JP6216179B2 - Curable resin composition and cured product - Google Patents

Description

  The present invention relates to a curable resin composition, a varnish for circuit board material, a cured product, a curable composite material, a composite material cured product, a laminate comprising the cured composite material and a metal foil, a metal foil with resin, and a circuit board material. .

  With the increase in information traffic in recent years, information communication in the high frequency band has been actively performed, and in order to reduce the transmission loss in the higher frequency band, more excellent electrical characteristics, in particular, low dielectric constant and low There is a need for an electrically insulating material having a dielectric loss tangent and a small change in dielectric properties after being subjected to a particularly severe thermal history. Furthermore, since printed circuit boards or electronic components using these electrical insulating materials are exposed to high-temperature solder reflow during mounting, a material having high heat resistance, that is, a high glass transition temperature is desired. In particular, recently, due to the use of lead-free solder having a high melting point due to environmental problems, there is an increasing demand for an electrically insulating material with higher heat resistance. In response to these requirements, conventionally, curable resin compositions containing vinylbenzyl ether compounds having various chemical structures have been proposed.

  As such a curable resin composition, for example, a curable resin containing a poly (vinylbenzyl) ether compound obtained by reacting a phenol aralkyl resin obtained by condensing a biphenyl compound with vinylbenzyl halide. A composition has been proposed (Patent Document 1). However, the poly (vinyl benzyl) ether compound disclosed therein has not been able to obtain sufficient characteristics in the initial dielectric properties, but also has a large change in dielectric properties due to severe thermal history, and insufficient heat resistance. It was a thing. In addition, thermosetting resins known as resins that can be used in combination with the poly (vinylbenzyl) ether compounds disclosed therein, such as vinyl ester resins, unsaturated polyester resins, maleimide resins, polyphenol polycyanate resins, epoxy Resins, phenol aralkyl resins, vinyl benzyl compounds, and the like are mentioned, but specifically, examples of compositions with these resins are not shown, and the effect is not clear.

  On the other hand, several poly (vinyl benzyl) ether compounds with a specific structure have been proposed as poly (vinyl benzyl) ether compounds, attempts to suppress changes in dielectric loss tangent when subjected to severe thermal history, and attempts to improve heat resistance. However, the improvement in characteristics has not been sufficient yet, and further improvement in characteristics has been desired. For this reason, the mounting material is not sufficient in reliability and workability (Patent Document 2, Patent Document 3, and Patent Document 4).

  Also, a curing containing a phenol aralkyl resin, a naphthol aralkyl resin, a biphenyl type phenol novolak resin or a curable resin in which a hydroxyl group of a biphenyl type naphthol novolak resin is converted to vinyl benzyl ether, and a compound having one or more maleimide groups in the molecule. A functional resin composition is disclosed in Patent Document 5. However, the curable resin composition disclosed therein is insufficient in initial characteristics of dielectric properties, and is not satisfactory as an insulating material for adhesion reliability after receiving heat and moisture history. Also, in terms of moldability, molding defects are likely to occur, which is not desirable.

  On the other hand, Patent Document 6 discloses an insulating sheet and a laminated structure capable of obtaining a cured product having a high handling property in an uncured state and a low relative dielectric constant, and forms the sheet and the structure. A curable resin composition containing a poly (vinylbenzyl) ether compound and an epoxy resin as materials is disclosed. Specific examples of the poly (vinylbenzyl) ether compound include hydroquinone, bisphenol A, bisphenol F, bisphenol S, biphenol, phenol novolac resin, a condensation product of phenol and benzaldehyde, or xylok type phenol resin with a vinylbenzyl ether group. In the examples, only the vinyl benzyl ether compound of Xylok type phenol resin was disclosed. The curable resin composition containing the poly (vinylbenzyl) ether compound and the epoxy resin disclosed therein has a large change in dielectric loss tangent when subjected to severe thermal history, and after the wet heat history The adhesion reliability was also insufficient.

  As described above, the conventional poly (vinylbenzyl) ether compound and the curable resin composition thereof satisfy the low dielectric loss tangent after the severe thermal history necessary for the electrical insulation material use, particularly the electrical insulation material application for high frequency. It did not give a cured product having heat resistance, and was insufficient in terms of adhesion reliability and workability.

Japanese Patent No. 459946 JP-T-1-503238 JP-A-9-31006 JP 2004-323730 A JP 2003-306591 A Japanese Patent Application Laid-Open No. 2011-124076

  The present invention is a cured product having high dielectric properties (low dielectric constant and low dielectric loss tangent) even after severe heat history, and high adhesion reliability even in severe environments such as high temperature and high humidity. An object of the present invention is to provide a curable resin composition that provides a curable resin and a cured product. Another purpose is to prevent molding defects such as warping in response to the recent demand for compactness and thinning as dielectric materials, insulating materials and heat-resistant materials in fields such as the electric / electronic industry, space / aircraft industry, etc. An object of the present invention is to provide a resin composition, a cured product or a composite material, a laminate, a resin-attached metal foil, a circuit board material, and the like that can provide a cured molded product that does not have a cured product.

  The inventors of the present invention provide a poly (vinylbenzyl) ether compound obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound, an aromatic system having two or more epoxy groups in a molecule, a cyanurate system, and / or The present inventors have found that an alicyclic epoxy resin and a curable resin composition containing a curing agent are effective for solving the above problems, and completed the present invention.

That is, the present invention provides (A) component: a poly (vinylbenzyl) ether compound represented by the following formula (1) obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound,
Component (B): Epoxy resin (B1) having two or more epoxy groups and aromatic structure in one molecule, Epoxy resin (B2) having two or more epoxy groups and cyanurate structure in one molecule and / or one molecule A curable resin composition comprising an epoxy resin (B3) having two or more epoxy groups and an alicyclic structure, and a component (C): a curing agent.

ここで、Ｒ^１はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、アリル基、または炭素数６〜１０のアリール基を表し、Ａｒ^１は炭素数６〜５０の２価の芳香族炭化水素基を表し、Ｒ^２はそれぞれ独立して水素原子、炭素数１〜１２のアルキル基、またはビニルベンジル基を表すが、Ｒ^２におけるビニルベンジル基の割合は６０〜１００モル％である。ｎは平均値で１〜２０の範囲であり、ｍは１〜６の数であり、ｒは１〜３の数である。但し、ｍ+ｒは６又は７を超えない。

Here, each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 10 carbon atoms, and Ar ¹ is a divalent aromatic having 6 to 50 carbon atoms. Represents a group hydrocarbon group, and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group, and the proportion of the vinylbenzyl group in R ² is 60 to 100 mol%. . n is an average value ranging from 1 to 20, m is a number from 1 to 6, and r is a number from 1 to 3. However, m + r does not exceed 6 or 7.

  The curable resin composition further comprises a high molecular weight resin having a weight average molecular weight of 10,000 or more as the component (D), a radical polymerization initiator as the component (E), an inorganic filler as the component (F), or ( G) A flame retardant can be contained as a component. When it contains (D)-(G) component, it can be arbitrary 1 type or a combination of 2 or more types.

  Moreover, this invention is a varnish for circuit board materials formed by dissolving said curable resin composition in a solvent. Moreover, this invention is a hardened | cured material formed by hardening | curing said curable resin composition. Furthermore, the present invention is a curable composite material comprising the above-mentioned curable resin composition and a base material, and is a composite material cured product obtained by curing the curable composite material, and It is a laminated body characterized by having a layer of the cured composite material and a metal foil layer.

  Furthermore, the present invention is a metal foil with a resin characterized by having a film formed from the above curable resin composition on one side of the metal foil. Moreover, this invention is circuit board material which uses said hardened | cured material, composite material hardened | cured material, or a laminated body.

The component (A) has a total halogen content of 600 ppm (wt) or less, and the peak area of the vinyl aromatic halomethyl compound summed with the peak area of the poly (vinylbenzyl) ether compound in gas chromatography (GC) measurement It is desirable that it is 1.0% or less with respect to the area, or a part of R ² in the above formula (1) is an alkyl group having 1 to 12 carbon atoms.

