TW201800437A - Poly(vinylbenzyl)ether compound, curable resin composition containing this and cured article - Google Patents

Abstract

To provide a resin material that satisfies a low dielectric tangent after severe thermal hysteresis, and combines heat resistance, fire retardancy, adhesion reliability and workability, and crack resistance, and a circuit board material therewith. A poly(vinylbenzyl)ether compound represented by the following formula (1), and a curing resin composition obtained by blending the poly(vinylbenzyl)ether compound and a polyfunctional epoxy resin. In the formula (1), Rrepresents 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, Arrepresents a divalent aromatic hydrocarbon group having 6 to 50 carbon atoms, Rrepresents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group, but a ratio of the vinylbenzyl group in the Ris 10 mol% or more and less than 60 mol%, and a ratio of hydrogen atoms is 40 mol% or more.

Description

Poly (vinylbenzyl) ether compound, curable resin composition containing the same, and cured product

The present invention relates to a poly (vinylbenzyl) ether compound, a curable resin composition containing a poly (vinylbenzyl) ether compound and an epoxy resin, a varnish for a circuit board material, a cured product, and a composite material containing the same A laminate of a cured product and a metal foil, a metal foil with a resin, and a circuit board material.

With the increase in the amount of information communication in recent years, information communication in the high-frequency band has begun actively. In order to have better electrical characteristics, in order to reduce transmission loss in the high-frequency band, a low-dielectric constant and Electrical insulation material with low dielectric tangent and small change in dielectric properties after being subjected to a particularly severe thermal history. Furthermore, printed circuit boards or electronic components using these electrical insulating materials are exposed to high-temperature reflow soldering during mounting. Therefore, a material having high heat resistance and flame retardancy, that is, exhibiting a high glass transition temperature is desired. In particular, recently, lead-free solder having a high melting point has been used due to environmental problems, and thus electrical insulation materials having higher heat resistance are becoming more demanding. To meet these requirements, a curable resin composition containing a vinyl benzyl ether compound having various chemical structures has been proposed.

As such a curable resin composition, for example, there is proposed a curable resin composition containing a polyphenol obtained by reacting a phenol aralkyl resin obtained by condensation with a biphenyl compound and a vinyl benzyl halide. (Vinyl benzyl) ether compound (Patent Document 1). However, the poly (vinylbenzyl) ether compounds disclosed in the aforementioned patent documents not only fail to obtain sufficient characteristics in terms of initial dielectric characteristics, but also have large changes in dielectric characteristics with respect to severe thermal history and heat resistance. 2. The flame retardancy is not sufficient.

As poly (vinylbenzyl) ether compounds, several poly (vinylbenzyl) ether compounds having specific structures have been proposed, and attempts have been made to suppress the change in dielectric tangent when subjected to severe thermal history, or to improve Attempts to heat resistance and flame retardance, but the improvement of characteristics is still not enough, and further improvement of characteristics is expected. Therefore, the mounting materials are insufficient in terms of reliability and processability (Patent Document 2, Patent Document 3, and Patent Document 4).

In addition, Patent Document 5 discloses a curable resin composition containing a hydroxyl group of a phenol aralkyl resin, a naphthol aralkyl resin, a biphenyl type phenol novolac resin, or a biphenyl type naphthol novolac resin. A curable resin obtained by etherification with vinyl benzyl, and a compound having one or more maleimide groups in the molecule. However, the curable resin composition disclosed in the patent document not only has insufficient initial characteristics of the dielectric characteristics, but also has an unsatisfactory adhesion reliability as an insulating material after being subjected to a wet heat history. In terms of moldability, It is easy to cause defective molding, which is not ideal.

Patent Document 6 discloses an insulating sheet and a laminated structure that can obtain a cured product with high operability in an uncured state and a low relative dielectric constant. As a material for forming the sheet and the structure, there is disclosed A curable resin composition containing a poly (vinylbenzyl) ether compound and an epoxy resin. Specific examples of the poly (vinylbenzyl) ether compound include vinylbenzyl ether group hydroquinone, bisphenol A, bisphenol F, bisphenol S, biphenol, phenol novolac resin, and phenol. Condensates with benzaldehyde or compounds substituted with a new phenol (Xylok) type phenol resin, etc. Further, in the examples, only vinyl benzyl ether compounds of the new phenol type phenol resin are disclosed. In addition, the curable resin composition containing a poly (vinylbenzyl) ether compound and an epoxy resin disclosed in the aforementioned patent document has a large change in dielectric tangent when subjected to a severe thermal history. The tightness reliability is also insufficient.

As described above, the conventional poly (vinylbenzyl) ether compound and the curable resin composition thereof are not those provided with a cured product that is used as an electrical insulating material, particularly an electrical insulating material corresponding to a high frequency. The required low-dielectric tangent heat resistance and flame retardance after satisfying a severe thermal history are also insufficient from the viewpoint of adhesion reliability and processability.

Patent Document 7 proposes a poly (vinylbenzyl) ether compound obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound as a solution to the problem of the poly (vinylbenzyl) ether compound Clickers.

However, in consideration of the recent trend of miniaturization, thinning, and multifunctionalization of electronic devices, there is a need for heat resistance and resistance of low dielectric tangent after satisfying a severe thermal history, in addition to the severe thermal history required so far. Insulating resin for circuit boards with new functions in addition to flammability, adhesion reliability and processability. For example, when an integrated circuit (IC) chip is mounted on a circuit board, if a bare chip method is used which is not enclosed in a package of an IC chip, it is compared with the previous mounting method. , Can achieve miniaturization of electronic equipment. In this aspect, the insulating resin for a circuit board is heated via solder or copper wiring. Due to the stress concentration caused by the heat, there is a possibility that cracks may occur in the insulating resin, solder, or copper wiring. Therefore, an insulating resin excellent in crack resistance is required.

However, the poly (vinylbenzyl) ether compound obtained by reacting the naphthol aralkyl resin with a vinyl aromatic halomethyl compound has room for further improvement in crack resistance. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2005-314556 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 1-503238 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 9-31006 [Patent Literature 4] Japanese Patent Laid-Open No. 2004-323730 [Patent Literature 5] Japanese Patent Laid-Open No. 2003-306591 [Patent Literature 6] Japanese Patent Laid-Open No. 2011-124076 [Patent Literature 7] WO2014 / 103926

[Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to provide a low dielectric tangent after satisfying a severe thermal history, and to have both heat resistance, flame retardancy, adhesion reliability, processability and crack resistance Resin materials, and circuit board materials using the same.

[Technical means to solve the problem] The present inventors have found that a poly (vinylbenzyl) ether compound in which a hydroxyl group of a naphthol aralkyl resin is substituted with a vinyl benzyl ether group at a specific ratio has been found to solve the problem. The subject is effective and the present invention has been completed.

（1） 此處，R¹ 分別獨立地表示氫原子、碳數1～6的烷基、烯丙基、或碳數6～10的芳基，Ar¹ 表示碳數6～50的二價的芳香族烴基，R² 分別獨立地表示氫原子、碳數1～12的烷基、或乙烯基苄基。其中，R² 中的乙烯基苄基的比例為10莫耳%以上、未滿60莫耳%，氫原子的比例為40莫耳%以上。n以平均值計為1～20的範圍，m為1～6的數，r為1～3的數，但m+r不超過6或7。That is, this invention is a poly (vinyl benzyl) ether compound represented by following formula (1). [Chemical 1]

(1) Here, R ¹ each 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 represents a divalent group having 6 to 50 carbon atoms. In an aromatic hydrocarbon group, R ² each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinyl benzyl group. Among them, the proportion of vinyl benzyl in R ² is 10 mol% or more and less than 60 mol%, and the proportion of hydrogen atoms is 40 mol% or more. 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, but m + r does not exceed 6 or 7.

The poly (vinylbenzyl) ether compound may be a naphthol aralkyl resin and a vinyl aromatic compound in which R ² in formula (1) is a hydrogen atom, or a hydrogen atom and an alkyl group having 1 to 12 carbon atoms. A halomethyl compound is obtained by a reaction.

Further, in the formula (1), preferably having one or more R in one molecule ^is a hydrogen atom, a benzyl group or a vinyl group OR ² (Y), and the average per molecule of OR ² groups (Y ) The number is 1.1 or more.

Furthermore, this invention is a curable resin composition characterized by including the following (A) component and (B) component. (A) component: the poly (vinylbenzyl) ether compound; (B) component: selected from epoxy resins having two or more epoxy groups and aromatic structures in one molecule, and two in one molecule At least one of the epoxy resin having the above epoxy group and cyanurate structure, and the epoxy resin having two or more epoxy groups and alicyclic structure in one molecule.

The said curable resin composition may further contain an epoxy resin hardener as (C) component.

