from the viewpoint of the storage stability of the polymer, the terminal of the silicon-containing polymer (A) needs to be any one of the aforementioned R ₁ , hydroxyl group and alkoxy group. Examples of the alkoxy group in this case include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  In this embodiment, the epoxy equivalent of the silicon-containing polymer (A) needs to be 100 g / eq or more and less than 500 g / eq, preferably 200 g / eq or more and less than 400 g / eq, more preferably 250 g. / Eq or more and less than 350 g / eq. When the epoxy equivalent is 500 g / eq or more, the compatibility between the silicon-containing polymer (A), the cyanate ester compound (B), and the maleimide compound (C) decreases, resulting in dielectric properties, glass transition temperature (Tg ) And the physical property balance of the coefficient of thermal expansion tend to decrease.

  In the present embodiment, the silicon-containing polymer (A) preferably has a random structure from the viewpoint of further improving the physical property balance between peel strength and dielectric properties. Here, the random structure means a structure in which the arrangement of the structural units is not regular and incomplete, and the silicon-containing polymer (A) has, for example, a nuclear magnetic field. This can be confirmed by resonance (NMR) or matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS).

The silicon-containing polymer (A) preferably further has a structural unit represented by the following formula (c) from the viewpoint of achieving both the fluidity and low warpage of the resin composition.
(Here, R ₂ is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and all R ₂ in the silicon-containing polymer may be the same or different.)

R ₂ in the general formula (c) is not limited to the following, but for example, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, Alkyl groups such as heptyl group, octyl group, 2-ethylhexyl group, alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, etc. Examples include aralkyl groups such as an aryl group, benzyl group, and phenethyl group, and a methyl group or a phenyl group is particularly preferable.

  In this embodiment, the softening point of the silicon-containing polymer (A) is preferably set to 40 ° C to 120 ° C, and more preferably set to 50 ° C to 100 ° C. If it is higher than 40 ° C, the mechanical strength of the cured product of the resin composition for printed wiring boards tends to increase. If it is lower than 120 ° C, the dispersibility of the silicon-containing polymer (A) in the resin composition is improved. Tend to. Examples of the method for adjusting the softening point of the silicon-containing polymer (A) include molecular weight of the silicon-containing polymer (A), structural bond units (for example, (a) to (c) content ratio, etc.), For example, setting the type of group.

  The weight average molecular weight (Mw) of the silicon-containing polymer (A) is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve, and is preferably 2000 or less, more preferably. Is 1800-1950. When Mw is 2000 or less, the compatibility between the silicon-containing polymer (A), the cyanate ester compound (B) and the maleimide compound (C) can be sufficiently ensured. As a result, dielectric properties and glass transition The physical property balance of temperature (Tg) and coefficient of thermal expansion tends to be further improved.

  The silicon-containing polymer (A) can be obtained by the production method shown below, but is commercially available as SQ502-8 manufactured by Arakawa Chemical Industries.

The manufacturing method of a silicon containing polymer (A) is not specifically limited, It can manufacture by a well-known method. For example, organochlorosilane, organoalkoxysilane, siloxane, or an organic solvent that can dissolve the raw materials and reaction products thereof, which can form the above units (a) to (c) by hydrolysis condensation reaction, and It can be obtained by mixing all the hydrolyzable groups of the raw material in a mixed solution with a hydrolyzable amount of water and subjecting it to a hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the resin composition, it is preferable to use organoalkoxysilane and / or siloxane as a raw material. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction.
Examples of the organoalkoxysilane and / or siloxane used as a raw material for the silicon-containing polymer (A) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxy Silane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxy Propyl (phenyl) dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) ) Diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and their hydrolysis condensates. It is done.
Moreover, about the thiol group which a silicon containing polymer (A) has, it can introduce | transduce by using the thiol group containing alkoxysilane represented by following formula (d) for a raw material.
R ¹ Si (OR ² ) ₃ (d)
(In formula (d), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R ² represents a hydrogen atom, carbon Represents a hydrocarbon group of formula 1 to 8, or an aromatic hydrocarbon group.)
Specific examples of thiol group-containing alkoxysilanes include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4-dimercapto 2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2, − Lucaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyl A tributoxysilane etc. are mentioned. These compounds can be used individually by 1 type or in combination of 2 or more types as appropriate. Among these, 3-mercaptopropyltrimethoxysilane is particularly preferable because of its high reactivity of hydrolysis reaction and easy availability.