  As the component (B), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolak type epoxy resin, xylylene modified phenol novolak type epoxy resin, xylylene modified alkylphenol novolak type epoxy resin, biphenyl type It is desirable to be at least one epoxy resin selected from the group consisting of epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantane type epoxy resins.

  As the component (C), o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolak resin, biphenyl type naphthol Novolak resin, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride and di It is desirable to be one or more epoxy resin curing agents selected from the group consisting of acid anhydrides having a cyclopentadiene skeleton and modified products of the acid anhydrides.

  The component (D) is selected from the group consisting of polysulfone resin, polyethersulfone resin, polyphenylene ether resin, phenoxy resin, polycycloolefin resin, hydrogenated styrene-butadiene copolymer and hydrogenated styrene-isoprene copolymer. It is desirable to be one or more high molecular weight resins.

  The curable resin composition of the present invention has a high dielectric property (low dielectric constant / low dielectric loss tangent) even after a severe heat history, and can provide a cured product having high adhesion reliability. Materials that can be used as dielectric materials, insulating materials, and heat-resistant materials in fields such as the electronics industry, the space / aircraft industry, and the like can be realized. In particular, it can be suitably used as a circuit board material such as single-sided, double-sided, multilayer printed board, flexible printed board, build-up board.

The present invention will be further described below.
The poly (vinyl benzyl) ether compound used as the component (A) of the present invention is a compound having a structure represented by the above formula (1), obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound. is there.

In Formula (1), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 10 carbon atoms. The aryl group may further have a substituent, for example, an alkyl group having 1 to 6 carbon atoms. Calculation of the carbon number of the aryl group does not include the carbon number of the substituent. Preferably, R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, from the viewpoint of a balance between solubility and dielectric properties, curability and flame retardancy, and more A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is particularly preferable.
M represents a number from 1 to 6, but preferably, from the viewpoint of the balance between solubility and flame retardancy, when R ¹ is a substituent other than hydrogen, the number (m ′) is from 0 to 2. is there.

R ² independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group. The proportion of vinyl benzyl group occupying in ^{R 2} (mol%) is from 60 to 100%, preferably from 90 to 100%. On the other hand, 0-40 mole% of the ^{R 2} is a hydrogen atom, an alkyl group or both. It is preferable that a part of R ² is an alkyl group having 1 to 12 carbon atoms because it gives excellent toughness, moldability and dielectric properties. More preferably, the ratio of alkyl group having 1 to 12 carbon atoms in ^{R 2} is 1 to 30 mol%, more preferably 1 to 10%. Moreover, when the ratio of a vinylbenzyl group is less than 60%, there are few polymerization active points, and the problem of insufficient curing occurs. Furthermore, when the sum of the vinylbenzyl group and the alkyl group having 1 to 12 carbon atoms in R ² is less than 61%, the dielectric properties tend to deteriorate.
R represents a number of 1 to 3, but preferably 1 or 2 from the viewpoint of solubility and toughness. m + r is a 6 or 7, 'When, m' the number of those wherein R ¹ is a substituent other than a hydrogen atom m + r is preferably 1-4.

Ar ¹ represents an aromatic hydrocarbon group having 6 to 50 carbon atoms. For example, -Ph -, - Ph-Ph -, - Np -, - Np-CH 2 -Np -, - Ph-CH 2 -Ph -, - Ph-C (CH 3) 2 -Ph -, - Ph- _{CH (CH 3) -Ph -,} - Ph-CH (C 6 H 5) -Ph -, - Ph-Flu-Ph-, and -Flu _{(CH 3) 2} - the number of carbon atoms from 6 selected from herd consisting of 50 aromatic hydrocarbon groups and the like. More preferably, it is an aromatic hydrocarbon group having 6 to 20 carbon atoms. Here, Ph represents a phenylene group (—C ₆ H ₄ —), Np represents a naphthylene group (—C ₁₀ H ₆ —), and Flu represents a fluorenyl group (—C ₁₃ H ₈ —). Here, Ph, Np, and Flu may have a substituent, for example, an alkyl group, an alkoxy group, or a phenyl group. Preferably, an alkyl group having 1 to 6 carbon atoms is used. Ar ¹ is more preferably unsubstituted, alkyl group-substituted, alkoxy group-substituted or phenyl group-substituted -Ph-, -Ph-Ph-, or -Np- from the viewpoints of solubility and flame retardancy. .

  N is an average value and represents a number of 1 to 20, preferably 1 to 10. When n exceeds 20, the viscosity is increased, which is not preferable in that the filling property to the fine pattern is lowered. In addition, when it has molecular weight distribution, it is a number average value.

  Furthermore, the poly (vinylbenzyl) ether compound represented by the above formula (1) has a peak area (a) based on the vinyl aromatic halomethyl compound in the gas chromatography (GC) measurement. It is preferably 1.0% or less with respect to the peak area (a + b) totaled with the peak area (b). Preferably, it is 0.5% or less, more preferably 0.2% or less. If this peak area exceeds 1.0%, the dielectric properties after receiving a thermal history of 250 ° C. or higher for a long time tend to deteriorate. Here, the peak area of the poly (vinylbenzyl) ether compound means a peak area based on a pure poly (vinylbenzyl) ether compound that satisfies the above formula (1). The poly (vinylbenzyl) ether compound used as the component (A) is a reaction product or a purified product thereof, and an impurity that does not satisfy the above formula (1) in addition to a pure poly (vinylbenzyl) ether compound As well as other ingredients.

The poly (vinylbenzyl) ether compound used as the component (A) preferably has a total halogen content of 600 ppm or less. More preferably, it is 450 ppm or less, More preferably, it is 200 ppm or less. When the total halogen content exceeds 600 ppm, the dielectric properties after receiving a thermal history of 250 ° C. or higher for a long time tend to be lowered. Since this halogen is mainly based on the aromatic halomethyl compound as a raw material, it is related to the peak area of the poly (vinylbenzyl) ether compound.
Moreover, when the halogen content is 600 ppm or less, it is preferable because an undesirable effect of avoiding a molding defect phenomenon such as warpage or transfer failure can be obtained. However, reducing the total halogen content and the vinyl aromatic halomethyl compound content more than necessary significantly reduces the purification yield. According to experiments, it has been found that if the total halogen content is 2 ppm or more, the above-mentioned problems relating to industrial implementation do not occur, so that purification beyond this is advantageous from the viewpoint of purification yield. I can not say.

The poly (vinylbenzyl) ether compound used as the component (A) is obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound as described above. This naphthol aralkyl resin is represented by the following formula (2).

In formulas (1) and (2), the same symbols have the same meaning. Therefore, R ¹ , Ar ¹ , n, m and r in formula (2) are the same as those in formula (1).

The reaction between the naphthol aralkyl resin represented by the above formula (2) and the vinyl aromatic halomethyl compound is not particularly limited. For example, the alkali metal hydroxide is dehalogenated in a liquid phase such as a polar solvent. This is carried out by reacting using a hydrogen agent. In this reaction, the phenolic hydroxyl group of the naphthol aralkyl resin and the CH ₂ X group of the vinyl aromatic halomethyl compound undergo a condensation reaction to generate deHCl and O—CH ₂ bond, thereby producing a poly (vinylbenzyl) ether compound. To do.

In addition, for the purpose of improving toughness, moldability and dielectric properties, a part of the phenolic hydroxyl group of the naphthol aralkyl resin represented by the above formula (2) is converted into an acidic catalyst according to, for example, the method described in Japanese Patent No. 4465257. By reacting with an alcohol having 1 to 12 carbon atoms in the presence thereof, an alkyl group having 1 to 12 carbon atoms in R ² of the formula (1) can also be introduced. When an alkyl group is introduced, the ratio of the alkyl group in R ² of the formula (1) is preferably 1 to 30 mol%.