Moreover, this invention is a hardened | cured material formed by hardening the said hardenable resin composition, the hardenable composite material containing the said hardenable resin composition and a base material, or the metal foil which has the above-mentioned A resin-coated metal foil of a film formed of a curable resin composition. Furthermore, this invention is a laminated body of the layer which has the said hardened | cured material, and a metal foil layer, or the circuit board material formed using the said hardened | cured material. The present invention is a varnish formed by dissolving the curable resin composition in a solvent, or the varnish used for a circuit board material. [Effect of the invention]

The poly (vinylbenzyl) ether compound of the present invention, or a resin composition formulated therewith, can provide high dielectric characteristics (low dielectric constant, low dielectric tangent) even after severe thermal history, and at high temperatures・ A hardened product that has high adhesion reliability and excellent crack resistance even under severe environments such as high humidity. Therefore, it can be suitably used as a dielectric material, an insulating material, and a heat-resistant material in fields such as the electrical and electronic industries, the space, and the aircraft industry. It can be particularly suitably used as a circuit board material such as a single-sided, double-sided, or multi-layer printed circuit board, a flexible printed circuit board, or a build-up substrate.

Hereinafter, the present invention will be described in detail. The poly (vinylbenzyl) ether compound of the present invention is represented by the formula (1). In Formula (1), R ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 30 carbon atoms. The aryl group may further have a substituent, for example, an alkyl group having 1 to 6 carbon atoms.

From the viewpoint of the balance between solubility and dielectric properties and hardenability and flame retardancy, R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably a hydrogen atom. , An alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is particularly preferred.

R ² each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinyl benzyl group. The proportion (mole%) of vinyl benzyl in R ² is 10 mol% or more and less than 60 mol%, but preferably 15 mol% to 59 mol%, and more preferably 20 mol. % To 55 mole%. Still more preferably, it is 20 mol% to 53 mol%. When the proportion of vinylbenzyl is 60 mol% or more, the polymerization active point is excessively increased, the flexibility of the resin is lost, and cracks are liable to occur in the reliability test. On the other hand, when the proportion of vinylbenzyl group is less than 10 mol%, the crosslinking density decreases, and the amount of carbides generated at 600 ° C, which affects flame retardancy or heat resistance, decreases.

When an epoxy resin is formulated, in order to efficiently perform a cross-linking reaction with the epoxy resin, the proportion of hydrogen atoms in R ² is preferably 40 mol% or more.

In the formula (1), it is preferable that one or more R ² is a hydrogen atom or an OR ² group (Y) of a vinyl benzyl group in one molecule, and an average OR ² group (Y) per 1 molecule The number is 1.1 or more. Here, an OR ² group in which R ² is a hydrogen atom or a vinyl benzyl group is referred to as an OR ² group (Y). The OR ² group (Y) is understood to R ² OR ² group other than an alkyl group having 1 to 12 carbon atoms. It is more preferable to have one or more OR ² groups (Y) in one molecule, and the average number of OR ² groups (Y) per molecule is 1.1 or more, and advantageously 2.2 or more. Still more preferably, the number of OR ² groups in which R ² is a vinyl benzyl group and a hydrogen atom is 1.1 or more in each molecule. In addition, it is preferable that the molecule contains 90 mol% or more of molecules in which the number of OR ² groups in which R ² is a vinyl benzyl group and a hydrogen atom is 1.1 or more in each molecule. Further, two or more molecules containing R ² which is 5 mol%, preferably 10 mol% or more, may be a vinylbenzyl group. Furthermore, when the poly (vinylbenzyl) ether compound of the present invention is a resin having a plurality of vinylbenzyl ether groups, but having a molecular weight distribution containing molecules with different n, as long as it is 1 mole% or more of all molecules What is necessary is just to have a several vinyl benzyl ether group.

In order to improve toughness, formability, and dielectric characteristics, it is preferable that a part of R ² be an alkyl group. The proportion of the alkyl group in R ² may be 1 mol% to 10 mol%, preferably 1 mol% to 6 mol%, and more preferably 1.5 mol% to 4 mol%. The alkyl group may be an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is preferred.

In Formula (1), m represents a number of 1 to 6, but from the viewpoint of the balance between solubility and flame retardancy, when R ¹ is a substituent other than hydrogen, the number (m) is preferably 0 to 2.

Although r represents a number of 1 to 3, a number of 1 to 2 is preferred from the viewpoint of solubility and toughness. m + r is 6 or 7. Specifically, in the formula (1), m + r is 7 in the naphthalene ring represented by the left end of the formula, and m + r is 6 in the naphthalene ring represented by the repeating structural unit. The sum of m and r per one naphthalene ring is preferably 1 to 4.

Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 50 carbon atoms. Examples thereof include: selected from the group consisting of -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- Aromatic hydrocarbon groups having 6 to 50 carbon atoms. An aromatic hydrocarbon group having 6 to 30 carbon atoms is preferred, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred. Here, Ph represents a phenylene group (-C ₆ H _4- ), Np represents a naphthyl group (-C ₁₀ H _6- ), and Flu represents a fluorenyl group (-C ₁₃ H _8- ). Here, Ph, Np, and Flu may have a substituent, and examples thereof include an alkyl group, an alkoxy group, and a phenyl group. Preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. In addition, as Ar ¹ , from the viewpoints of solubility and flame retardancy, unsubstituted, alkyl-substituted, alkoxy-substituted, or phenyl-substituted -Ph-, -Ph-Ph-, or Np-.

n represents the number of 1-20 as an average value, Preferably it is 1-10. When n exceeds 20, viscosity increases, and it is not preferable in that the filling property with respect to a fine pattern decreases. In addition, when it has a molecular weight distribution, it is a number average. Furthermore, it is preferable that the peak area (a) of the poly (vinylbenzyl) ether compound based on the vinyl aromatic halomethyl compound is higher than that of the poly (ethylene) in gas chromatography (GC) measurement. The peak area (a) of the sum of the peak areas (b) of the benzyl) ether compound is 1.0% or less. It is preferably 0.5% or less, and more preferably 0.2% or less. When the peak area exceeds 1.0%, there is a tendency that the dielectric characteristics are deteriorated after being subjected to a thermal history of 250 ° C. or higher for a long period of time. Here, the peak area (b) of the poly (vinylbenzyl) ether compound refers to a peak area based on a pure poly (vinylbenzyl) ether compound that satisfies the formula (1). The poly (vinylbenzyl) ether compound of the present invention is a reaction product or a product obtained by purifying the poly (vinylbenzyl) ether compound. In addition to the pure poly (vinylbenzyl) ether compound, it may contain a small amount that does not satisfy the formula (1). Other ingredients as impurities.

The poly (vinylbenzyl) ether compound of the present invention preferably has a total halogen content of 600 ppm (wt) or less. It is more preferably 450 ppm or less, and still more preferably 200 ppm or less. When the total halogen content exceeds 600 ppm, there is a tendency that the dielectric characteristics are deteriorated after being subjected to a thermal history of 250 ° C. or higher for a long period of time. Since said halogen is mainly based on the aromatic halomethyl compound as a raw material, it is related to the said peak area (a).

In addition, if the total halogen content is 600 ppm or less, unexpected effects such as warping and poor molding can be obtained, which is also preferable. However, excessively lowering the total halogen content or the content of the vinyl aromatic halomethyl compound significantly reduces the purification yield. According to experiments, it has been found that if the total halogen content is 2 ppm or more, the problems related to industrial implementation as described above do not occur, and therefore purification beyond this is not advantageous in terms of the yield of purification.

（2）As described above, as an example, the poly (vinylbenzyl) ether compound of the present invention can be obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound. The naphthol aralkyl resin is represented by the following formula (2). [Chemical 2]

(2)

In the formulas (1) and (2), the same symbols have the same meanings. Thus, R (2) in the formula ^1, the meaning of Ar ^1, n, m and r and R in the formula (1) is ^1, Ar ^1, the same n, m and r.

The reaction of the naphthol aralkyl resin represented by the formula (2) and the vinyl aromatic halomethyl compound is not particularly limited, and it can be performed, for example, in a liquid phase such as a polar solvent by dissolving an alkali The metal hydroxide is used as a dehydrohalogenating agent to perform the reaction. In the reaction, a phenolic hydroxyl group of a naphthol aralkyl resin is subjected to a condensation reaction with a CH ₂ X group of a vinyl aromatic halomethyl compound, and a vinyl benzyl ether compound is formed after de-HX.

In addition, in order to improve toughness, moldability, and dielectric properties, for example, the naphthol aralkyl group represented by the formula (2) may be made in the presence of an acidic catalyst in accordance with the method described in Japanese Patent No. 4465257. A part of the phenolic hydroxyl group of the resin is reacted with an alcohol having 1 to 12 carbon atoms, whereby an alkyl group having 1 to 12 carbon atoms is introduced as a part of R ² in the formula (1).

