WO2014103926A1

WO2014103926A1 - Poly(vinyl benzyl) ether compound, method for producing same, curable composition containing same, and cured article

Info

Publication number: WO2014103926A1
Application number: PCT/JP2013/084237
Authority: WO
Inventors: 川辺　正直; スレスタ・ニランジャン・クマール
Original assignee: 新日鉄住金化学株式会社
Priority date: 2012-12-27
Filing date: 2013-12-20
Publication date: 2014-07-03
Also published as: JPWO2014103926A1; JP6277134B2; TW201434953A; TWI620786B

Abstract

Provided are: a poly(vinyl benzyl) ether compound which can have high dielectric properties (a low dielectric constant, a low dielectric tangent) even after undergoing a thermal history at a high temperature and enables the production of a cured article having a high glass transition temperature and high flame retardancy; and a curable composition. A poly(vinyl benzyl) ether compound produced by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound, said poly(vinyl benzyl) ether compound being characterized by having a total halogen content of 600 ppm or less, and also having a ratio of a peak area derived from the vinyl aromatic halomethyl compound to the total peak area, which is the sum total of the peak area derived from the vinyl aromatic halomethyl compound and a peak area derived from the poly(vinyl benzyl) ether compound, is 1.0% or less as measured by gel permeation chromatography.

Description

Poly (vinylbenzyl) ether compound, process for producing the same, curable composition containing the same, and cured product

The present invention relates to a poly (vinylbenzyl) ether compound, a production method thereof, a hard curable composition containing the compound, a cured product, a composite material, a cured product thereof, a laminate comprising the cured product and a metal foil, and a resin. It relates to metal foil.

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, cured resins using vinyl benzyl ether compounds having various chemical structures have been proposed.

As such a cured resin, for example, a cured resin such as divinylbenzyl ether of bisphenol or a poly (vinylbenzyl) ether compound of phenol novolac type has been proposed (Patent Document 1, Patent Document 2). However, these poly (vinyl benzyl) ether compounds have not been able to provide sufficient properties in the initial dielectric properties, but also cannot provide a cured resin with a small change in dielectric properties due to severe thermal history, The heat resistance was not high enough.

Several poly (vinyl benzyl) ether compounds with specific structures have been proposed as poly (vinyl benzyl) ether compounds with improved properties. Attempts to suppress changes in dielectric loss tangent when subjected to severe thermal history, and heat resistance Attempts have been made to improve the characteristics, but 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 3, Patent Document 4, and Patent Document 5).
And a curable resin containing at least one hydroxyl group selected from the group consisting of a phenol aralkyl resin, a naphthol aralkyl resin, a biphenyl type phenol novolak resin, and a biphenyl type naphthol novolak resin. A curable resin composition (Patent Document 6) is disclosed. However, the vinyl benzyl etherified curable resin synthesized in accordance with the production method disclosed in the document has a large total halogen content and a large amount of residual vinyl aromatic halomethyl compound, and therefore has a severe heat history. The dielectric loss tangent and the heat resistance are not satisfactory as an insulating material corresponding to a high frequency, and the moldability is not desirable because it tends to cause molding defects. Further, in the literature, the naphthol aralkyl resins are exemplified as specific examples, since it is one which does not contain an alkyl group of 1 to 12 carbon atoms as R ² of formula (1), the alkyl-modified of R ² Effect About was not clear.

Thus, conventional poly (vinyl benzyl) ether compounds satisfy the low dielectric loss tangent after severe thermal history that can withstand lead-free soldering, which is necessary for electrical insulation materials, especially for high frequency electrical insulation materials. It does not give a cured product having heat resistance, and is insufficient in terms of reliability and workability.

JP 63-68537 A JP-A 64-65110 JP-T-1-503238 JP-A-9-31006 JP 2004-323730 A JP 2003-306591 A

The present invention relates to a poly (vinylbenzyl) ether compound that has a high dielectric property (low dielectric constant and low dielectric loss tangent) even after severe thermal history, and gives a cured product having a high glass transition temperature and flame retardancy, and Providing a curable composition, and providing a resin composition, a cured product, or a material containing the same that can be used as a dielectric material, an insulating material, and a heat-resistant material in fields such as the electric / electronic industry, space / aircraft industry, etc. The purpose is to do.

The present inventors have found that a poly (vinylbenzyl) ether compound represented by the following formula (1) is effective for solving the above problems, and completed the present invention.

That is, the present invention is a poly (vinylbenzyl) ether compound represented by the following formula (1) obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound, and has a total halogen content of 600 ppm (wt). Below, in gel permeation chromatography (GPC) measurement, the peak area derived from the vinyl aromatic halomethyl compound is 1.0% or less with respect to the total peak area totaled with the peak area of the poly (vinylbenzyl) ether compound. It is related with the poly (vinyl benzyl) ether compound characterized by the above-mentioned.