  The reaction for introducing the alkyl group may be before or after the reaction with the vinyl aromatic halomethyl compound, but in order to avoid polymerization of the vinyl group, the reaction is preferably performed. In the former case, a naphthol aralkyl resin in which a part of hydrogen atoms of the phenolic hydroxyl group is substituted with an alkyl group (hereinafter referred to as “partially modified naphthol aralkyl resin”) is synthesized first, and then vinyl aromatic. This is a method of obtaining a partially alkylated poly (vinylbenzyl) ether compound (hereinafter referred to as “partially modified poly (vinylbenzyl) ether compound”) by reacting with a halomethyl compound. In the latter case, a naphthol aralkyl resin and a vinyl aromatic halomethyl compound are reacted to obtain a poly (vinylbenzyl) ether compound, and then a part of the remaining hydrogen atoms of the phenolic hydroxyl group is alkylated. This is a method for obtaining a partially modified poly (vinylbenzyl) ether compound. Here, the partially modified poly (vinylbenzyl) ether compound is naturally included in the poly (vinylbenzyl) ether compound referred to in the present specification. Further, the partially modified naphthol aralkyl resin is included in the naphthol aralkyl resin referred to in this specification.

  In addition, as a part or all of the raw material of the naphthol aralkyl resin, a hydroxynaphthalene having a part or all of the hydrogen atom of the phenolic hydroxyl group as an alkyl group can be used. It can also be used in combination with hydroxynaphthalenes whose atoms are not alkylated.

  Also, the naphthol aralkyl resin may be a mixture of one in which all of the hydrogen atoms of the phenolic hydroxyl group are alkylated and one in which all of the hydrogen atoms of the phenolic hydroxyl group remain, which is also partially modified Naphthol aralkyl resin.

As the naphthol aralkyl resin represented by the above formula (2), in addition to the naphthol aralkyl resin obtained by the above reaction, a commercially available one can also be used. For example, SN170, SN180, SN190, SN475, SN485 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , SN495 and the like can be preferably used. More preferable are SN475, SN485, SN495, SN485V, and SN495V in terms of solubility, toughness, and flame retardancy. From the viewpoints of dielectric properties, toughness and formability, SN485V and SN495V are particularly preferable.
The naphthol aralkyl resin represented by the above formula (2) can also be produced by a known method. For example, JP-A-2001-213946, JP-A-11-255868, JP-A-11-228673, JP-A-08-073570, JP-A-08-048755, JP-A-10-310634. And JP-A-11-116647. The naphthol aralkyl resin represented by the above formula (2) may be used alone or in combination of two or more.

The vinyl aromatic halomethyl compound is represented by CH ₂ ═CH—Ar ² —CH ₂ X. Here, Ar ² is a phenylene group or a substituted phenylene group. Examples of the substituent in the case of a substituted phenylene group include an alkyl group, an alkoxy group, and a phenyl group. Preferably, an alkyl group having 1 to 6 carbon atoms is used. Ar ² is more preferably an unsubstituted, alkyl group-substituted, alkoxy group-substituted or phenyl group-substituted phenylene group from the viewpoints of solubility and flame retardancy. More preferred are unsubstituted and alkyl group-substituted phenylene groups, which are industrially easy to produce. Since this vinyl aromatic halomethyl compound provides a vinylbenzyl group of R ² , it is understood that the vinylbenzyl group may be a substituted vinylbenzyl group having a substituent on its benzene ring.

  Preferred vinyl aromatic halomethyl compounds include p-vinyl benzyl chloride, m-vinyl benzyl chloride, a mixture of p-vinyl benzyl chloride and m-vinyl benzyl chloride, p-vinyl benzyl bromide, m-vinyl benzyl bromide, p. A mixture of vinylbenzyl bromide and m-vinylbenzyl bromide can be mentioned. Among them, when a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride is used, a poly (vinylbenzyl) ether compound having excellent solubility is obtained, and compatibility with other materials and workability are good. Therefore, it is preferable. When a mixture of p-vinylbenzyl halide and m-vinylbenzyl halide is used, the composition ratio is not particularly limited, but p-form / m-form = 90/10 to 10/90 (mol / mol). It is preferably 70/30 to 30/70 (mol / mol), more preferably 60/40 to 40/60 (mol / mol).

  Next, the epoxy resin which has two or more epoxy groups in 1 molecule used as (B) component of this invention is demonstrated. As this epoxy resin, an epoxy resin (B1) having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin (B2) having two or more epoxy groups and a cyanurate structure in one molecule, or one molecule In addition, at least one epoxy resin (B3) having two or more epoxy groups and an alicyclic structure is used. The epoxy resin (B1) is also called an aromatic epoxy resin, the epoxy resin (B2) is also called a cyanurate epoxy resin, and the epoxy resin (B3) is also called an alicyclic epoxy resin. The alicyclic epoxy resin preferably has an alicyclic structure having 3 to 8 carbon atoms.

  Preferred examples of the epoxy resin having two or more epoxy groups in one molecule used as the component (B) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and alkylphenol novolac type epoxy resin. , Xylylene-modified phenol novolac type epoxy resin, xylylene-modified alkylphenol novolak type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, naphthalene Type epoxy resin, triglycidyl isocyanurate, cyclohexane type epoxy resin, adamantane type epoxy resin and the like. These epoxy resins may be used alone or in combination of two or more.

  Examples of the bisphenol F type epoxy resin include, for example, an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, and 4,4′-methylenebis (2,3,6). -Trimethylphenol) -based epoxy resin, and 4,4'-methylenebisphenol diglycidyl ether as the main component. Among them, an epoxy resin mainly composed of 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl ether is preferable. The bisphenol F-type epoxy resin is commercially available as a trade name YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

  Examples of the biphenyl type epoxy resin include epoxy resins such as 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl. As said biphenyl type epoxy resin, it can obtain as Mitsubishi Chemical Corporation brand name YX-4000, YL-6121H as a commercial item.

  Examples of the dicyclopentadiene type epoxy resin include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

  As naphthalene type epoxy resins, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene , And 1,2,5,6-tetraglycidylnaphthalene, naphthol / aralkyl epoxy resin, naphthalene skeleton modified cresol novolac epoxy resin, methoxynaphthalene modified cresol novolac epoxy resin, naphthylene ether epoxy resin, methoxynaphthalenedylene methylene Modified naphthalene type epoxy resins such as type epoxy resins.

  Examples of the adamantane type epoxy resin include 1- (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4-triglycidyloxyphenyl) adamantane, and 1,3-bis (2,4-diphenyl). Glycidyloxyphenyl) adamantane, 1,3-bis (2,3,4-triglycidyloxyphenyl) adamantane, 2,2-bis (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4) -Trihydroxyphenyl) adamantane, 1,3-bis (2,4-dihydroxyphenyl) adamantane, 1,3-bis (2,3,4-trihydroxyphenyl) adamantane, and 2,2-bis (2, 4-dihydroxyphenyl) adamantane and the like.

  Among the above epoxy resins, from the viewpoint of compatibility with the component (A), dielectric characteristics, and small warpage of the molded product, bisphenol F type epoxy resin, alkylphenol novolac type epoxy resin, xylylene modified phenol novolak type epoxy Resins, xylylene-modified alkylphenol novolac type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantene type epoxy resins are preferably used.

  The weight average molecular weight (Mw) of the epoxy resin used as the component (B) is preferably less than 10,000. More preferable Mw is 600 or less, and more preferably 200 or more and 550 or less. When Mw is less than 200, the volatility of the component (B) tends to be high, and the handleability of the cast film / sheet tends to deteriorate. On the other hand, if Mw exceeds 10,000, the cast film / sheet tends to be hard and brittle, and the adhesiveness of the cured product of the cast film / sheet tends to be lowered.

  As for content of (B) component, it is preferable that a minimum is 5 weight part and an upper limit is 100 weight part with respect to 100 weight part of (A) component. More preferably, the more preferable lower limit of the content of the component (B) is 10 parts by weight with respect to 100 parts by weight of the component (A). On the other hand, a more preferred upper limit is 80 parts by weight, and a still more preferred upper limit is 60 parts by weight. When content of (B) component satisfy | fills the said preferable minimum, the adhesiveness of the hardened | cured material of a cast film sheet can be improved further. When content of (B) component satisfy | fills the said preferable upper limit, the handleability of the cast film sheet in an uncured state will become still higher.

  Next, the curing agent used as the component (C) will be described. The curing agent for component (C) is not particularly limited as long as it cures the epoxy resin that is component (B). As the curing agent for component (C), only one type may be used, or two or more types may be used in combination.