The reaction for introducing an alkyl group may be before the reaction with the vinyl aromatic halomethyl compound or after the reaction with the vinyl aromatic halomethyl compound. However, in order to avoid polymerization of the vinyl group, it is preferred to react with the vinyl aromatic halomethyl compound. Before the reaction of the halomethyl compound. When the reaction for introducing an alkyl group is before the reaction with a vinyl aromatic halomethyl compound, the following method is adopted: first, a part of hydrogen atoms of a phenolic hydroxyl group is substituted with an alkyl substituted naphthol aralkyl resin (hereinafter, referred to as Is a part of a modified naphthol aralkyl resin), and then reacted with a vinyl aromatic halomethyl compound to obtain a part of an alkylated poly (vinylbenzyl) ether compound. When the reaction of introducing an alkyl group is followed by a reaction with a vinyl aromatic halomethyl compound, the method is as follows: a naphthol aralkyl resin is reacted with a vinyl aromatic halomethyl compound to obtain a poly (vinylbenzyl Group) ether compound, and then a part of hydrogen atoms of the remaining phenolic hydroxyl group is alkylated to obtain a poly (vinylbenzyl) ether compound. Here, a part of the modified naphthol aralkyl resin is included in the naphthol aralkyl resin described in this specification.

In addition, as a part or all of the raw materials of the naphthol aralkyl resin, a hydroxynaphthalene having a part or all of the hydrogen atoms of the phenolic hydroxyl group as an alkyl group may be used. In addition, the naphthol aralkyl resin may be a mixture of all alkylated hydrogen atoms of a phenolic hydroxyl group and a residue of all hydrogen atoms of a phenolic hydroxyl group. The naphthol aralkyl resin is also included in a part of the modified naphthol aralkyl groups. In resin.

As the naphthol aralkyl resin represented by the formula (2), in addition to the reaction obtained by the reaction, a commercially available one can be used. For example, SN170 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. can be suitably used. , SN180, SN190, SN475, SN485, SN495, etc. In terms of solubility, toughness, and flame retardancy, SN475, SN485, SN495, SN485V, and SN495V are more preferable. From the viewpoint of dielectric properties, toughness, and formability, SN485V and SN495V are particularly preferred.

The naphthol aralkyl resin represented by the formula (2) can also be produced by a known method. The manufacturing method is described in, for example, Japanese Patent Laid-Open No. 2001-213946, Japanese Patent Laid-Open No. 11-255868, Japanese Patent Laid-Open No. 11-228673, Japanese Patent Laid-Open No. 08-073570, and Japanese Patent Laid-Open No. 08-073570. It is described in 08-048755, Japanese Patent Laid-Open No. 10-310634, or Japanese Patent Laid-Open No. 11-116647. The naphthol aralkyl resin represented by the formula (2) may be used alone or in combination of two or more kinds.

The vinyl aromatic halomethyl compound is represented by CH ₂ = CH-Ar ² -CH ₂ X. Here, Ar ₂ is phenylene or substituted phenylene. Examples of the substituent in the case of substituted phenylene include an alkyl group, an alkoxy group, and a phenyl group. Preferred is an alkyl group having 1 to 6 carbon atoms. In addition, as Ar ² , in terms of solubility and flame retardancy, unsubstituted, alkyl-substituted, alkoxy-substituted, or phenyl-substituted phenylene is more preferable. Furthermore, unsubstituted and alkyl substituted phenylene which is easy to manufacture industrially is more preferable. The vinyl aromatic halomethyl compound provides a vinyl benzyl group of R ² and is thus understood to be a substituted vinyl benzyl group having a substituent on its benzene ring. In addition, X is halogen, and chlorine or bromine is preferred.

Preferred vinyl aromatic halomethyl compounds include p-vinylbenzyl chloride, m-vinylbenzyl chloride, a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride, and p-vinylbenzyl Bromine, m-vinylbenzyl bromide, a mixture of p-vinylbenzyl bromide and m-vinylbenzyl bromide. Among them, when a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride is used, a poly (vinylbenzyl) ether compound having excellent solubility can be obtained, and compatibility and workability with other materials become high. Good, so preferred. When a mixture of p-vinylbenzyl halide and m-vinylbenzyl halide is used, the composition ratio is not particularly limited, but it is preferred that the pair / intermediate = 90/10 to 10/90 (mole / mole), and more It is preferably 70/30 to 30/70 (mol / mol), and more preferably 60/40 to 40/60 (mol / mol).

When a naphthol aralkyl resin is reacted with a vinyl aromatic halomethyl compound as described above to obtain a poly (vinylbenzyl) ether compound, the vinylbenzyl group deviates from the naphthol aralkyl group. Since the OH group of the resin reacts, the number of vinylbenzyl groups per molecule varies. In addition, two or more vinylbenzyl groups per molecule are mixed with less than two vinylbenzyl groups per molecule, and two or more vinylbenzyl groups per molecule are cross-linked and polymerized. Provide hardened resin. Those having less than two vinyl benzyl groups per molecule control the degree of crosslinking and impart properties such as flexibility to the resin. Those who do not have a vinyl benzyl group do not participate in the polymerization of the vinyl group. Therefore, it is desirable that the amount is small. However, the hardened resin can be reacted by converting an OH group to a cyanate group, etc., or reacting with an epoxy resin. Make a contribution.

As described later, the poly (vinylbenzyl) ether compound of the present invention is preferably mixed with an epoxy resin to perform polymerization (also referred to as crosslinking). In addition, it may be polymerized by mixing with an epoxy compound other than an epoxy resin, and it may also be used as a cyanate resin or dicis-butene difluorene by cyanating a hydroxyl group by a known method. Amine-triazine resin. As described above, for example, a printed wiring board material having a low dielectric constant and excellent heat resistance and flame retardancy can be obtained.

Next, the curable resin composition of the present invention will be described. The curable resin composition of this invention contains the said (A) component and (B) component.

The component (A) is the poly (vinylbenzyl) ether compound, and the component (B) is a polyfunctional epoxy resin having two or more epoxy groups in one molecule. As a polyfunctional epoxy resin having two or more epoxy groups in one molecule, there are an epoxy resin (B1) having an aromatic structure, an epoxy resin (B2) having a cyanurate structure, and an alicyclic structure. Epoxy resin (B3), or a mixture of these. Hereinafter, the epoxy resin (B1) is also called an aromatic epoxy resin, the epoxy resin (B2) is called a cyanurate epoxy resin, and the epoxy resin (B3) having an alicyclic structure is also called It is an alicyclic epoxy resin. The alicyclic epoxy resin may have an alicyclic structure having 3 to 12 carbons, and preferably 5 to 10 carbons.

Preferred examples of the epoxy resin of 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. 2, xylyl modified phenol novolac epoxy resin, xylyl modified alkyl phenol novolac epoxy resin, biphenyl epoxy resin, phenols and condensates of aromatic aldehydes with phenolic hydroxyl groups Aromatic epoxy resins such as epoxy, naphthalene epoxy resin, cyanurate epoxy resins such as isocyanurate triglycidyl ester, cyclohexane epoxy resin, dicyclopentadiene type Alicyclic epoxy resins such as epoxy resins and adamantane epoxy resins. These epoxy resins may be used alone, or two or more of them may be used in combination.

Examples of the bisphenol F-type epoxy resin include epoxy resins containing 4,4'-methylenebis (2,6-dimethylphenol) diglycidyl ether as a main component, and 4,4 '-Methylenebis (2,3,6-trimethylphenol) diglycidyl ether as the main component of epoxy resin, 4,4'-methylenebisphenol diglycidyl ether as the main component Epoxy. Among these, epoxy resins containing diglycidyl ether of 4,4′-methylenebis (2,6-dimethylphenol) as a main component are preferred. The bisphenol F-type epoxy resin can be obtained as YSLV-80XY (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

Examples of the biphenyl type epoxy resin include 4,4'-diglycidyl biphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl. Epoxy. The biphenyl epoxy resin can be obtained as YX-4000, YL-6121H (manufactured by Mitsubishi Chemical Corporation).

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

Examples of the naphthalene-type epoxy resin include 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-glycidyl naphthalene, triglycidyl naphthalene, and 1,2,5,6-tetraglycidyl naphthalene, naphthol / aralkyl epoxy resin, naphthalene skeleton modified cresol novolac Modified epoxy resin, methoxynaphthalene modified cresol novolac epoxy resin, modified naphthyl ether epoxy resin, modified naphthalene epoxy resin, etc. .