The content of the silicon-containing polymer (A) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of more excellent physical properties balance of dielectric properties, glass transition temperature (Tg) and coefficient of thermal expansion, 1-25 mass parts is preferable with respect to 100 mass parts of resin solid content, More preferably, it is 3-15 mass parts, More preferably, it is 5-10 mass parts.
In the present embodiment, the “resin solid content” refers to a component excluding the solvent and filler in the resin composition of the present embodiment, unless otherwise specified, and “resin solid content of 100 parts by mass”. Means that the total of the components excluding the solvent and filler in the resin composition of the present embodiment is 100 parts by mass. That is, the mass of the silicon-containing polymer (A) is also included in the resin solid content.

(Cyanate ester compound (B))
The cyanate ester compound contained in the resin composition in the present embodiment is not particularly limited as long as it is a compound having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group). A resin composition using a cyanate ester compound has excellent properties such as glass transition temperature, low thermal expansion, plating adhesion and the like when cured.

  Examples of the cyanate ester compound include, but are not limited to, those represented by the following formula (1).

In the above formula (1), Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings. When there are a plurality, 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, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. A group to which an aryl group is bonded is shown. 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 represents 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 single-bonded. . t represents the average number of repetitions and ranges from 0 to 50. The cyanate ester 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— (wherein 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 in the above formula (1) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).
The hydrogen atom in the alkyl group in formula (1) and the aryl group in Ra 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, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, Examples include 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, cyclohexyl group, and trifluoromethyl group.
Specific examples of the aryl group include, but are not limited to, phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyano. Examples thereof include a phenyl group, a trifluorophenyl group, a methoxyphenyl group, and an o-, m- or p-tolyl group.
Examples of the alkoxyl group include, but are not limited to, 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 of the formula (1) are not limited to the following, but include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, and trimethyl. Examples include 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, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the formula (1) include, but are not limited to, an imino group and a polyimide group.

  Moreover, as an organic group of X in the said Formula (1), what is a structure represented by following formula (2) or following formula (3) is mentioned, for example.

(In the above formula (2), 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 or different from each other. Rb, Rc , Rf, and Rg each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxy 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.)

(In formula (3), 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 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 a cyanato group. And at least one substituted aryl group, v represents an integer of 0 to 5, but v may be a mixture of different compounds.

  Furthermore, as X in Formula (1), the bivalent group represented by a following formula is mentioned.

(In the above formula, z represents an integer of 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Specific examples of Ar ₃ in the formula (2) Ar ₂ and (3) of the two carbon atoms shown in formula (2), or two oxygen atoms shown in the formula (3), 1,4 Benzenetetrayl group bonded to 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 ′ 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, 6 Naphthalenetetrayl group bonded to the 1-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.
Rb, Rc, Rd, Re, Rf and Rg in formula (2), and the alkyl group and aryl group in Ri and Rj in formula (3) have the same meanings as in formula (1) above.

  Specific examples of the cyanato-substituted aromatic compound represented by the above formula (1) are not limited to the following, but 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, cyanato Nonylbenzene, 2- (4-cyanphenyl) -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-acetamino Benzene, 4-cyanatobenzophenone, 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-dimethylbenzene, 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-dicyanatosinaphthalene, 2,2'- Is 4,4′-dicyanatobiphenyl, 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-dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bi (4-cyanatophenyl) pentane, 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-si Anatophenyl) hexane, 2,2-bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanato) Phenyl) -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-si Anatophenyl) -1-pheni Ethane, bis (4-cyanatophenyl) 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 ( Phenolphthalein cyanate), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o -Cresolphthalein cyanate), 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- ( -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 ′-(hexafluoro Isopropylidene) diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl)- 3,3-bis (4-cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1 3,3-bis (4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