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 represents an aryl group having 6 to 50 carbon atoms. , R ² each 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. However, m + r does not exceed 8.

In the formula (1), the ratio of the alkyl group in R ² is preferably 0.1 to 50 mol%, and more preferably 1 to 30 mol%.

The present invention also relates to a curable composition characterized by containing the above poly (vinylbenzyl) ether compound and a radical polymerization initiator, and a cured product obtained by curing the curable composition.

The present invention also relates to a curable composite material comprising the above curable composition and a substrate, a composite material cured product obtained by curing the curable composite material, and a layer and a metal foil of the composite material cured product. It is related with the laminated body which has a layer. Moreover, this invention relates to the metal foil with resin which has the film | membrane formed from said curable composition on the single side | surface of metal foil.

Furthermore, the present invention provides a naphthol aralkyl resin obtained by condensing a hydroxynaphthalene represented by the following formula (2) and an aromatic compound represented by the following formula (3). Reacting with a group halomethyl compound in the presence of an alkali metal hydroxide to obtain a reaction product containing a poly (vinylbenzyl) ether compound, and purifying it with a mixed solvent comprising water and alcohols. The present invention relates to a method for producing the above-mentioned poly (vinylbenzyl) ether compound.

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, m is a number from 1 to 6, and r is a number from 1 to 3. . However, m + r does not exceed 8.

Here, Ar ¹ represents an aryl group having 6 to 50 carbon atoms, and X represents a fluorine atom, a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group.

In the above hydroxynaphthalene or naphthol aralkyl resin, part of the OH group is an alkoxy group (OR group; R is an alkyl group having 1 to 12 carbon atoms), or part or all of the OH group is A mixture of an alkoxy group and a non-alkoxy group is also preferable.

Some preferred embodiments of such a production method are as follows.
The above poly (vinylbenzyl) ether compound obtained by obtaining a naphthol aralkyl resin, then alkoxylating a part of the OH group of the naphthol aralkyl resin, and then reacting the partially modified naphthol aralkyl resin with a vinyl aromatic halomethyl compound Manufacturing method.

Partially modified naphthol aralkyl resin synthesizes naphthol aralkyl resin by condensing hydroxy naphthalene represented by formula (2) and aromatic compound represented by formula (3) wherein X is methoxy group or ethoxy group In this case, methanol or ethanol by-produced by the reaction is refluxed into the reaction system, whereby a part of the OH group of the naphthol aralkyl resin is alkoxylated to obtain an OR group. A method for producing a (vinylbenzyl) ether compound.

In the partially modified naphthol aralkyl resin, the hydroxy naphthalenes represented by the formula (2) and a part or all of the OH groups of the formula (2) are OR groups (R is an alkyl group having 1 to 12 carbon atoms). A mixture of hydroxynaphthalenes including alkoxynaphthalene or a hydroxynaphthalene in which a part of the OH group of formula (2) is an OR group (R is an alkyl group having 1 to 12 carbon atoms) is represented by the formula (3 The method for producing a poly (vinylbenzyl) ether compound as described above, which is obtained by condensing with an aromatic compound represented by

In the poly (vinylbenzyl) ether compound of the present invention, since the total halogen content and the content of the vinyl aromatic halomethyl compound are controlled to be below a certain level, the curable composition containing this compound has a low dielectric loss tangent. Thus, a material having high flame retardancy and low dielectric loss tangent and excellent heat reliability can be realized.

The present invention will be further described below.
The poly (vinylbenzyl) ether compound of the present invention is obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound, and is represented by the formula (1). A typical compound of the poly (vinyl benzyl) ether compound is poly (vinyl benzyl) ether.

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. These groups may further have a substituent, for example, an alkyl group having 1 to 6 carbon atoms. 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, preferably 6 in view of the balance between solubility and dielectric properties and curability and flame retardancy. And particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
M represents a number from 1 to 6. Preferably, from the viewpoint of the balance between solubility and flame retardancy, m is a number from 0 to 2 when R ¹ is a functional group excluding hydrogen.

R ² each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group. The proportion (mol%) of the vinylbenzyl group in R ² is 60 to 100%, preferably 90 to 100%. 0 to 40%, preferably 0 to 10% is a hydrogen atom, an alkyl group or both. When the proportion of the vinylbenzyl group is less than 60%, the polymerization active point is small and the phenolic hydroxyl group is large, which causes problems such as insufficient curing and deterioration of dielectric properties, which is not preferable.
R represents a number of 1 to 3, preferably 1 or 2 from the viewpoint of solubility and toughness. m + r is 8 or less, preferably 1 to 4.