Examples of the adamantane-type epoxy resin include 1- (2,4-diglycidyloxyphenyl) adamantane, 1- (2,3,4-triglycidyloxyphenyl) adamantane, 1 , 3-bis (2,4-diglycidyloxyphenyl) 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.

Among the epoxy resins, bisphenol F-type epoxy resins and alkylphenols can be suitably used from the viewpoint of compatibility with the component (A), dielectric properties, and small warpage of the molded product. Novolac epoxy resin, phenol aralkyl epoxy resin, alkylphenol aralkyl epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, Triglycidyl isocyanurate, cyclohexane epoxy resin, adamantane epoxy resin.

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

The lower limit of the content of the (B) component relative to 100 parts by weight of the (A) component is preferably 5 parts by weight and the upper limit is 100 parts by weight. More preferably, the lower limit of the content of the (B) component is 10 parts by weight based on 100 parts by weight of the (A) component. On the other hand, a more preferable upper limit is 80 weight part, and a further more preferable upper limit is 60 weight part. When the content of the component (B) satisfies the above-mentioned preferred lower limit, the adhesion of the cured product of the cast film and sheet can be further improved. When the content of the component (B) satisfies the preferable upper limit, the operability of the cast film and sheet in an unhardened state is further improved.

The curable resin composition of the present invention may contain an epoxy resin hardener as the component (C). The component (C) is not particularly limited as long as it hardens the epoxy resin as the component (B). These hardeners may be used alone or in combination of two or more.

The curing agent of the component (C) is preferably a phenol resin, an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a hydrogenated product or a modified product of these acid anhydrides. By using these hardeners, a hardenable resin composition can be obtained which is a hardened product excellent in the balance of heat resistance, flame retardancy, moisture resistance, and electrical properties.

The phenol resin used as the hardener is not particularly limited. Specific examples of the phenol resin include phenol novolac, o-cresol novolac, p-cresol novolac, third butyl novolac, dicyclopentadiene cresol, poly-p-vinylphenol, Bisphenol A novolac, phenol aralkyl resin, naphthol aralkyl resin, biphenyl phenol novolac resin, biphenyl naphthol novolac resin, decahydronaphthalene modified novolac, poly (di-ortho) Hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane. Among them, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferred because it can further improve the flexibility and flame retardancy of the insulating sheet.

Examples of commercially available phenol resins include MEH-8005, MEH-8010, and NEH-8015 (manufactured by Meiwa Chemical Co., Ltd.), YLH903 (manufactured by Japan Epoxy Resins), LA-7052, LA-7054, LA-77751, LA-1356, and LA-3018-50P (manufactured by DIC), and PS6313 and PS6492 (manufactured by Qunrong Chemical Co., Ltd.).

The structure of the acid anhydride, an hydride, or a modified product thereof having an aromatic skeleton used as a hardener is not particularly limited. Examples include: styrene / maleic anhydride copolymer, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenyl Ethynyl phthalic anhydride, glycerol bis (dehydrated trimellitate) monoacetate, ethylene glycol bis (dehydrated trimellitate), methyltetrahydrophthalic anhydride, methylhexahydro Phthalic anhydride, trialkyltetrahydrophthalic anhydride, Nadic methyl anhydride, trialkyltetrahydrophthalic anhydride, etc.

Examples of the commercially available product of the acid anhydride having an aromatic skeleton, its hydride, or modified product include SMA resin EF30, SMA resin EF40, SMA resin EF60, and SMA resin EF80 (Sartomer Japan) (Manufactured by the company), ODPA-M and PEPA (manac), Rikacid MTA-10, Rikacid MTA-15, Rikacid TMTA , Rikacid TMEG-100, Rikacid TMEG-200, Rikacid TMEG-300, Rikacid TMEG-500, Rikacid ( Rikacid) TMEG-S, Rikacid TH, Rikacid HT-1A, Rikacid HH, Rikacid MH-700, Rikacid (Rikacid) MT-500, Rikacid DSDA and Rikacid TDA-100 (manufactured by New Japan Physicochemical Corporation), and EPICLON B4400, EPICLON B650 , And EPICLON B570 (manufactured by Dickson).

The acid anhydride having an alicyclic skeleton or a modified product of the acid anhydride is preferably an acid anhydride having a polyalicyclic skeleton or an alicyclic compound obtained by an addition reaction of a terpene-based compound and maleic anhydride. A skeleton acid anhydride or a modification thereof. In this case, the flexibility, moisture resistance, or adhesion of the insulating sheet can be further improved. Examples of the acid anhydride or a modified product thereof having an alicyclic skeleton include methyl nadic acid anhydride, an acid anhydride or a modified product thereof having a dicyclopentadiene skeleton, and the like. The alicyclic skeleton includes a skeleton having an unsaturated bond, such as a dicyclopentadiene skeleton, and a skeleton having no unsaturated bond, such as a cyclopentane skeleton, and may be any one. In addition, it may be a hydrogenated acid anhydride or a modification thereof obtained by hydrogenating a skeleton having an unsaturated bond, and the hydrogenated skeleton may be a skeleton having no unsaturated bond or a part of a hydrogenated part. Hydride. The hydrogenated product of the acid anhydride having an aromatic skeleton may correspond to an acid anhydride having an alicyclic skeleton.

Examples of commercially available products of the acid anhydride and the modified product having an alicyclic skeleton include Rikacid HNA and Rikacid HNA-100 (manufactured by New Japan Physicochemical Corporation), and Epicure YH306, Epicure YH307, Epicure YH308H, and Epicure YH309 (the above are all manufactured by Japan Epoxy Resin Company).

From the viewpoints of compatibility with the component (A), moisture resistance, and adhesiveness, as the curing agent of the component (C), o-cresol novolac, p-cresol novolac, and third butylphenol are more preferable. Novolac, dicyclopentadiene cresol, poly-p-vinylphenol, p-xylyl modified novolac, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di -P-hydroxyphenyl) methane, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, or an acid anhydride having a dicyclopentadiene skeleton, or a modified product of these acid anhydrides.

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

Specific examples of the component (D) include polyphenylene sulfide resin, polyarylate resin, polyfluorene resin, polyether fluorene resin, polyphenylene ether resin, polycarbonate resin, polyvinyl acetal resin, Polyimide resin, polyimide resin, polybenzoxazole resin, phenoxy resin, styrene resin, (meth) acrylic resin, polycyclopentadiene resin, polycycloolefin resin , Polyetheretherketone resin, polyetherketone resin, or known thermoplastic elastomers, such as styrene-ethylene-propylene copolymers, styrene-ethylene-butene copolymers, styrene-butadiene copolymers, benzene Ethylene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc., or rubbers, such as high molecular weight resins such as polybutadiene and polyisoprene .

Among these high molecular weight resins, from the viewpoints of compatibility with the component (A) and adhesion reliability, polyfluorene resins, polyether resins, polyphenylene ether resins, phenoxy resins, and polyether resins are suitably used. High molecular weight resins such as cycloolefin resin, hydrogenated styrene-butadiene copolymer, and hydrogenated styrene-isoprene copolymer.

The preferred lower limit of the glass transition temperature Tg of the high molecular weight resin of the component (D) is -40 ° C, the more preferred lower limit is 50 ° C, and the most preferred lower limit is 90 ° C. A preferred upper limit is 250 ° C, and a more preferred upper limit is 200 ° C. When Tg satisfies the preferable lower limit, it is difficult for the resin to be thermally deteriorated. When Tg satisfies the preferable upper limit, the compatibility of the (D) component with other resins becomes high. As a result, the operability of the cast film and sheet in the unhardened state, and the heat resistance and flame retardancy of the cured product of the cast film and sheet can be further improved.

The preferable lower limit of Mw of the high molecular weight resin is 20,000, the more preferable lower limit is 30,000, the preferable upper limit is 1 million, and the more preferable upper limit is 250,000. If Mw satisfies the preferable lower limit, the insulating sheet is less likely to be thermally deteriorated, and if the preferable upper limit is satisfied, the compatibility of the (D) component with other resins becomes high. As a result, the operability of the cast film and sheet in the unhardened state, and the heat resistance and flame retardancy of the cured product of the cast film and sheet can be further improved.

When the (A) component to (D) component are contained in the curable resin composition of the present invention, the (D) component is 100 wt% (weight percentage) of the total of all resin components (hereinafter, also referred to as all resin components X). The content in) is preferably in the range of 10 wt% to 60 wt%. A more preferred lower limit of the content of the (D) component in a total of 100 wt% of all the resin components X is 20 wt%, and a more preferred upper limit is 50 wt%. When the content of the (D) component satisfies the preferable lower limit, the operability of the cast film and sheet in the unhardened state can be further improved. When the content of the (D) component satisfies the preferable upper limit, dispersion of the inorganic filler as the (F) component described later becomes easy. In addition, all resin components X are the sum of (A) component, (B) component, (C) component, (D) component, and other resin components added as needed. The component which becomes a resin component after hardening, such as a hardener, is calculated as a resin component, but does not contain the inorganic filler of a (F) component, or the flame retardant of a (G) component mentioned later.