Moreover, as another specific example of the compound represented by the above formula (1), although not limited to the following, a phenol novolak resin and a cresol novolak resin (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, Formaldehyde and paraformaldehyde and other formaldehyde compounds reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound) And 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (known methods) _{More, Ar 4 - (CH 2 Y} ) 2 (. Ar 4 represents a phenyl group, Y represents a halogen atom and the same in this paragraph.) And bishalogenomethyl compounds represented by the phenol compound An acid catalyst or non-catalyzed reaction, a reaction between a bis (alkoxymethyl) compound represented by Ar ₄ — (CH ₂ OR) ₂ and a phenol compound in the presence of an acidic catalyst, or A reaction product of a bis (hydroxymethyl) compound represented by Ar ₄ — (CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound. Polycondensed), phenol-modified xylene formaldehyde resin (by known methods, xylene formaldehyde resin and phenol compound) In the presence of an acidic catalyst), modified naphthalene formaldehyde resin (reacted naphthalene formaldehyde resin and hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclo Pentadiene resin, phenol resin having polynaphthylene ether structure (by polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule by dehydration condensation in the presence of a basic catalyst And the like, and those prepolymers obtained by cyanating a phenol resin such as) by the same method as described above.

  The above-mentioned cyanate ester compounds can be used alone or in combination of two or more.

  Among the above-described cyanate ester compounds, bisphenol A-type cyanate ester compounds, bisphenol E-type cyanate ester compounds, bisphenol-type cyanate ester compounds such as bisphenol F-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, and the like Phenol novolac type cyanate ester compounds are preferred. That is, in this embodiment, the cyanate ester compound includes at least one selected from the group consisting of a bisphenol-type cyanate ester compound, a naphthol aralkyl-type cyanate ester compound, and a phenol novolac-type cyanate ester compound. preferable. Furthermore, it is more preferable that the cyanate ester compound contains a diallyl bisphenol A type cyanate ester compound.

  The content of the cyanate ester compound can be appropriately set according to the desired properties and is not particularly limited, but from the viewpoint of further improving the physical properties balance of dielectric properties, glass transition temperature (Tg) and coefficient of thermal expansion. 30-100 mass parts is preferable with respect to 100 mass parts of resin solid content, More preferably, it is 35-80 mass parts, More preferably, it is 40-70 mass parts.

[Maleimide compound (C)]
The maleimide compound (C) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. For example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane Bis (3,5-diethyl-4-maleimidophenyl) methane, maleimide compounds represented by the following formula (4), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Among these, 2,2′-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and the following formula (4) At least one selected from the group consisting of maleimide compounds is preferred. By including such a maleimide compound (C), the thermal expansion coefficient of the obtained cured product is further lowered, and the glass transition temperature tends to be more excellent. From the same viewpoint, it is more preferable that the maleimide compound (C) contains at least one selected from the group consisting of maleimide compounds represented by the following formula (4).

Here, in Formula (4), each R ₅ independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Moreover, in Formula (4), n1 represents an integer greater than or equal to ₁ , Preferably it is an integer below 10, More preferably, it is an integer below 7.

  The content of the maleimide compound (C) in the present embodiment is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, and further preferably 25 to 25 parts by mass with respect to 100 parts by mass of the resin solid content. 50 parts by mass. When content of a maleimide compound (C) exists in the said range, it exists in the tendency for the thermal expansion coefficient of the hardened | cured material obtained to fall more, and for heat resistance to improve more.

  The resin composition of this embodiment can further contain one or more selected from the group consisting of an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. Hereinafter, each of these components will be described.

(Epoxy resin)
As the epoxy resin, any known epoxy resin can be used as long as it has two or more epoxy groups in one molecule, and the kind thereof is not particularly limited, but the above-mentioned silicon-containing polymer (A ) Is different. Specifically, 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, polyfunctional phenol type epoxy resin, naphthalene 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 ester Carboxy resin, a polyol type epoxy resins, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, compounds of the double bonds epoxidized in butadiene, such as a compound obtained by reaction of a hydroxyl-group-containing silicon resin 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.

(Phenolic resin)
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. Specific examples thereof 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, aralkyl novolac 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, biphenyl type phenolic resin Nord resins, alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, 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.

(Oxetane resin)
As the oxetane resin, generally known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (trade name, manufactured by Toagosei Co., Ltd.) Although it is mentioned, it is not particularly limited. These oxetane resins can be used alone or in combination.

(Benzoxazine compound)
As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical), P -D type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Fa type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like can be mentioned, but are not particularly limited. These benzoxazine compounds can be used alone or in combination.