Ar ¹ represents an aryl 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- 6 to 6 carbon atoms selected from the group consisting of CH (CH ₃ ) -Ph-, -Ph-CH (C ₆ H ₅ ) -Ph-, -Ph-Flu-Ph-, and -Flu (CH ₃ ) _2- 50 aryl groups and the like. More preferred is an aryl 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. An alkyl group having 1 to 6 carbon atoms is preferable. Ar ¹ is more preferably unsubstituted, alkyl group substituted, alkoxy group substituted or phenyl group substituted -Ph-, -Ph-Ph- or -Np- from the viewpoint of solubility and flame retardancy. . More preferred is unsubstituted or alkyl group-substituted -Ph-.

In addition, n is an average value and represents a number from 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 an average value (number average).

Furthermore, the poly (vinylbenzyl) ether compound represented by the formula (1) of the present invention has a peak area derived from a vinyl aromatic halomethyl compound in gel permeation chromatography (GPC) measurement, which is a poly (vinylbenzyl) ether compound. It is 1.0% or less with respect to the total peak area totaled with the peak area. Preferably, it is 0.5% or less, more preferably 0.2% or less. If the peak area exceeds 1.0%, it is not preferable because the deterioration of the dielectric characteristics after receiving a thermal history of 250 ° C. or higher for a long time becomes large. Here, the peak area of the poly (vinylbenzyl) ether compound means a peak area based on a pure poly (vinylbenzyl) ether compound. The poly (vinylbenzyl) ether compound of the present invention is a reaction product or a purified product thereof, and contains a small amount of other components in addition to the pure poly (vinylbenzyl) ether compound.

The poly (vinylbenzyl) ether compound represented by the formula (1) of the present invention has a total halogen content of 600 ppm or less. Preferably, it is 450 ppm or less, More preferably, it is 200 ppm or less. If the total halogen content exceeds 600 ppm, it is not preferable because the deterioration of dielectric properties after receiving a heat history of 250 ° C. or higher for a long time becomes large. Since this halogen is mainly derived from the aromatic halomethyl compound as a raw material, it is related to the peak area of the poly (vinylbenzyl) ether compound.

Next, a method for producing the poly (vinylbenzyl) ether compound represented by the formula (1) of the present invention will be described below.

The poly (vinylbenzyl) ether compound represented by the formula (1) of the present invention is obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound. Naphthol aralkyl resin is represented by the following formula (4). The production method of the naphthol aralkyl resin is not particularly limited, but is preferably obtained by subjecting the hydroxynaphthalene represented by the above formula (2) and the aromatic compound represented by the above formula (3) to a condensation reaction. It is done.

In the formulas (1) to (4), common symbols have the same meanings unless otherwise specified.

The reaction of the naphthol aralkyl resin and the vinyl aromatic halomethyl compound is carried out by reacting in the liquid phase in the presence of an alkali metal hydroxide. In this reaction, the OH group of the naphthol aralkyl resin and the CH2X group of the vinyl aromatic halomethyl compound undergo a condensation reaction to generate deHCl and an O—CH2 bond, thereby producing a poly (vinylbenzyl) ether compound.

Further, for the purpose of improving toughness and moldability, a part of the phenolic hydroxyl group of the naphthol aralkyl resin represented by the above formula (4) is, for example, in the presence of an acidic catalyst according to the method described in Japanese Patent No. 4465257. By reacting with an alcohol having 1 to 12 carbon atoms, 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 0.1 to 50 mol%. More preferably, it is 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 the front is preferable in order to avoid polymerization of the vinyl group. In the previous case, a partially alkylated naphthol aralkyl resin (partially modified naphthol aralkyl resin) in which a part of the hydrogen atom of the hydroxyl group is substituted with an alkyl group is synthesized first, and then reacted with a vinyl aromatic halomethyl compound. This is a method for obtaining a partially alkylated poly (vinylbenzyl) ether compound. In the latter case, a naphthol aralkyl resin and a vinyl aromatic halomethyl compound were reacted to obtain a poly (vinylbenzyl) ether compound, and then a part of the remaining hydroxy group was alkylated to be partially alkoxylated. This is a method for obtaining a poly (vinylbenzyl) ether compound. Here, the partially alkylated poly (vinylbenzyl) ether compound is also included in the poly (vinylbenzyl) ether compound of the present invention. The partially alkylated naphthol aralkyl resin is also referred to as a partially modified naphthol aralkyl resin, which is included in the naphthol aralkyl resin used in the present invention.

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 OH group as an alkoxy group can also be used. It can also be used in combination. When using an OH group having a part of an alkoxy group, it is not necessary to use a hydroxynaphthalene in which the OH group is not modified.

Further, the naphthol aralkyl resin may be a mixture of an OH group in which all of the OH groups are alkoxylated and a resin in which all of the OH groups remain, and this is also partially included in the modified naphthol aralkyl resin.