In addition to the components, the curable resin composition of the present invention may contain a radical polymerization initiator (also referred to as a radical polymerization catalyst) as the (E) component as desired. For example, the curable resin composition of the present invention undergoes a crosslinking reaction and hardens by a method such as heating as described later, but by adding the component (E), the reaction temperature at this time can be lowered or the crosslinking reaction of unsaturated groups can be promoted. .

Examples of the (E) component include benzamyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5 -Dimethyl-2,5-bis (third butyl peroxide) hexyne-3, bis-third butyl peroxide, third butylcumyl peroxide, α, α'-bis ( Third butyl-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (third butyl peroxide) hexane, dicumyl peroxide, m-xylylene peroxide Di-tertiary butyl formate, tertiary butyl peroxybenzoate, 2,2-bis (tertiary butyl peroxide) butane, 2,2-bis (tertiary butyl peroxide) octane, 2 , 5-dimethyl-2,5-bis (benzylidene peroxide) hexane, bis (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, etc. The oxide is not limited to these examples. In addition, 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 the hardening of this resin composition are not limited to these examples.

When the compounding amount of the (E) component is in the range of 0.01 to 10 parts by weight with respect to the (A) component, the reaction proceeds well without hindering the curing reaction. In addition, if necessary, another polymerizable monomer that can be copolymerized with the component (A) may be blended in the curable resin composition of the present invention to be cured. When the other polymerizable monomer is formulated, it is included in all resin components X.

Examples of the other polymerizable monomer include styrene, styrene dimer, α-methylstyrene, α-methylstyrene dimer, divinylbenzene, vinyltoluene, and tert-butyl Styrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, fluorene, divinylbenzyl ether, allylphenyl ether, and the like.

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

The hardening accelerator is not particularly limited. Specific examples of the hardening accelerator include, for example, tertiary amines, imidazoles, imidazolines, triazines, organophosphorus compounds, quaternary phosphonium salts, and diazabicycloolefins such as organic acid salts. Examples of the hardening accelerator include organometallic compounds, quaternary ammonium salts, and metal halides. Examples of the organometallic compounds include zinc octoate, tin octoate, and acetoacetone aluminum complex.

As the hardening accelerator, a high melting point imidazole hardening accelerator, a high melting point dispersive latent hardening accelerator, a microcapsule type latent hardening accelerator, an amine salt type latent hardening accelerator, and a high temperature dissociation type can also be used. Thermal cationic polymerization type latent hardening accelerator, etc. Only one type of hardening accelerator may be used, or two or more types may be used in combination.

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

The hardening accelerator is preferably an organic phosphorus-based compound and a high-melting imidazole-based hardening accelerator. By using an organic phosphorus-based compound and a high-melting imidazole-based hardening accelerator, the reaction system can be easily controlled, and the hardening speed of the cast film and sheet, and the physical properties of the hardened product of the cast film and sheet can be adjusted more easily. A high-melting hardening accelerator having a melting point of 100 ° C. or higher is excellent in handleability. Therefore, the melting point of the hardening accelerator is preferably 100 ° C or higher.

Of the total 100 wt% of all the resin components X, the preferred lower limit of the content of the (C) component is 1 wt%, and the preferred upper limit is 40 wt%. A more preferred lower limit is 5 wt%, and a more preferred upper limit is 25 wt%. If the content of the component (C) satisfies the preferable lower limit, it is easy to sufficiently harden the cast film and sheet, and if the preferable upper limit is satisfied, it is difficult to generate an excess hardener which does not participate in hardening, and the hardened material can be hardened. The crosslinking is fully carried out. Therefore, the heat resistance, flame retardancy, and adhesiveness of the hardened | cured material of a cast film and sheet can be improved further.

Furthermore, it is known that the relationship between epoxy resin and hardener is preferably a ratio (equivalent ratio) of epoxy groups in epoxy resin to functional groups (active hydrogen, etc.) in the hardener of about 1: 1. The curable resin composition can also be formulated so that the ratio becomes 0.5 to 2: 1, and preferably 0.8 to 1.2: 1. In this case, since the OH group contained in the component (A) functions as a hardener, the calculation of the hardener includes the component (A).

In the curable resin composition of the present invention, in order to further reduce the thermal expansion coefficient of the insulating layer obtained from the curable resin composition, an inorganic filler may be added as the (F) component. Examples of the component (F) include silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. Among these, amorphous silica and fused silica are particularly suitable. , Crystalline silicon dioxide, synthetic silicon dioxide and other silicon dioxide. As the silicon dioxide, spherical silica is preferred.

(F) A component may be used in combination of 2 or more types. The average particle diameter of the inorganic filler is not particularly limited, but from the viewpoint of forming fine wiring on the insulating layer, it is preferably 5 μm or less, more preferably 1 μm or less, and still more preferably 0.7 μm or less. Furthermore, if the average particle diameter of the (F) component becomes too small, when the curable resin composition of the present invention is made into a resin varnish, the viscosity of the varnish tends to increase and the handleability tends to decrease. Therefore, the average particle diameter is preferred. Above 0.05 μm. The average particle diameter of the (F) component can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the component (F) can be prepared on a volume basis using a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, it is preferable to use a product obtained by dispersing the (F) component in water by ultrasonic waves. As a laser diffraction type particle size distribution measuring device, LA-500 manufactured by Horiba, Ltd., etc. can be used.

The component (F) is preferably one that is surface-treated with a surface treatment agent such as an epoxy silane coupling agent, an amino silane coupling agent, or a titanate-based coupling agent to improve its moisture resistance. The amount of the component (F) added is preferably in the range of 20 to 400 parts by mass, more preferably in the range of 30 to 350 parts by mass, and more preferably 100 parts by mass of the non-volatile component of the curable resin composition. A range of 40 parts by mass to 300 parts by mass. When the content of the (F) component exceeds 400 parts by mass, the cured product tends to become brittle or the peel strength tends to decrease. On the other hand, when the content of the (F) component is less than 20 parts by mass, the thermal expansion coefficient does not decrease sufficiently.

The curable resin composition of the present invention may contain a flame retardant as the (G) component within a range that does not impair the effects of the present invention. Examples of the (G) component include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone-based flame retardant, and a metal hydroxide. Examples of the organic phosphorus-based flame retardant include phenanthrene phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko (Co., Ltd.), and phosphorus-containing benzoxamines such as HFB-2006M manufactured by Showa Polymer (Co., Ltd.) Azine compound, Reofos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ manufactured by Beixing Chemical Industry (Shares), OP930 manufactured by Clariant (Shares), PX200 manufactured by Big Eight Chemicals (Shares), and other phosphate ester compounds, and FX289 manufactured by Totsu Kasei (Shares) Phosphorous epoxy resins such as FX305, phosphorus phenoxy resins such as ERF001 manufactured by Toto Chemical Co., Ltd., and phosphorous epoxy resins such as YL7613 manufactured by Japan Epoxy Resins (stock). Examples of organic phosphorus compounds containing nitrogen include phosphoric acid ammonium compounds such as SP670 and SP703 manufactured by Shikoku Chemical Industries, Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP manufactured by Fushimi Manufacturing Co., Ltd. -Series and other phosphazene compounds. Examples of the metal hydroxide include magnesium hydroxides such as UD65, UD650, and UD653 manufactured by Ube Material (stock), and B-30, B-325, B-315, B manufactured by Ba Industries (stock) -308, B-303, UFH-20 and other aluminum hydroxide.

The curable resin composition of the present invention can be used as a varnish for a circuit board material by being dissolved in a known solvent. Preferred solvents include toluene, xylene, tetrahydrofuran, and dioxolane, as long as they do not react with the curable resin composition and have good solubility. Moreover, the circuit board material of this invention is manufactured using the hardened | cured material, composite hardened | cured material, or laminated body of this invention. Specific examples include single-sided, double-sided, or multi-layer printed boards, flexible printed boards, and build-up boards.

The hardened | cured material of this invention is obtained by hardening the curable resin composition of this invention. The shape of the cured product is not limited, and it can be used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film according to the application. For example, the hardened material of the semiconductor sealing material is a cast product or a molded product. As a method of obtaining the hardened product of the above-mentioned application, the hardened product can be obtained by hardening using a casting, injection molding machine, injection molding machine, or the like. The resin composition is molded, and further heated at 80 ° C to 230 ° C for 0.5 to 10 hours. In addition, it is advantageous that the cured product of the circuit board varnish is a laminate. As a method of obtaining the cured product of the circuit board varnish, first, the circuit board varnish is impregnated with glass fiber, carbon fiber, polyester fiber, and polyamide. Fiber, alumina fiber, paper, and other known substrates are heated and dried to obtain a prepreg. The prepreg may be laminated on each other, or the prepreg and a metal foil such as a copper foil may be laminated and hot-pressed to obtain a cured product of the varnish for a circuit board.