  The curing agent of component (C) is preferably a phenol resin, or an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride. By using these preferable curing agents, it is possible to obtain a curable resin composition that becomes a cured product having an excellent balance of heat resistance, moisture resistance and electrical properties.

  The phenol resin used as the curing agent for the component (C) is not particularly limited. Specific examples of the phenol resin include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, phenol aralkyl resin, naphthol aralkyl resin, Biphenyl type phenol novolak resin, biphenyl type naphthol novolak resin, decalin modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, etc. Is mentioned. Especially, since the softness | flexibility and flame retardance of an insulating sheet can be improved further, the phenol resin which has a melamine skeleton, the phenol resin which has a triazine skeleton, or the phenol resin which has an allyl group is preferable.

  Commercially available products of the phenol resin include MEH-8005, MEH-8010 and NEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Japan Epoxy Resin Co., Ltd.), LA-7052, LA-7054, and LA-7751. LA-1356 and LA-3018-50P (all of which are manufactured by DIC), PS6313 and PS6492 (manufactured by Gunei Chemical Co., Ltd.), and the like.

  The structure of the acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride used as a curing agent for the component (C) is not particularly limited. Examples of the acid anhydride having an aromatic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, benzophenone tetracarboxylic acid anhydride, pyromellitic acid anhydride, Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride, etc. Is mentioned.

  Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (any of the above Is also manufactured by Sartomer Japan), ODPA-M and PEPA (all of which are manufactured by Manac), Rikagit MTA-10, Rikagit MTA-15, Rikagit TMTA, Rikagit TMEG-100, Rikagit TMEG-200, Rikagit TMEG-300, Rikagit TMEG-500, Rikagit TMEG-S, Rikagit TH, Rikagit HT-1A, Rikagit HH, Rikagit MH-700, Rikagit MT-500, Rikagit DSDA and Rikagit TDA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.), and PICLON B4400, EPICLON B650, and EPICLON B570 (all manufactured by both DIC Corporation).

  The acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. In this case, the flexibility, moisture resistance or adhesion of the insulating sheet can be further enhanced. Examples of the acid anhydride having the alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid. Examples of the modified product include anhydrides.

  Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include Rikagit HNA and Rikagit HNA-100 (all manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

  The curing agent used as the component (C) of the present invention includes o-cresol novolak, p-cresol novolak, and t-butylphenol novolak from the viewpoint of compatibility with (A) of the present invention, moisture resistance, and adhesiveness. , Dicyclopentadiene cresol, polyparavinylphenol, xylylene modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, methyl nadic An acid anhydride, trialkyltetrahydrophthalic anhydride, an acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride is more preferable.

  As the component (D), a high molecular weight resin having an Mw of 10,000 or more can be added to the curable resin composition of the present invention. The high molecular weight resin of component (D) is not particularly limited as long as Mw is 10,000 or more, and only one type may be used or two or more types may be used in combination.

  Specific examples of the component (D) include polyphenylene sulfide resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polybenzoxazole resin, Phenoxy resin, styrene resin, (meth) acrylic resin, polycyclopentadiene resin, polycycloolefin resin, polyether ether ketone resin, polyether ketone resin, or a known thermoplastic elastomer such as styrene-ethylene-propylene Copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene Isoprene copolymers and or gums such as polybutadiene, a high molecular weight resin such as polyisoprene could be used.

  Among these high molecular weight resins, those that are preferably used are polysulfone resins, polyether sulfone resins, polyphenylene ether resins, phenoxy resins from the viewpoint of compatibility with the component (A) of the present invention and adhesion reliability. , High molecular weight resins such as polycycloolefin resin, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer.

  (D) The minimum with a preferable glass transition temperature Tg of a component is -40 degreeC, a more preferable minimum is 50 degreeC, and a most preferable minimum is 90 degreeC. A preferable upper limit is 250 ° C., and a more preferable upper limit is 200 ° C. When Tg satisfies the above preferable lower limit, the resin is hardly thermally deteriorated, and when Tg satisfies the above preferable upper limit, the compatibility between the component (D) and another resin is increased. As a result, the handling property of the cast film / sheet in an uncured state and the heat resistance of the cured product of the cast film / sheet can be further enhanced.

  The preferable lower limit of Mw of the high molecular weight resin (D) is 20,000, the more preferable lower limit is 30,000, the preferable upper limit is 1,000,000, and the more preferable upper limit is 250,000. When Mw satisfies the preferable lower limit, the insulating sheet is hardly thermally deteriorated, and when the preferable upper limit is satisfied, the compatibility between the component (D) and another resin is increased. As a result, the handling property of the cast film / sheet in an uncured state and the heat resistance of the cured product of the cast film / sheet can be further enhanced.

  In the resin composition of the present invention, when the components (A) to (D) are included, the component (D) occupies the total 100% by weight of the total resin components (hereinafter sometimes abbreviated as the total resin component X). The content is preferably in the range of 10 to 60% by weight. The more preferable lower limit of the content of the component (D) in the total 100% by weight of all the resin components X is 20% by weight, and the more preferable upper limit is 50% by weight. When content of (D) component satisfy | fills the said preferable minimum, the handleability of the cast film sheet in an uncured state can be improved further. When content of (D) component satisfy | fills the said preferable upper limit, dispersion | distribution of the inorganic filler which is (F) component will become easy. The total resin component X refers to the sum of the components (A), (B), (C), (D) and other resin components added as necessary. Although the component which becomes a resin component after hardening, such as a hardening | curing agent, is calculated as a resin component, the inorganic filler of (F) component and the flame retardant of (G) component are not contained.

  The curable resin composition of the present invention may contain a radical polymerization initiator (also referred to as a radical polymerization catalyst) as the component (E) as desired, in addition to the above components. As the radical polymerization initiator, for example, as described later, the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like, but the reaction temperature at that time is lowered or the crosslinking reaction of unsaturated groups is performed. For the purpose of accelerating the reaction, a radical polymerization initiator may be contained. Since the radical polymerization initiator is a radical polymerization catalyst, it is represented below by a radical polymerization initiator.

  Typical examples of radical polymerization initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl- 2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di ( There are peroxides such as, but not limited to, trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst). However, the catalyst and radical polymerization initiator used for curing the resin composition are not limited to these examples.

  If the blending amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight with respect to the poly (vinylbenzyl) ether compound as component (A), the reaction proceeds well without inhibiting the curing reaction. To do.

  Moreover, you may mix | blend the other polymerizable monomer copolymerizable with the poly (vinyl benzyl) ether compound of (A) component in the curable resin composition of this invention as needed, and you may make it harden | cure.

  Examples of copolymerizable monomers include styrene, styrene dimer, alphamethyl styrene, alphamethyl styrene dimer, divinylbenzene, vinyl toluene, t-butyl styrene, chlorostyrene, dibromostyrene, vinyl naphthalene, vinyl biphenyl, acenaphthylene, divinyl. Examples thereof include benzyl ether and allyl phenyl ether.

  In addition, a curing accelerator may be added to the curable resin composition of the present invention in combination with the component (C) in order to adjust the curing speed or the physical properties of the cured product.

  The said hardening accelerator is not specifically limited. Specific examples of the curing accelerator include tertiary amines, imidazoles, imidazolines, triazines, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes such as organic acid salts, and the like. Examples of the curing accelerator include organometallic compounds, quaternary ammonium salts, metal halides, and the like. Examples of the organometallic compounds include zinc octylate, tin octylate and aluminum acetylacetone complex.

  Curing accelerators include high melting point imidazole curing accelerators, high melting point dispersion type latent curing accelerators, microcapsule type latent curing accelerators, amine salt type latent curing accelerators, and high temperature dissociation type and thermal cationic polymerization. A mold latent curing accelerator or the like can also be used. As for a hardening accelerator, only 1 type may be used and 2 or more types may be used together.

  Examples of the high melting point dispersion type latent accelerator include dicyandiamide and amine addition type accelerators in which an amine is added to an epoxy monomer or the like. Examples of the microcapsule type latent accelerator include a microcapsule type latent accelerator in which the surface of an imidazole, phosphorus or phosphine accelerator is coated with a polymer. Examples of the high temperature dissociation type and thermal cationic polymerization type latent curing accelerator include Lewis acid salt or Bronsted acid salt.