(Compound having a polymerizable unsaturated group)
As the compound having a polymerizable unsaturated group, generally known compounds can be used. For example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, Mono- or polyhydric alcohol (meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol And epoxy (meth) acrylates such as A-type epoxy (meth) acrylate and bisphenol F-type epoxy (meth) acrylate, and benzocyclobutene resin. But it is not particularly limited. These compounds having an unsaturated group can be used alone or in combination. The “(meth) acrylate” is a concept including acrylate and methacrylate corresponding to the acrylate.

[Filler (D)]
The resin composition of the present embodiment preferably further contains a filler (D) from the viewpoints of thermal expansion characteristics, dimensional stability, flame retardancy, thermal conductivity, dielectric characteristics, and the like. 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, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, Oxides such as zirconium oxide, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated products (heat treatment of aluminum hydroxide was performed to reduce some of the crystal water ), Boehmite, metal hydrates such as magnesium hydroxide, 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-gala , L-glass, D-glass, 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, In addition to inorganic fillers (D) such as spherical glass, styrene type, butadiene type, acrylic type rubber powder, core shell type rubber powder, and organic type fillers such as silicone resin powder, silicone rubber powder, and silicone composite powder A material (D) etc. are mentioned. These fillers (D) can be used alone or in combination of two or more.
From the viewpoint of further improving the thermal conductivity of the resin composition, among the above, fused silica or aluminum oxide is preferable, and aluminum oxide is more preferable.

  The content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to the desired properties, and is not particularly limited, but from the viewpoint of moldability of the resin composition, the resin solid content is When it is 100 mass parts, it is preferable to set it as 50-1600 mass parts, More preferably, it is 50-750 mass parts, More preferably, it is 50-300 mass parts, Most preferably, it is 50-200 mass parts. .

  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 the silane coupling agent include, but are not limited to, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxylane, and γ-glycid. Epoxysilanes such as xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri (β-methoxyethoxy) silane, N Examples include cationic silanes such as -β- (N-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, but are not limited to, Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, BYK-W940 and the like manufactured by Big Chemie Japan Co., Ltd. It is done. Wet dispersants can be used alone or in combination of two or more.

(Curing accelerator)
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, azo compounds such as azobisisobutyronitrile, and N, N-dimethylaminopyridine. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

(Other additives)
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. Specific examples of the flame retardant compound include, but are not limited to, bromine compounds such as 4,4′-dibromobiphenyl, phosphoric acid esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and benzoguanamine, and oxazine Examples thereof include a ring-containing compound and a silicone compound. Examples of various additives include, but are not limited to, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, and flow modifiers. , 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.

(Organic solvent)
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 the organic solvent 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, methyl lactate, methyl acetate, ethyl acetate, butyl acetate, and isoamyl acetate. , Ester solvents such as ethyl lactate, 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 It is done. 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 the resin composition uniformly contains the cyanate ester compound (B), the maleimide compound (C) and other optional components described above in the present embodiment. If it is a method by which a thing is obtained, the preparation method will not be specifically limited. For example, the cyanate ester compound (B), maleimide compound (C) and other optional components described above in this embodiment are sequentially blended in a solvent, and the resin composition of this embodiment is easily prepared by sufficiently stirring. can do.

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

The resin composition of this 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 applying the resin composition of the present embodiment to a substrate, it is semi-cured by a method of drying for about 2 to 15 minutes in a dryer at 120 to 220 ° C. The prepreg of the 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 the present embodiment has at least one or more of the above-described prepregs laminated and a metal foil disposed on one or both sides of the prepreg. 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 foils, such as a rolled copper foil and a dip copper foil, are 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 As a result, 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 method for producing a multilayer board, for example, a 35 μm copper foil is disposed on both surfaces of one prepreg described above, laminated under the above conditions, an inner layer circuit is formed, and blackening treatment 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 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.

  The resin sheet of the present embodiment refers to a support and the resin composition layer (laminated sheet) disposed on the surface of the support, and only the resin composition layer from which the support is removed (single layer sheet) ). That is, the resin sheet of this embodiment has at least the resin composition of this embodiment. This laminated 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. As a coating method, for example, a solution in which the above resin composition is dissolved in a solvent is coated on the support with a bar coater, a die coater, a doctor blade, a baker applicator, etc. Is a method of producing a laminated sheet in which are integrated. Moreover, a single layer sheet | seat can also be obtained by peeling or etching a support body from the resin sheet obtained by drying after application | coating. In addition, the solution obtained by dissolving or dissolving the resin composition of the present embodiment in a solvent is supplied into a mold having a sheet-like cavity and dried to form a sheet, thereby supporting the support. A single layer sheet can also be obtained without using.