In addition, an inorganic high-dielectric powder such as barium titanate or an inorganic magnetic body such as ferrite is added to the curable resin composition of the present invention as a material for electronic parts, particularly a high-frequency electronic part material. it works.

In addition, like the hardened composite material described later, the hardenable resin composition of the present invention can be bonded to a metal foil (including the meaning of a metal plate. The same applies hereinafter), or can be used by being coated on the metal foil.

The curable resin composition of the present invention can be made into a curable composite material by being impregnated into a known substrate. The curable composite material is one form of a curable resin composition. By making into a hardenable composite material, for example, a circuit board material having high mechanical strength and excellent dimensional stability can be obtained.

As known substrates used in hardenable composite materials, various glass cloths such as non-twisting roving cloth, cloth, chopped mat, and surfacing mat, and asbestos cloth can be used individually. , Metal fiber cloth and other synthetic or natural inorganic fiber cloth, woven or non-woven cloth obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, polybenzoxazole fibers, and polyethylene Woven or non-woven fabrics obtained from synthetic fibers such as base alcohol fibers, polyester fibers, acrylic fibers, natural fiber cloths such as cotton, linen, felt, carbon fiber cloths, kraft paper, cotton paper, and paper-glass mixed fiber Cloth and other cloth, paper, etc., or a combination of two or more.

The proportion of the substrate in the hardenable composite material may be 5 wt% to 90 wt%, preferably 10 wt% to 80 wt%, and more preferably 20 wt% to 70 wt%. If the base material is less than 5 wt%, there is a tendency that the dimensional stability or strength of the composite material after curing is reduced. In addition, when the base material is more than 90 wt%, the dielectric properties of the composite material tend to decrease. In the curable composite material of the present invention, a coupling agent may be used as necessary in order to improve the adhesion between the interface between the resin and the substrate. As the coupling agent, general coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and an aluminum-zirconium coupling agent can be used.

As a method for producing the curable composite material, for example, a method of uniformly dissolving or dispersing the curable resin composition of the present invention and other components as needed in the aromatic, ketone, and other solvents In the mixed solvent or the mixed solvent, the substrate is impregnated and then dried. Impregnation is performed by dipping, coating, or the like. The impregnation may be repeated as many times as necessary. In addition, multiple impregnations with different compositions or concentrations may be used to repeat the impregnation at this time, and the desired resin composition and resin amount may be finally adjusted.

The hardened composite material can be hardened by a method such as heating to obtain a hardened composite material. The said composite hardened | cured material is one form of the hardened | cured material of this invention. The manufacturing method is not particularly limited. For example, a plurality of hardenable composite materials can be superimposed and heat-cured while adhering to each other under heat and pressure to obtain a hardened composite material of a desired thickness. In addition, a cured composite material having a new layer structure may be obtained by combining a cured composite material that has undergone primary adhesion hardening and a curable composite material. Lamination molding and curing are usually performed simultaneously by hot pressing or the like, but they may be performed separately and separately. That is, the unhardened or semi-hardened composite material obtained by performing the lamination in advance may be hardened by heat treatment or processing by other methods.

Molding and hardening can be performed at a temperature of 80 ° C to 300 ° C, a pressure of 0.1 kg / cm ² to 1000 kg / cm ² , and a time of 1 minute to 10 hours. A more preferred temperature is 150 ° C to 250 ° C and a pressure of 1 kg. / cm ² to 500 kg / cm ² , time: within a range of 1 minute to 5 hours.

The laminated body of this invention contains the layer of the hardened | cured material of this invention, and the metal foil layer. Examples of the metal foil used herein include copper foil, aluminum foil, and the like. The thickness is not particularly limited, but is in the range of 3 μm to 200 μm, and more preferably in the range of 3 μm to 105 μm.

As a method for producing the laminated body of the present invention, for example, a method may be mentioned in which the hardened material or the hardenable composite material and a metal foil are laminated in a layer structure corresponding to the purpose, and the layers are adhered under heat and pressure. Heat-cured at the same time. In the laminated body of this invention, a hardened | cured material or a composite hardened | cured material, and a metal foil are laminated | stacked by arbitrary layer constitutions. Metal foil can be used as a surface layer or as an intermediate layer. In addition to the above, multilayering may be performed by repeating lamination and curing multiple times.

Adhesives can also be used for adhesion to metal foil. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited to these adhesives. The lamination molding and hardening can be performed under the same conditions as the production of the composite hardened material.

The curable resin composition of the present invention may be formed into a film shape. The thickness is not particularly limited, but is in the range of 3 μm to 200 μm, and more preferably in the range of 5 μm to 105 μm.

The method for producing the film is not particularly limited, and examples thereof include a method of uniformly dissolving or dispersing the curable resin composition and other components as needed in an aromatic or ketone-based solvent or a mixed solvent thereof. In the process, it is coated on a resin film such as a polyethylene terephthalate (PET) film and then dried. The coating may be repeated as many times as necessary. In this case, multiple coatings with different compositions or concentrations may be used for repeated coating, and finally adjusted to the desired resin composition and resin amount.

The metal foil with a resin of this invention has the film formed from the curable resin composition of this invention on one surface of a metal foil. The metal foil used here can be the same as the metal foil which comprises the laminated body of this invention.

The method for producing the resin-containing metal foil of the present invention is not particularly limited, and examples thereof include a method of uniformly dissolving or dispersing a curable resin composition and other components as needed in an aromatic or ketone system. In a solvent such as this or a mixed solvent, the metal foil is applied to a metal foil and then dried. The coating may be repeated as many times as necessary. In this case, multiple coatings with different compositions or concentrations may be used for repeated coating, and finally adjusted to the desired resin composition and resin amount. [Example]

Hereinafter, the present invention will be described by examples, but the present invention is not limited by these examples. In addition, the parts in each case are all parts by weight. In addition, the measurement results in the examples are obtained by sample preparation and measurement by the methods shown below.

1) Structural analysis and composition analysis of poly (vinyl benzyl) ether compounds. Gel Permeation Chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), solvent: Tetrahydrofuran (THF), Flow: 1.0 ml / min, column temperature: 40 ° C for implementation), infrared spectroscopic analysis (Frontier Gold Fourier Transform Infrared Spectroscopy, FTIR manufactured by PerkinElmer Japan) ) System, KBr method) and 1H-Nuclear Magnetic Resonance (NMR) analysis (JNM-LA600-type nuclear magnetic resonance spectrometer manufactured by Japan Electronics, solvent: chloroform-d1), to confirm the product and analyze the structure.

In addition, total chlorine was measured by elemental analysis (automatic combustion-ion chromatography, automatic combustion section: AQF-100 manufactured by Mitsubishi Kasei, and ion chromatography section: ICS-1000 manufactured by Thermo Fisher). content. In addition, the presence of an unreacted portion of chloromethylstyrene as a raw material was confirmed by gas chromatography (GC-2010, Shimadzu Corporation, hydrogen flame ionization detector).

2) Tensile strength and elongation The tensile strength and elongation (tensile elongation at break) of the hardened film are based on JIS K7161-1994, using a universal testing machine (manufactured by Toyo Seiki, Strograph) VES05D. ). The elongation is a value obtained by dividing the elongation at the breaking point by the distance between the chucks.

3) Evaluation of flame retardancy Using a thermal balance (Thermal Gravimetric Analysis (TGA), under nitrogen gas flow, heating rate: 10 ° C / min), the thermal decomposition starting temperature obtained by the tangent method and 600 ° C were measured. Carbide formation ratio below.

4) Evaluation of crack resistance A glass cloth (E glass, weight per unit area: 71 g / m ² ) was immersed in a curable resin composition to be impregnated, and dried in an air oven at 50 ° C. for 30 minutes to prepare Prepreg.