  The curing accelerator is preferably an organophosphorus compound and a high melting point imidazole curing accelerator. By using organophosphorus compounds and high melting point imidazole curing accelerators, the reaction system can be easily controlled, and the curing speed of cast films and sheets and the physical properties of the cured products of cast films and sheets are further improved. Easy to adjust. A high-melting-point curing accelerator having a melting point of 100 ° C. or higher is excellent in handleability. Accordingly, the melting accelerator preferably has a melting point of 100 ° C. or higher.

  In the total 100% by weight of all the resin components X, the content of the component (C) has a preferable lower limit of 1% by weight and a preferable upper limit of 40% by weight. A more preferred lower limit is 5% by weight, and a more preferred upper limit is 25% by weight. When the content of the component (C) satisfies the above preferable lower limit, it becomes easy to sufficiently cure the cast film and sheet, and when the preferable upper limit is satisfied, it becomes difficult to generate an excessive curing agent not involved in curing, Crosslinking of the cured product can be sufficiently advanced. For this reason, the heat resistance and adhesiveness of the hardened | cured material of a cast film sheet can be improved further.

  In the curable resin composition of the present invention, an inorganic filler may be added as the component (F) in order to further reduce the thermal expansion coefficient of the insulating layer obtained from the curable resin composition. Examples of the component (F) include silica, alumina, barium sulfate, talc, creni, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and barium tetanate. Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, etc. Is particularly preferred. The silica is preferably spherical.

  (F) You may use the inorganic filler of a component in combination of 2 or more types. The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.7 μm or less from the viewpoint of forming fine wiring on the insulating layer. In addition, when the average particle size of the component (F) becomes too small, when the curable resin composition of the present invention is used as a resin varnish, the viscosity of the varnish tends to increase and the handleability tends to decrease. The particle size is preferably 0.05 μm or more. The average particle diameter of the component (F) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the component (F) on a volume basis with a laser diffraction particle size distribution measuring device and setting the median diameter as an average particle size. As the measurement sample, one obtained by dispersing the component (F) in water by ultrasonic waves can be preferably used. As a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

  The inorganic filler of component (F) is preferably one that has been surface treated with a surface treatment agent such as an epoxy silane coupling agent, an amino silane coupling agent, or a titanate coupling agent to improve its moisture resistance. The amount of component (F) added is preferably in the range of 20 to 400 parts by weight, more preferably in the range of 30 to 350 parts by weight, and 40 to 300 parts by weight with respect to 100 parts by weight of the nonvolatile content of the curable resin composition. The range of is more preferable. When content of (F) component exceeds 400 mass parts, it exists in the tendency for hardened | cured material to become weak and for the peel strength to fall. On the other hand, when the content of the component (F) is less than 20 parts by mass, the coefficient of thermal expansion does not sufficiently decrease.

  In the curable resin composition of this invention, you may contain a flame retardant as (G) component in the range which does not impair the effect of this invention. Examples of the flame retardant of component (G) include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. Examples of organophosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd. Leophos 30, 50, 65, 90, 110, Fine Techno Co., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ made by Hokuko Chemical Co., Ltd., Clariant ( Phosphoric acid ester compounds such as OP930 made by Daihachi Chemical Co., Ltd., PX200 made by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 made by Toto Kasei Co., Ltd., phosphorus such as ERF001 made by Toto Kasei Co., Ltd. And a phosphorus-containing epoxy resin such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd. Examples of organic nitrogen-containing phosphorus compounds include phosphoric ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPEl00 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Manufacturing Co., Ltd. Examples thereof include phosphazene compounds. As metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 etc. made by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308, B made by Sakai Kogyo Co., Ltd. -303, UFH-20 and other aluminum hydroxides.

  The curable resin composition of the present invention can be used as a varnish for circuit board materials. The varnish for circuit board material of the present invention can be produced by dissolving the curable resin composition of the present invention in a solvent such as toluene, xylene, tetrahydrofuran, dioxolane and the like. The circuit board material of the present invention is manufactured using the cured product, composite material cured product or laminate of the present invention. Specifically, a printed wiring board, a printed circuit board, a flexible printed wiring board, a build-up wiring board, etc. are mentioned.

  The cured product obtained by curing the curable resin composition of the present invention can be used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film. For example, the cured product of the semiconductor sealing material is a cast product or a molded product. As a method for obtaining a cured product for such use, a curable resin composition is cast, a transfer molding machine, an injection molding machine, or the like. The cured product can be obtained by molding at 80 to 230 ° C. for 0.5 to 10 hours. Further, the cured product of the circuit board varnish is advantageously a laminate. As a method of obtaining this cured product, the circuit board varnish is made of glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper It can be obtained by impregnating a base material such as the above to obtain a prepreg by heating and laminating them with each other or with a metal foil such as a copper foil and hot pressing.

  Further, it is useful as a material for electronic parts, particularly as a high frequency electronic part material, by blending inorganic high dielectric powder such as barium titanate or inorganic magnetic substance such as ferrite.

  Moreover, the curable resin composition of this invention can be used together with metal foil (it is the meaning containing a metal plate. The following is the same) similarly to the hardening composite material mentioned later.

  Next, the curable composite material of the curable resin composition of the present invention and the cured product thereof will be described. A base material is added to the curable composite material of the curable resin composition of the present invention in order to increase mechanical strength and increase dimensional stability.

  Such base materials include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth, wholly aromatic polyamide fiber, wholly aromatic Woven or non-woven fabrics obtained from liquid crystal fibers such as polyester fibers and polybenzoxal fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers and acrylic fibers, and natural fiber fabrics such as cotton cloth, linen cloth and felt. , Carbon fiber cloth, kraft paper, cotton paper, cloth such as natural cellulosic cloth such as paper-glass mixed paper, paper, etc. are used singly or in combination of two or more.

The proportion of the substrate is 5 to 90 wt%, preferably 10 to 80 wt%, more preferably 20 to 70 wt% in the curable composite material. When the base material is less than 5 wt%, the dimensional stability and strength after curing of the composite material tend to decrease. Further, when the substrate content exceeds 90 wt%, the dielectric properties of the composite material tend to be lowered.
In the curable composite material of the present invention, a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate, if necessary. As the coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent can be used.

  As a method for producing the curable composite material of the present invention, for example, the curable resin composition of the present invention and, if necessary, other components in the above-mentioned aromatic or ketone solvent or a mixed solvent thereof. A method of uniformly dissolving or dispersing, impregnating the base material, and then drying is exemplified. Impregnation is performed by dipping or coating. The impregnation can be repeated multiple times as necessary, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.

  A cured product of the composite material is obtained by curing the curable composite material of the present invention by a method such as heating. The production method is not particularly limited. For example, a plurality of curable composite materials are stacked, and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed to obtain a cured composite material having a desired thickness. Can do. It is also possible to obtain a composite material cured product having a new layer structure by combining the cured composite material once bonded and cured and the curable composite material. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

Molding and curing are performed at a temperature of 80 to 300 ° C., a pressure of 0.1 to 1000 kg / cm ² , a time of 1 minute to 10 hours, and more preferably a temperature of 150 to 250 ° C. and a pressure of 1 to 500 kg / cm. ^2. Time: 1 minute to 5 hours.

  The laminate of the present invention is composed of a layer of the composite material cured product of the present invention and a metal foil layer. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

  As a method for producing the laminate of the present invention, for example, the curable composite composition of the present invention described above and a curable composite material obtained from a base material, and a metal foil are laminated in a layer configuration according to the purpose, An example is a method in which the respective layers are bonded under heat and pressure, and at the same time, thermally cured. In the laminate of the curable resin composition of the present invention, the composite material cured product and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as a surface layer or an intermediate layer. In addition to the above, it is possible to make a multilayer by repeating lamination and curing a plurality of times.

  An adhesive can also be used for adhesion to the metal foil. Examples of the adhesive include, but are not limited to, epoxy, acrylic, phenol, and cyanoacrylate. The above lamination molding and curing can be performed under the same conditions as in the production of the cured composite material cured product of the present invention.

Moreover, the curable resin composition of this invention can also be shape | molded in a film form. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.
The method for producing the film is not particularly limited. For example, the curable resin composition and other components as required are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof. And a method of drying after applying to a resin film such as a PET film. The application can be repeated multiple times as necessary. In this case, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally the desired resin composition and resin amount can be adjusted. It is.