  In addition, in preparation of the resin sheet or single layer sheet of this embodiment, the drying conditions at the time of removing a solvent are not specifically limited, However, It is preferable to make it dry for 1 to 90 minutes at the temperature of 20 to 200 degreeC. 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 suppressed. Moreover, the thickness of the resin layer in the resin sheet or single layer sheet of this embodiment can be adjusted with the density | concentration and application | coating thickness of the resin composition of this embodiment, and is not specifically 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.

  Hereinafter, the present embodiment will be described more specifically using examples and comparative examples. This embodiment is not limited at all by the following examples.

[Synthesis Example 1] Synthesis of cyanate ester compound of diallyl bisphenol A (hereinafter abbreviated as DABPA-CN) 700 g of diallyl bisphenol A (hydroxyl group equivalent 154.2 g / eq.) (OH group equivalent 4.54 mol) (DABPA , Manufactured by Daiwa Kasei Kogyo Co., Ltd.) and 459.4 g (4.54 mol) of triethylamine (1.0 mol with respect to 1 mol of hydroxyl group) were dissolved in 2100 g of dichloromethane.
474.4 g (7.72 mol) of cyanogen chloride (1.7 mol with respect to 1 mol of hydroxyl group), 1106.9 g of dichloromethane, 735.6 g (7.26 mol) of 36% hydrochloric acid (1. 1 mol with respect to 1 mol of hydroxyl group). 6 mol) and 4560.7 g of water were poured over 90 minutes while stirring at a liquid temperature of −2 to −0.5 ° C. After the completion of the pouring of the solution 1, after stirring at the same temperature for 30 minutes, 459.4 g (4.54 mol) of triethylamine (1.0 mol per mol of hydroxyl group) was dissolved in 459.4 g of dichloromethane ( Solution 2) was poured over 25 minutes. After the end of pouring 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 an organic phase and an aqueous phase. The obtained organic phase was washed with 2 L of 0.1N hydrochloric acid and then washed 6 times with 2000 g of water. The electrical conductivity of the waste water in the sixth washing with water was 20 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 805 g of the intended cyanate ester compound DABPA-CN (light yellow liquid). The IR spectrum of the obtained cyanate ester compound DABPA-CN showed an absorption of 2264 cm ⁻¹ (cyanate ester group) and no absorption of a hydroxyl group.

Example 1
DABPA-CN 47.5 parts by mass, 47.5 parts by mass of a novolac-type bismaleimide compound (Daiwa Kasei Kogyo Co., Ltd., BMI-2300), silicon-containing polymer (Arakawa Chemical Industries, SQ502-8, epoxy equivalent 276 g / eq) ) 5.0 parts by mass, epoxy silane-treated fused silica (manufactured by Admatechs, SC2050MB) 100.0 parts by mass, 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts by mass, octyl Varnish was obtained by mixing 0.10 parts by mass of zinc oxide (manufactured by Nippon Chemical Industry Co., Ltd.). In addition, it was 1832 when the weight average molecular weight of said SQ502-8 was measured. The weight average molecular weight was measured as follows. That is, 4.1 g of SQ502-8 was weighed and 10 μL of a solution dissolved in 100 g of tetrahydrofuran (solvent) was injected into high performance liquid chromatography (high performance liquid chromatograph LachromElite manufactured by Hitachi High-Technologies Corporation) for analysis. did. Two columns are TSKgel GMHHR-M (length 30 cm × inner diameter 7.8 mm) manufactured by Tosoh Corporation, the mobile phase is tetrahydrofuran, and the flow rate is 1 mL / min. The detector was RI. The weight average molecular weight Mw was determined using polystyrene as a standard substance by the GPC method.

(Example 2)
A varnish was obtained in the same manner as in Example 1 except that the fused silica as the filler was changed to 100 parts by mass of aluminum oxide and the amount of zinc octylate used was 0.3 parts by mass.

(Comparative Example 1)
A varnish was obtained in the same manner as in Example 1 except that SQ502-8 was not used and the amounts of DABPA-CN and BMI-2300 were changed to 50.0 parts by mass, respectively.