Regarding the prepreg, the copper foil of the FR-4 substrate (having a thickness of 0.8 mm) was completely dissolved and removed on both sides of the substrate by etching, so that the thickness after forming was about 0.6 mm to 1.0 mm. Eight pieces of the prepreg were stacked, and copper foils having a thickness of 18 μm were placed on both sides, and the temperature was increased from 30 ° C / min at room temperature to 180 ° C at 30 kg / cm ² using an extrusion molding machine. It was shape-hardened under the condition of holding for 60 minutes, and the laminated body was obtained. In order to form a circuit pattern on the obtained laminate (the outer layer circuit has a shape of 2 mm square), an etching resist (H-K425, Hitachi Chemical Co., Ltd.) was used at 100 ° C, 0.5 m / min, and a pressure of 0.5 MPa. Industrial Co., Ltd. (trade name) is laminated on the copper surface of the laminate. Thereafter, exposure was performed through a photomask (the exposure amount was 80 mJ / cm ² ). Then, using a developing solution of a 1.0% aqueous solution of sodium carbonate, development was performed at 30 ° C., a pressure of 0.1 MPa, and a developing time of 60 seconds, and the resist was stripped with an aqueous sodium hydroxide solution and dried. Then, copper was etched using an aqueous solution of ferric chloride to obtain a crack resistance evaluation pattern in which the outer layer circuit became 2 mm square.

The crack resistance evaluation pattern sample obtained in the above manner was subjected to a cold-heat cycle test at -55 ° C to 125 ° C, and cracks in the insulating resin easily generated in the 2 mm square corner portion of the outer layer circuit were observed with a microscope, and the cracks were maintained until The number of cycle tests until cracks were formed was used to evaluate crack resistance.

Example 1

To a four-necked flask equipped with a temperature regulator, a stirring device, a cooling condenser, and a dropping funnel, SN495V (naphthol aralkyl resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; OH equivalent of phenolic hydroxyl group is 232 g / eq. ., The methoxyl modification amount of phenolic hydroxyl group: 2.7%, the methoxyl content derived from p-xylylene glycol dimethyl ether: ND 195, CMS-AM (manufactured by Seimi Chemical) 44 parts of chloromethylstyrene, 9.6 parts of tetra-n-butylammonium bromide, 0.152 parts of 2,4-dinitrophenol, 255 parts of methyl ethyl ketone, and the solution was stirred and dissolved to change the liquid temperature to 75 ° C. 42 parts of 50% sodium hydroxide aqueous solution was added dropwise over 20 minutes, and stirring was 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 three times with 1500 ml of water.

The obtained organic phase was distilled and concentrated until the organic phase became 460 parts, and methanol / water = 75/25 (vol / vol) 1,000 parts were added to reprecipitate the product. The reprecipitation under the same conditions was repeated twice more. The obtained resin precipitate was filtered and dried to obtain a vinyl benzylnaphthol aralkyl resin (VBE25) as a poly (vinylbenzyl) ether compound as a reaction product of SN495V and vinylbenzyl chloride. -SN495V) 178.1 copies.

The product was confirmed by GPC and 1H nuclear magnetic resonance spectroscopy (1H-NMR). As a result, it was confirmed that in the recovered reaction product, the peak derived from the raw material disappeared in the recovered reaction product, and a new peak was generated on the high molecular weight side. In 1H-NMR, the resonance line of protons derived from chloromethylstyrene disappeared. Instead, the resonance lines of protons derived from benzyl ether group were near 5.02 ppm, and the resonance lines of protons derived from benzyl ether group were near 5.25 ppm, 5.77 ppm and 6.73 ppm. The resonance line of the vinyl proton had a resonance line of a proton derived from a phenolic hydroxyl group near 5.15 ppm, and it was confirmed that a poly (vinylbenzyl) ether compound (VBE25-SN495V) was obtained. Further, the methyl content corresponding to R ² of formula (1) was 2.6 mol%, the vinyl benzyl content (that is, the vinyl benzyl ether modification rate) was 25.4 mol%, and the hydrogen atom was 72 mol. %. The total chlorine content was measured by elemental analysis and found to be 140 ppm. As a result of GC measurement, no peak derived from chloromethylstyrene was observed. In addition, a thermal balance (TGA) was used to measure the thermal decomposition behavior under a nitrogen gas flow at a heating rate: 10 ° C / min. As a result, the thermal decomposition starting temperature obtained by the tangent method: 346 ° C, the amount of carbides generated at 600 ° C It was 41.8 wt%. The average number of OR ² groups per molecule was 10.

Example 2 A four-necked flask equipped with a temperature regulator, a stirring device, a cooling condenser, and a dropping funnel was charged with 195 parts of SN495V, 86.6 parts of CMS-AM, 9.6 parts of tetra-n-butylammonium bromide, and 2,4- 0.152 parts of dinitrophenol and 255 parts of methyl ethyl ketone were dissolved by stirring. The liquid temperature was changed to 75 ° C., 82.5 parts of a 50% sodium hydroxide aqueous solution was added dropwise over 20 minutes, and the stirring was 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 three times with 1500 ml of water.

The obtained organic phase was distilled and concentrated until the organic phase became 440 parts, and methanol / water = 75/25 (vol / vol) 1,000 parts were added to reprecipitate the product. The reprecipitation under the same conditions was repeated twice more. The precipitate of the obtained resin was filtered and dried to obtain 202.5 parts of a vinyl benzylated naphthol aralkyl resin (VBE50-SN495V) as a reaction product of SN495V and vinyl benzyl chloride.

The product was confirmed in the same manner as described above. As a result, it was confirmed that the peak derived from the raw material disappeared, a new peak was generated on the high molecular weight side, and the resonance line of the proton derived from chloromethylstyrene disappeared. Instead, a source near 5.02 ppm Resonance lines of protons from benzyl ether groups have resonance lines of protons derived from vinyl groups near 5.25 ppm, 5.77 ppm, and 6.73 ppm, and resonance lines of protons derived from phenolic hydroxyl groups near 5.15 ppm. Thus, a vinyl benzylated naphthol aralkyl resin (VBE50-SN495V) was obtained. Further, the methyl content of R ² corresponding to the formula (1) was 2.6%, the vinyl benzyl content was 50.2%, and the hydrogen atom was 47.2 mole%. The total chlorine content was measured by elemental analysis, and it was 152 ppm. As a result of GC measurement, no peak derived from chloromethylstyrene was observed. In addition, the thermal decomposition onset temperature: 370 ° C, the amount of carbide formation at 600 ° C was 39.0 wt%. The average number of OR ² groups per molecule was 10.

Comparative Example 1 In a four-necked flask equipped with a temperature regulator, a stirring device, a cooling condenser, and a dropping funnel, 195 parts of SN495V, 160.1 parts of CMS-AM, 9.6 parts of tetra-n-butylammonium bromide, and 2,4- 0.152 parts of dinitrophenol and 255 parts of methyl ethyl ketone were stirred and dissolved, the liquid temperature was changed to 75 ° C., and 160 parts of 50% sodium hydroxide aqueous solution was added dropwise over 20 minutes, and the stirring was 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 three times with 1500 ml of water.

The obtained organic phase was distilled and concentrated until the organic phase became 500 parts, and methanol / water = 75/25 (vol / vol) 1,000 parts was added to reprecipitate the product. The reprecipitation under the same conditions was repeated twice more. The precipitate of the obtained resin was filtered and dried to obtain a vinyl benzylnaphthol aralkyl resin (VBE) as a poly (vinylbenzyl) ether compound as a reaction product of SN495V and vinylbenzyl chloride. -SN495V) 246.7 copies.

As a result of confirming the product, it was confirmed that the peak derived from the raw material disappeared, a new peak was generated on the high molecular weight side, the phenolic hydroxyl group disappeared, and the resonance line of the proton derived from chloromethylstyrene disappeared. Instead, it had a source near 5.02 ppm The resonance lines of protons from benzyl ether groups had resonance lines of protons derived from vinyl groups in the vicinity of 5.25 ppm, 5.77 ppm, and 6.73 ppm, and it was confirmed that VBE-SN495V was obtained. Further, the methyl content corresponding to R ² in formula (1) was 2.6%, the vinyl benzyl content was 97.4%, and the hydrogen atom was 0 mole%. That is, a phenolic hydroxyl group cannot be detected. In addition, the total chlorine content was 167 ppm. No peak derived from chloromethylstyrene was observed. In addition, a differential scanning calorimeter (Differential Scanning Calorimeter, DSC) was used to measure the thermal phase transition behavior at a temperature rise rate of 10 ° C / min under a nitrogen gas flow. As a result, no melting peaks derived from crystals were observed, and the thermal decomposition onset temperature was not observed. : 402 ° C, the amount of carbide formation at 600 ° C was 36.1 wt%.

Example 5 A four-necked flask equipped with a temperature regulator, a stirring device, a cooling condenser, and a dropping funnel was charged with 195 parts of SN495V, 30.5 parts of CMS-AM, 9.6 parts of tetra-n-butylammonium bromide, and 2,4- 0.152 parts of dinitrophenol and 255 parts of methyl ethyl ketone were stirred and dissolved. The liquid temperature was changed to 75 ° C, and 42 parts of a 50% sodium hydroxide aqueous solution was added dropwise over 20 minutes, and the stirring was 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 three times with 1500 ml of water.