  The metal foil with resin of the present invention is composed of the curable resin composition of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

  The method for producing the resin-coated metal foil of the present invention is not particularly limited. For example, the curable resin composition and other components as necessary in an aromatic or ketone solvent or a mixed solvent thereof. And a method of uniformly dissolving or dispersing in a metal foil, applying to a metal foil, and drying. The application can be repeated a plurality of times as necessary. At this time, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited by these. In addition, all the parts in each example are parts by weight. In addition, the measurement results in the examples are those obtained by sample preparation and measurement by the following methods.

1) Molecular weight and molecular weight distribution of poly (vinyl benzyl) ether compound Molecular weight and molecular weight distribution measurement uses GPC (manufactured by Tosoh Corporation, HLC-8120GPC), solvent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, column temperature. : Performed at 40 ° C. The molecular weight was measured as a polystyrene-converted molecular weight using a calibration curve of monodisperse polystyrene.

2) Structure of poly (vinylbenzyl) ether compound The structure was determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d ₁ was used as a solvent. The resonance line of tetrachloroethane -d ₂ is an NMR measurement solvent was used as an internal standard.

3) Linear expansion coefficient, glass transition temperature (Tg) and softening temperature measurement After the curable resin composition solution was uniformly applied to a glass substrate so that the thickness after drying was 20 μm, using a hot plate, Heated at 90 ° C. for 30 minutes and dried. The obtained resin film on the glass substrate is set in a TMA (thermomechanical analyzer) measuring device together with the glass substrate, heated to 220 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream, and further 220 ° C. The remaining solvent was removed by heat treatment for 20 minutes. After allowing the glass substrate to cool to room temperature, the measurement probe is brought into contact with the sample in the TMA measuring apparatus, and measurement is performed by scanning from 30 ° C. to 360 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream. The softening temperature was determined by the tangential method. Further, Tg was determined from the inflection point at which the linear expansion coefficient changes. Furthermore, the average linear expansion coefficient (CTE) was calculated from the dimensional change of the test piece at 0 to 40 ° C.
The Tg of the cured film obtained by hot press molding was measured using a dynamic viscoelasticity measuring device at a temperature rising rate of 2 ° C./min, and determined from the peak of the loss elastic modulus.

4) Tensile strength and elongation rate The tensile strength and elongation rate of the cured film were measured using a tensile test apparatus. The elongation was measured from a tensile test chart.
5) Dielectric constant and dielectric loss tangent In accordance with the JIS C2565 standard, cured after being stored in a room at 23 ° C. and 50% humidity for 24 hours using a cavity resonator method dielectric constant measuring device manufactured by AET Co., Ltd. The dielectric constant and dielectric loss tangent of the physical film at 2 GHz were measured.
Moreover, after leaving the cured film for 60 minutes at 200 ° C., the dielectric constant and dielectric loss tangent were measured, and the dielectric constant and dielectric loss tangent after the heat resistance test were measured.
6) Copper foil peel strength A curable resin composition varnish was applied onto the copper foil, the solvent was removed at 80 ° C., and after drying, a resin-coated copper foil was obtained. And the laminated board which removed the copper foil from the copper clad laminated board by etching, and the copper foil with the resin coated with the curable resin composition varnish were laminated using a pressure vacuum press molding machine, and the laminated body cured product It was created. A test piece having a width of 20 mm and a length of 100 mm was cut out from the cured laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then continuously at a speed of 50 mm / min in the direction of 90 ° with respect to the surface. The copper foil was peeled off, the stress at that time was measured with a tensile tester, and the minimum value of the stress was recorded as the copper foil peel strength. (Conforms to JIS C 6481).
The copper foil peel strength test after the wet heat resistance test was measured in the same manner as described above after the test piece was left at 85 ° C. and a relative humidity of 85% for 500 hours.
7) Formability An uncured film of a curable resin composition is laminated on a blackened copper-clad laminate, and vacuum is applied at a temperature of 110 ° C. and a press pressure of 0.1 MPa using a vacuum laminator. Lamination was performed, and evaluation was performed based on the adhesion state between the blackened copper foil and the film. Evaluation was evaluated as “◯” when the adhesion state of the blackened copper foil and the film was good, and “x” when the blackened copper foil and the film could be easily peeled off. .

Synthesis example 1
In a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel, SN495V (Naphthol aralkyl resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; OH equivalent of 232 g / eq of phenolic hydroxyl group, methoxy modification amount of phenolic hydroxyl group: 2.7%, methoxy group content derived from p-xylylene glycol dimethyl ether: ND) 195 parts (1.0 equivalent), CMS-AM (chloromethylstyrene manufactured by Seimi Chemical Co.) 160.1 parts (1 .05 equivalents), 9.6 parts of tetra-n-butylammonium bromide, 0.152 parts of 2,4-dinitrophenol, and 255 parts of methyl ethyl ketone were charged and dissolved by stirring, the liquid temperature was adjusted to 75 ° C., and 50% aqueous sodium hydroxide solution was added. 160 parts (2.0 equivalents) was added dropwise over 20 minutes, and stirring was further continued at 75 ° C. for 4 hours. Next, after neutralizing the inside of the flask with a 10% hydrochloric acid aqueous solution, 400 parts of toluene was added, and the organic layer was washed with 1500 ml of water three times.

  By distilling the obtained organic phase, the organic phase was concentrated to 500 parts, and 1,000 parts of methanol / water = 75/25 (vol / vol) was added to reprecipitate the product. Reprecipitation under the same conditions was repeated twice more. The obtained resin precipitate was filtered and dried to obtain 246.7 parts of vinylbenzylated naphthol aralkyl resin (VBE-SN495V) as a poly (vinylbenzyl) ether compound which is a reaction product of SN495V and vinylbenzyl chloride. It was.

When the product was confirmed by GPC, infrared spectrum (IR), 1H nuclear magnetic resonance spectrum ( ¹ H-NMR), in the reaction product recovered from GPC, the peak derived from the raw material disappeared, and the high molecular weight A new peak is formed on the side, the phenolic hydroxyl group disappears from IR, and the resonance line of the proton derived from chloromethylstyrene disappears in ¹ H-NMR, instead, around 5.02 ppm It is confirmed that the proton resonance line derived from the benzyl ether group has proton resonance lines derived from the vinyl group in the vicinity of 5.25 ppm, 5.77 ppm and 6.73 ppm, and VBE-SN495V is obtained. It was confirmed. The methoxy group content was 2.6%, the vinylbenzyl ether group content was 97.4%, and no phenolic hydroxyl group could be detected. The total chlorine content measured by elemental analysis was 167 ppm. When GC measurement was performed, no peak derived from chloromethylstyrene was observed. Further, when the thermal phase transition behavior was measured with a differential scanning calorimeter (DSC) under a nitrogen stream at a rate of temperature increase of 10 ° C./min, no melting peak derived from the crystals was observed. Further, when a thermal decomposition behavior was measured using a thermobalance (TGA) under a nitrogen stream at a heating rate of 10 ° C./min, the thermal decomposition starting temperature by the tangential method was 405.7 ° C. and 600 ° C. The amount of carbide produced in was 37.8 wt%.

Synthesis example 2
In a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel, SN475N (Naphthol aralkyl resin made by Nippon Steel & Sumikin Chemical; hydroxyl equivalent of 218 g / eq of phenolic hydroxyl group, methoxy modification amount of phenolic hydroxyl group: N D., methoxy group content derived from p-xylylene glycol dimethyl ether: ND) 195 parts (1.0 equivalent), CMS-AM (vinyl benzyl chloride manufactured by Seimi Chemical Co.) 160.1 parts (1. 05 equivalents), 9.6 parts of tetra-n-butylammonium bromide, 0.152 parts of 2,4-dinitrophenol and 255 parts of methyl ethyl ketone were charged and dissolved by stirring, the liquid temperature was brought to 75 ° C., and a 50% aqueous sodium hydroxide solution 160 was added. Part (2.0 equivalents) was added dropwise over 20 minutes, and stirring was further continued at 75 ° C. for 4 hours. Next, after neutralizing the inside of the flask with a 10% hydrochloric acid aqueous solution, 400 parts of toluene was added, and the organic layer was washed with 1500 ml of water three times.