[Method for producing copper-clad laminate]
The varnish obtained as described above was impregnated and applied to an E glass cloth having a thickness of 0.1 mm, and 165 ° C., 4 ° C. using a dryer (fireproof explosion-proof steam dryer, manufactured by Takasugi Seisakusho Co., Ltd.). The mixture was heat-dried for 46 minutes to obtain a prepreg having a resin composition of 46% by mass. 8 prepregs are stacked, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) is placed on both sides, vacuum pressed for 120 minutes at a pressure of 40 kg / cm ² and a temperature of 230 ° C. A 0.8 mm 12 μm copper-clad laminate was obtained. The following evaluation was performed using the obtained copper-clad laminate.

[Copper foil peel strength]
Using a test piece (30 mm × 150 mm × 0.8 mm thickness) of a double-sided copper-clad laminate with an insulating layer thickness of 0.8 mm, which will be described later, a copper-clad laminate test method for printed wiring boards according to JIS C6481 (5.7 drawing) According to the peel strength, the peel strength of the copper foil was measured three times, and the average of the lower limit values was taken as the measured value.

[Dielectric constant (Dk)]
Using the test piece (n = 3) from which the copper foil of the copper-clad laminate was removed, the dielectric constants of 2 GHz and 10 GHz were measured by a cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies), The average value was obtained.

〔Thermal conductivity〕
Next, the following heat resistance evaluation was performed using the copper-clad laminate obtained as described above from the varnish of Example 2.
The copper foil on the surface of the obtained copper foil clad laminate having an insulating layer thickness of 0.8 mm was removed by etching to obtain a measurement sample. The density of the obtained sample was measured, the specific heat was measured by DSC (TA Instrument Q100 type), and the thermal diffusivity was further measured by a xenon flash analyzer (Bruker: LFA447 Nanoflash). Next, the thermal conductivity in the thickness direction was calculated from the following equation.
Thermal conductivity (W / m · K) = density (kg / m ³ ) × specific heat (kJ / kg · K) × thermal diffusivity (m ² / s) × 1000

(Reference example)
In order to evaluate the thermal conductivity in Example 2, the following samples were prepared.
A varnish was obtained in the same manner as in Example 2 except that SQ502-8 was not used and the amounts of DABPA-CN and BMI-2300 were changed to 50.0 parts by mass, respectively.

  The resin composition of the present invention has industrial applicability as a material for prepregs, metal foil-clad laminates, resin sheets, printed wiring boards and the like.

Claims (10)

A silicon-containing polymer having a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), wherein the polymerization terminals are each independently R ₁ , a hydroxyl group or an alkoxy group. A silicon-containing polymer (A) having an epoxy equivalent of 100 g / eq or more and less than 500 g / eq;
A cyanate ester compound (B);
A maleimide compound (C);
Containing a resin composition.
(In the formulas (a) and (b), each R ₁ independently represents a thiol group or a glycidyl group, and X represents a thiol group, a glycidyl group, a hydroxyl group, or a methoxy group, At least one of R ₁ and X is a glycidyl group, and at least one is a thiol group, and a plurality of R ₁ present in the silicon-containing polymer (A) may be the same or different. In addition, a plurality of Xs that may exist in the silicon-containing polymer (A) may be the same or different.   The resin composition according to claim 1, wherein the silicon-containing polymer (A) has a random structure.   The resin composition of Claim 1 or 2 whose content in the resin composition of the said silicon-containing polymer (A) is 1-25 mass parts with respect to 100 mass parts of resin solid content.   Furthermore, the resin composition as described in any one of Claims 1-3 containing a filler (D).   The resin composition according to claim 4, wherein the filler (D) is fused silica or aluminum oxide.   The resin composition of Claim 4 or 5 whose content in the resin composition of the said filler (D) is 50-1600 mass parts with respect to 100 mass parts of resin solid content. A substrate;
The resin composition according to any one of claims 1 to 6, impregnated or coated on the base material,
Having a prepreg. The prepreg according to claim 7, wherein at least one sheet is laminated,
A metal foil disposed on one or both sides of the prepreg;
A metal foil-clad laminate.   The resin sheet which has the resin composition as described in any one of Claims 1-6. An insulating layer;
A conductor layer formed on the surface of the insulating layer;
Have
The printed wiring board in which the said insulating layer contains the resin composition as described in any one of Claims 1-6.