The obtained organic phase was distilled and concentrated until the organic phase became 460 parts, and methanol / water = 75/25 (vol / vol) 1,000 parts were added to reprecipitate the product. The reprecipitation under the same conditions was repeated twice more. The precipitate of the obtained resin was filtered and dried to obtain 270.0 parts of a vinyl benzylnaphthol aralkyl resin (VBE15-SN495V) as a reaction product of SN495V and vinyl benzyl chloride.

The product was confirmed in the same manner as described above. As a result, it was confirmed that the peak derived from the raw material disappeared, a new peak was generated on the high molecular weight side, and the resonance line of the proton derived from chloromethylstyrene disappeared. Instead, it had a source near 5.02 ppm. Resonance lines of protons from benzyl ether groups have resonance lines of protons derived from vinyl groups near 5.25 ppm, 5.77 ppm, and 6.73 ppm, and resonance lines of protons derived from phenolic hydroxyl groups near 5.15 ppm. Thus, a vinyl benzylated naphthol aralkyl resin (VBE15-SN495V) was obtained. Further, the methyl content of R ² corresponding to the formula (1) was 2.6%, the vinyl benzyl content was 15.0%, and the hydrogen atom was 82.4 mole%. The total chlorine content was measured by elemental analysis and found to be 121 ppm. As a result of GC measurement, no peak derived from chloromethylstyrene was observed. The thermal decomposition onset temperature was 340 ° C, and the amount of carbides generated at 600 ° C was 42.6 wt%. The average number of OR ² groups per molecule was 10.

Example 7 In a 1 L four-neck separable flask, 288 g of 1-naphthol and 1,5-dichloromethylnaphthalene (1,5-dichloromethyl 95.6%, other dichloromethyl) were weighed out. 3.0%, monochloromethyl (1.4%), 135 g, and 840 g of toluene. Under a nitrogen stream, the temperature was gradually increased while stirring, and the reaction was carried out under reflux at about 116 ° C for 2 hours. Thereafter, the temperature was raised to 180 ° C. while distilling off toluene, and the reaction was performed in the above state for 1 hour. After the reaction, the unreacted 1-naphthol and the solvent were removed by distillation under reduced pressure at 200 ° C to obtain 224 g of a brown resin (polyhydroxy resin A). The hydroxyl equivalent of the obtained polyhydroxy resin A was 230 g / eq.

To a four-necked flask equipped with a temperature regulator, a stirring device, a cooling condenser, and a dropping funnel, 195 parts of polyhydric hydroxy resin A, 44 parts of CMS-AM (chloromethylstyrene manufactured by Kiyomi Chemical Co., Ltd.), and tetrabromide -9.6 parts of n-butylammonium, 0.152 parts of 2,4-dinitrophenol, 255 parts of methyl ethyl ketone and stir to dissolve. The liquid temperature was changed to 75 ° C, and a 50% sodium hydroxide aqueous solution was added dropwise over 20 minutes. 42 The mixture was further stirred 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 three times with 1500 ml of water.

The obtained organic phase was distilled and concentrated until the organic phase became 460 parts, and methanol / water = 75/25 (vol / vol) 1,000 parts were added to reprecipitate the product. The reprecipitation under the same conditions was repeated twice more. The precipitate of the obtained resin was filtered and dried to obtain a vinyl benzylnaphthol resin (VBE25) as a poly (vinylbenzyl) ether compound as a reaction product of a polyhydroxy resin A and vinylbenzyl chloride. -Polyol resin A) 198.1 parts.

As a result of confirming the product, it was confirmed that the peak derived from the raw material disappeared, a new peak was generated on the high molecular weight side, the phenolic hydroxyl group disappeared, and the resonance line of the proton derived from chloromethylstyrene disappeared. Instead, it had a source near 5.02 ppm The resonance lines of protons from benzyl ether groups had resonance lines of protons derived from vinyl groups in the vicinity of 5.25 ppm, 5.77 ppm, and 6.73 ppm, and it was confirmed that VBE-polyhydroxy resin A was obtained. The vinyl benzyl content corresponding to R ² in formula (1) was 25.2%, and the hydrogen atom was 74.8 mole%. In addition, the total chlorine content was 138 ppm. No peak derived from chloromethylstyrene was observed.

The abbreviations are shown below. YDCN-700-3: Cresol novolac epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Epotohto YDCN-700-3) MEH-7851-S: biphenyl phenol novolac resin (Made by Kasei Corporation, MEH-7851-S) XD-1000: Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) A1535: Hydrogenated styrene butadiene block copolymer (Nippon Kraton Polymer) (Kraton Polymer Japan) (KRATON) A1535, Mw = 223,000) Percumyl D: Dicumyl peroxide (manufactured by Nippon Oil Company, Percumyl D) ) AO-60: Pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (manufactured by Adeka (Shares), Idecosta ( Adekastab) AO-60) SE2050 SPE: Amorphous spherical silicon dioxide treated with a phenylsilane coupling agent (manufactured by Admatechs, SE2050 SPE, average particle size 0.5 μm)

Example 3 40 g of VBE25-SN495V obtained in Example 1, 5 g of YDCN-700-3 as epoxy resin, 5 g of MEH-7851-S as phenol resin, and 50 g of thermoplastic Elastomer A1535, 1.0 g of Percumyl D as a polymerization initiator, 0.4 g of Triphenylphosphine (TPP) as a hardening accelerator, 0.2 g of AO-60 as an antioxidant It was dissolved in 82.8 g of xylene to obtain a curable resin composition (varnish A). The prepared varnish A was coated on a PET film and the solvent was removed at 80 ° C. After drying, the coating film was peeled from the PET film, and the separated cast film was vacuum-added at 180 ° C and 3 MPa for 1 hour. It is pressed and thermally hardened to obtain a hardened film. Various characteristics were measured about the obtained varnish A and hardened | cured material film.

Example 4 and Example 6 The test was performed under the same conditions as in Example 3 except that a varnish was prepared with the formulation shown in Table 1. In Table 1, when there is no description of the unit, the blending amount of the blending component is wt%. In addition, a blank indicates that the component is not contained. The test results are shown in Table 2. Comparative Example 2 and Comparative Example 3 A varnish was prepared under the same conditions as in Example 3 except that the varnish was prepared with the formulation shown in Table 1, and a test was performed. The test results are shown in Table 2.

[Table 1]

[Table 2]

no

no

no

Claims (12)

A poly (vinylbenzyl) ether compound represented by the following formula (1),

(1) Here, R ¹ each 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 represents a divalent group having 6 to 50 carbon atoms. Aromatic hydrocarbon groups, R ² each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinyl benzyl group; wherein the proportion of the vinyl benzyl group in R ² is 10 mol% or more and less than 60 Molar%, the proportion of hydrogen atoms is 40 Molar% or more; n is in the range of 1 to 20 as an average, m is a number from 1 to 6, and r is a number from 1 to 3, but m + r does not exceed 6 Or 7. The poly (vinylbenzyl) ether compound according to item 1 of the scope of the patent application, wherein the poly (vinylbenzyl) ether compound is such that R ² in formula (1) is a hydrogen atom, or a hydrogen atom and A naphthol aralkyl resin having an alkyl group of 1 to 12 is obtained by reacting a vinyl aromatic halomethyl compound. The poly (vinylbenzyl) ether compound according to item 1 or item 2 of the scope of patent application, wherein in the formula (1), R ² having one or more in one molecule is a hydrogen atom, or The vinyl benzyl group has an OR ² group (Y), and the average number of OR ² groups (Y) per molecule is 1.1 or more. A curable resin composition comprising: (A) a component, such as the poly (vinylbenzyl) ether compound described in any one of items 1 to 3 of the scope of patent application; and (B) a component, selected 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 two epoxy molecules in one molecule At least one epoxy resin among the above epoxy groups and alicyclic epoxy resins. The curable resin composition according to item 4 of the scope of patent application, further comprising an epoxy resin hardener as the (C) component. A hardened material is formed by hardening the hardenable resin composition according to item 4 or 5 of the scope of patent application. A hardenable composite material comprising a hardenable resin composition and a substrate as described in item 4 or 5 of the scope of patent application. A resin-equipped metal foil having a film made of a curable resin composition as described in item 4 or 5 of the patent application scope on one side of the metal foil. A laminated body comprising a layer of a hardened material as described in item 6 of the scope of patent application and a metal foil layer. A circuit board material formed using a hardened body as described in item 6 of the patent application scope. A varnish which is formed by dissolving a curable resin composition as described in claim 4 or 5 in a solvent. The varnish according to item 11 of the scope of patent application, which is used for circuit substrate materials.