  By distilling the obtained organic phase, the organic phase was concentrated to 500 parts, and 1,000 parts of methanol / water = 75/25 (vol / vol) was added to reprecipitate the product. Reprecipitation under the same conditions was repeated twice more. The resulting resin precipitate was filtered and dried to obtain 223.5 parts of vinylbenzylated naphthol aralkyl resin (VBE-SN475N) which is a reaction product of SN475N and vinylbenzyl chloride.

When the product was confirmed, in the reaction product recovered from GPC, the peak derived from the raw material disappeared, a new peak was formed on the high molecular weight side, and the phenolic hydroxyl group disappeared from IR. ¹ H-NMR, the proton resonance line derived from chloromethylstyrene disappeared, and instead, the proton resonance line derived from the benzyl ether group around 5.02 ppm, 5.25 ppm, 5.77 ppm and It was confirmed to have a proton resonance line derived from a vinyl group in the vicinity of 6.73 ppm, and it was confirmed that VBE-SN475N was obtained. The vinylbenzyl ether group content was 99.5% or more, while no methoxy group or phenolic hydroxyl group in which the phenolic hydroxyl group of 1-naphthol was modified could be detected. The total chlorine content measured by elemental analysis was 178 ppm. As a result of GC measurement, the content of chloromethylstyrene was 0.02%. Further, when the thermal phase transition behavior was measured with a differential scanning calorimeter (DSC) under a nitrogen stream at a rate of temperature increase of 10 ° C./min, no melting peak derived from the crystals was observed. Further, when a thermal decomposition behavior was measured using a thermobalance (TGA) under a nitrogen stream at a heating rate of 10 ° C./min, the thermal decomposition starting temperature by the tangential method was 412.0 ° C. and 600 ° C. The amount of carbide produced in was 40.1 wt%.

Synthesis example 3
While purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas purge, 414 parts of phenol, 251 parts of 4,4′-bis (chloromethyl) -1,1′-biphenyl, p-toluenesulfonic acid 13 The portion was charged and heated up to 80 ° C. with stirring to be dissolved. After stirring for 4 hours, 700 parts of methyl isobutyl ketone was added and then washed three times with 300 parts of water until the washing water became neutral. Then, unreacted phenol and methyl isobutyl ketone were removed from the oil layer under a pressure of 1.3 kPa. In the formula (2), 310 parts of a phenol aralkyl resin (P) in which R ¹ is a hydrogen atom and n is 1.5 was obtained. The obtained phenol aralkyl resin had a softening point of 65 ° C. and a hydroxyl group equivalent of 202 g / eq.

  While purging a flask equipped with a thermometer, condenser, and stirrer with nitrogen gas purge, 404 parts of the obtained phenol aralkyl resin (P), 848 parts of methyl ethyl ketone, 320 parts of 4-vinylbenzyl chloride, tetra-n-butyl 12 parts of ammonium bromide was added and dissolved by stirring to bring the liquid temperature to 70 ° C. Thereto, 320 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and stirring was further continued at 70 ° C. for 6 hours. Next, after neutralizing the flask contents with 35% hydrochloric acid, liquid separation was performed, and the organic layer was washed three times with 400 parts of water, and unreacted raw materials and methyl ethyl ketone were distilled off under reduced pressure to give phenol containing a biphenyl structure. 512 parts of poly (vinylbenzyl) ether compound (VB1) having an n of 1.5, in which the aralkyl resin was converted to vinylbenzyl ether were obtained. The resulting poly (vinylbenzyl) ether compound had a softening point of 54 ° C., and as a result of infrared absorption spectrum measurement, absorption due to the phenolic hydroxyl group of the raw material disappeared. The total chlorine content measured by elemental analysis was 980 ppm. When GC measurement was performed, the content of chloromethylstyrene was 0.58%. Further, when the thermal phase transition behavior was measured with a differential scanning calorimeter (DSC) under a nitrogen stream at a rate of temperature increase of 10 ° C./min, no melting peak derived from the crystals was observed. Further, when a thermal decomposition behavior was measured using a thermobalance (TGA) at a rate of temperature increase of 10 ° C./min under a nitrogen stream, the thermal decomposition starting temperature by the tangential method was 376 ° C., and the carbide at 600 ° C. The production amount was 31.8 wt%.

Abbreviations are as follows:
YDCN-700-3: Cresol novolak type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototo YDCN-700-3)
MEH-7851-S: Biphenyl type phenol novolac resin (Maywa Kasei Co., Ltd., MEH-7851-S)
ESN-475V: Naphthol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., ESN-475V, epoxy equivalent 340, solid content 65 wt% MEK solution)
Epicoat 828US: Bisphenol A type liquid epoxy resin (Japan Epoxy Resin, Epicoat 828US, Mw = 370)
Oncoat EX1011: Fluorene skeleton epoxy resin (Osaka Gas Chemical Co., Ltd., Oncoat EX1011, Mw = 486)
PS-6492; Melamine skeleton phenol resin (manufactured by Gunei Chemical Industry Co., Ltd., PS-6492)
YL7553BH30: Phenoxy resin (weight average molecular weight 37000, manufactured by Mitsubishi Chemical Corporation, YL7553BH30, a 1: 1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass)
A1535: Hydrogenated styrene butadiene block copolymer (manufactured by Kraton Polymer Japan, KRATON A1535, Mw = 223,000)
Park mill D: Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D)
Park Mill P: Diisopropylbenzene hydroperoxide (Nippon, Park Mill P)
AO-60: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adeka Co., Ltd., Adeka Stub AO-60)
SE2050 SPE: Amorphous spherical silica treated with phenylsilane coupling agent (manufactured by Admatechs, SE2050 SPE, average particle size 0.5 μm)

Example 1
80 g of VBE-SN495V obtained in Synthesis Example 1, 10 g of YDCN-7 as an epoxy resin, 10 g of MEH-7851-S as a phenol resin, 1.0 g of Parkmill D as a polymerization initiator, and triphenylphosphine ( 0.4 g of TPP) and 0.2 g of AO-60 as an antioxidant were dissolved in 43.5 g of toluene to obtain a curable resin composition (varnish A).

  The prepared varnish A is dropped on a mold, the solvent is removed by devolatilization at 80 ° C. under reduced pressure, and after drying, the mold is assembled, and then subjected to a vacuum press for 1 hour at 180 ° C. and 3 MPa. The cured sheet having a thickness of 0.2 mm obtained by thermosetting was measured for various properties including a dielectric constant of 2.0 GHz and a dielectric loss tangent. Further, the dielectric constant and dielectric loss tangent after being left in an oven at 200 ° C. for 1 hour were measured, and the change rate of the dielectric constant and dielectric loss tangent before and after being left was measured. The results obtained from these measurements are shown in Table 1.

Comparative Example 1
80 g of VB1 obtained in Synthesis Example 3, 10 g of YDCN-700-3 as an epoxy resin, 10 g of MEH-7851-S as a phenol resin, 1.0 g of Parkmill D as a polymerization initiator, and 0.4 g of TPP as a curing accelerator As a antioxidant, 0.2 g of AO-60 was dissolved in 43.5 g of toluene to obtain a curable resin composition (varnish B).

  The prepared varnish B was dropped onto the mold, the solvent was removed by devolatilization at 80 ° C. under reduced pressure, and after drying, the mold was assembled and then subjected to a vacuum pressure press at 180 ° C. and 3 MPa for 1 hour. The cured sheet having a thickness of 0.2 mm obtained by thermosetting was measured for various properties including a dielectric constant of 2.0 GHz and a dielectric loss tangent. Further, the dielectric constant and dielectric loss tangent after being left in an oven at 200 ° C. for 1 hour were measured, and the change rate of the dielectric constant and dielectric loss tangent before and after being left was measured. The results obtained from these measurements are shown in Table 1.

Example 2
60 g of VBE-SN475N obtained in Synthesis Example 2, 10 g of YDCN-700-3 as an epoxy resin, 10 g of MEH-7851-S as a phenol resin, and a hydrogenated styrene butadiene block copolymer (Clayton Polymer Japan ( Co., Ltd., trade name: KRATON A1535, Mw = 223,000) 20 g, Parkmill D 1.0 g as a polymerization initiator, TPP 0.4 g as a curing accelerator, AO-60 0.2 g as an antioxidant xylene 82 Dissolved in 0.8 g, a curable resin composition (varnish C) was obtained.

  The prepared varnish C was applied onto a PET film, the solvent was removed at 80 ° C., the coating film was peeled off from the PET film after drying, and the isolated cast film was vacuum-pressed for 1 hour under the conditions of 180 ° C. and 3 MPa. And thermosetting, and various properties of the obtained cured film were measured. Further, a 0.2 mm thick film press cured product was cut into 0.3 cm × 10 cm to prepare a test piece, and a dielectric constant and dielectric loss tangent of 2.0 GHz were measured. Further, the dielectric constant and dielectric loss tangent after being left in an oven at 200 ° C. for 1 hour were measured, and the change rate of the dielectric constant and dielectric loss tangent before and after being left was measured.

Separately, varnish C was coated on the copper foil, the solvent was removed at 80 ° C., and after drying, a resin-coated copper foil was obtained. From this resin-coated copper foil, a test piece was cut out under the conditions described in the measurement of copper foil peel strength, and the copper foil peel strength was measured. Moreover, the copper foil peeling strength after a wet heat resistance test was measured.
Furthermore, the cast film was laminated on the copper-clad laminate subjected to the blackening treatment, and the moldability was evaluated.
The results obtained by these measurements are shown in Table 2.

Comparative Example 2
YBCN-700-3 10 g as VB1 30 g epoxy resin obtained in Synthesis Example 3, 10 g MEH-7851-S as phenol resin, 20 g A1535 as thermoplastic elastomer, 1.0 g Parkrim D as polymerization initiator, curing accelerator As above, 0.4 g of TPP and 0.2 g of AO-60 as an antioxidant were dissolved in 82.8 g of xylene to obtain a curable resin composition (varnish D).

  The solution viscosity of the prepared varnish D was measured using an E-type viscometer. The prepared varnish D is applied onto a PET film, the solvent is removed at 80 ° C., the coating film is peeled off from the PET film after drying, and the isolated cast film is pressed under vacuum at 180 ° C. and 3 MPa for 1 hour. The cured film thus obtained was subjected to heat treatment, and various properties were measured in the same manner as in Example 2. The results are shown in Table 2.

Example 3
A glass cloth (E glass, basis weight 71 g / m ² ) was immersed in the varnish C obtained in Example 2 for impregnation, and dried in an air oven at 50 ° C. for 30 minutes. The resin content (RC) of the obtained prepreg was 52%.
Using this prepreg, when a core material having a thickness of 0.8 mm in which through holes having a diameter of 0.35 mm were arranged at a pitch of 5 mm was bonded, the number of through holes not filled with resin was 0 out of 4500 holes. .

A plurality of the above curable composite materials are stacked as necessary so that the thickness after molding becomes approximately 0.6 mm to 1.0 mm, and a copper foil having a thickness of 18 μm is placed on both sides thereof by a press molding machine. Molded and cured to obtain a laminate. The curing condition of each example was to raise the temperature at 3 ° C./min and hold at 180 ° C. for 60 minutes. The pressure was 30 kg / cm ^{2 in} all cases.

Various physical properties of the laminate thus obtained were measured by the following methods.
1) Trichlorethylene resistance: The laminate from which the copper foil had been removed was cut into 25 mm squares, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed (based on JIS C6481).
2) Solder heat resistance: The laminate from which the copper foil had been removed was cut into 25 mm squares, floated in a 260 ° C. solder bath for 120 seconds, and the change in appearance was visually observed (conforms to JIS C6481).

  In the trichlorethylene resistance test, no change was observed in the appearance of the laminate. In the solder heat resistance test, no change was observed in the appearance of the laminate.

Example 4
Varnish C obtained in Example 2 was applied onto an 18 μm electrolytic copper foil, air-dried for 10 minutes, and then dried in an air oven at 80 ° C. for 10 minutes. The resin thickness on the copper foil was 50 μm. The copper foil with resin and the laminate of Example 5 were stacked and cured by heating and pressing at 180 ° C. for 90 minutes at a pressure of 30 kg / cm ² . When through holes were observed, no through holes that were not filled with resin were confirmed.

Examples 5-10
The test was performed under the same conditions as in Example 2 except that the varnish was prepared with the formulation shown in Table 3. The results obtained from the tests are shown in Table 3.
In Table 3, the blending amount of the blending component is wt% when no unit is described.

Claims (19)

(A) component: The following formula (1) obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound

(Here, R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 10 carbon atoms, and Ar ¹ is a divalent divalent having 6 to 50 carbon atoms. Represents an aromatic hydrocarbon group, and each R ² independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group, and the ratio of the vinylbenzyl group in R ² is 60 to 100 mol%. N is an average value ranging from 1 to 20, m is a number from 1 to 6, and r is a number from 1 to 3, provided that m + r does not exceed 6 or 7.
A poly (vinylbenzyl) ether compound represented by:
Component (B): an epoxy resin having two or more epoxy groups and an aromatic structure in one molecule, an epoxy resin having two or more epoxy groups and a cyanurate structure in one molecule, and / or two or more epoxies in one molecule An epoxy resin having a group and an alicyclic structure, and (C) component: containing a curing agent, and containing 5 to 100 parts by weight of (B) component with respect to 100 parts by weight of (A) component. Curable resin composition.



  Furthermore, the high molecular weight resin whose weight average molecular weight is 10,000 or more is contained as (D) component, The curable resin composition of Claim 1 characterized by the above-mentioned.   Furthermore, a radical polymerization initiator is contained as (E) component, The curable resin composition of Claim 1 or Claim 2 characterized by the above-mentioned.   Furthermore, an inorganic filler is contained as (F) component, The curable resin composition in any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, a flame retardant is contained as (G) component, The curable resin composition in any one of Claims 1-4 characterized by the above-mentioned.   The varnish for circuit board materials formed by dissolving the curable resin composition in any one of Claims 1-5 in a solvent.   Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-5.   A curable composite material comprising the curable resin composition according to claim 1 and a substrate.   A cured composite material obtained by curing the curable composite material according to claim 8.   A laminate comprising the composite material cured product layer according to claim 9 and a metal foil layer.   A metal foil with a resin, comprising a film formed from the curable resin composition according to claim 1 on one side of the metal foil.   A circuit board material using the cured product according to claim 7.   A circuit board material using the cured composite material according to claim 9.   A circuit board material using the laminate according to claim 10.   The total of the component (A), the total halogen content being 600 ppm (wt) or less, and the peak area of the vinyl aromatic halomethyl compound summed with the peak area of the poly (vinylbenzyl) ether compound in gas chromatography (GC) measurement It is 1.0% or less with respect to a peak area, The curable resin composition in any one of Claims 1-5. The curable resin composition according to any one of claims 1 to 5, wherein a part of R ² in the formula (1) is an alkyl group having 1 to 12 carbon atoms.   The component (B) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolak type epoxy resin, xylylene modified phenol novolak type epoxy resin, xylylene modified alkylphenol novolak type epoxy resin, biphenyl type epoxy. It is one or more epoxy resins selected from the group consisting of resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, triglycidyl isocyanurate, cyclohexane type epoxy resins and adamantane type epoxy resins. The curable resin composition described in 1.   The component (C) is o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, phenol aralkyl resin, naphthol aralkyl resin, biphenyl type phenol novolak resin, biphenyl type naphthol novolak. Resins, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride and dicyclo The curable resin composition according to any one of claims 1 to 5, which is at least one epoxy resin curing agent selected from the group consisting of an acid anhydride having a pentadiene skeleton and a modified product of the acid anhydride.   The component (D) is selected from the group consisting of polysulfone resins, polyether sulfone resins, polyphenylene ether resins, phenoxy resins, polycycloolefin resins, hydrogenated styrene-butadiene copolymers and hydrogenated styrene-isoprene copolymers. It is 1 or more types of high molecular weight resin, The curable resin composition in any one of Claims 2-5.