In the formulas (1) to (4), the same symbols have the same meaning. Therefore, R ¹ , R ² , Ar ¹ , n, m and r in formulas (2) to (4) are the same as those in formula (1). X in Formula (3) represents a fluorine atom, a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group.

Next, a naphthol aralkyl resin and a vinyl aromatic halomethyl compound are reacted in the presence of an alkali metal hydroxide to obtain a reaction product containing a poly (vinylbenzyl) ether compound, which is obtained from water and alcohols. To be purified with a mixed solvent.

The hydroxy naphthalenes represented by the above formula (2) are preferably α-naphthol, β-naphthol, naphthalene diol, 2-methyl-1-naphthol, 3-methyl-2-naphthol, trihydroxynaphthalene, etc. Hydroxynaphthalene is mentioned, These can be used 1 type or 2 or more types. From the viewpoints of solubility, flame retardancy, and availability of raw materials, α-naphthol, β-naphthol, or naphthalenediol is more preferable.

In the above formula (3), X is a condensation active group and represents a fluorine atom, a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group, but preferably in the ease of condensation and in industrial practice. From the viewpoint of availability of raw materials, it is a chlorine atom or a hydroxyl group. Examples of the aromatic compound represented by the formula (3) include 4,4′-bis (fluoromethyl) -1,1′-biphenyl, 4,4′-bis (chloromethyl) -1,1′- Biphenyl, 4,4′-bis (bromomethyl) -1,1′-biphenyl, 4,4′-bis (hydroxymethyl) -1,1′-biphenyl, 4,4′-bis (hydroxyethyl) -1, 1'-biphenyl, di (chloromethyl) benzene, di (bromomethyl) benzene, di (chloromethyl) naphthalene, di (chloromethyl) biphenyl ether, xylylene glycol, xylylene glycol dimethyl ether, xylylene glycol diethyl ether, xylylene Glycol dipropyl ether, xylylene glycol dibutyl ether, xylylene glycol monomethyl ether Such as xylylene glycol mono- or di-lower alcohol ethers, such as xylylene glycol monoethyl ether. More preferred is xylylene glycol, xylylene glycol dimethyl ether, dichloromethylbenzene, or 4,4'-bis (chloromethyl) -1,1'-biphenyl. Particularly preferred is xylylene glycol dimethyl ether.

As the naphthol aralkyl resin represented by the above formula (4), 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 (4) can also be produced by a known method. For example, JP-A No. 2001-213946, JP-A No. 11-255868, JP-A No. 11-228673, JP-A No. 08-073570, JP-A No. 08-048755, and JP-A No. 10-310634. And JP-A-11-116647. The naphthol aralkyl resin represented by the above formula (4) may be used alone or in combination of two or more.

Although not particularly limited, a naphthol aralkyl resin represented by the above formula (4) (including the above partially modified naphthol aralkyl resin; the same shall apply hereinafter) and a vinyl aromatic halomethyl compound giving a vinyl benzyl group moiety; To synthesize a poly (vinylbenzyl) ether compound.

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. An alkyl group having 1 to 6 carbon atoms is preferable. 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.

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 Mention may be made of mixtures of -vinylbenzyl bromide and m-vinylbenzyl bromide. In particular, 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. The composition ratio of p-vinylbenzyl halide and m-vinylbenzyl halide is not particularly limited, but is preferably p-form / m-form = 90/10 to 10/90 (mol / mol), 70/30 More preferably, it is ˜30 / 70 (mol / mol), more preferably 60/40 to 40/60 (mol / mol).

The reaction between the naphthol aralkyl resin represented by the above formula (4) and the vinyl aromatic halomethyl compound is not particularly limited. For example, the naphthol aralkyl resin and the vinyl aromatic halomethyl compound are treated with an alkali metal water in a polar solvent. The method of making it react using an oxide as a dehydrohalogenating agent is mentioned.

The blending ratio of the naphthol aralkyl resin and the vinyl aromatic halomethyl compound is preferably 100: 95 to 100: 120 in terms of an equivalent ratio (OH: halomethyl molar ratio). When the equivalent ratio is within this range, an amount close to the total amount of the naphthol aralkyl resin charged reacts with the vinyl aromatic halomethyl compound, and the hydroxyl group in the naphthol aralkyl resin is vinylbenzyl etherified, and almost remains in the reaction product. By eliminating, the curing reaction to be performed later proceeds sufficiently, and good dielectric properties are exhibited, which is preferable.

The production method in the case of introducing an alkyl group having 1 to 12 carbon atoms into R ² of the formula (1) is not particularly limited, but preferably a mixture of naphthols and alkoxynaphthalene is represented by the above formula (3). It can be produced by reacting an aromatic compound with an acidic catalyst. In that case, the ratio of the hydrogen atom (H) occupying the structural unit represented by R ² present as an average in the resin and the alkyl group (R) having 1 to 12 carbon atoms is not limited, but dielectric properties, moldability From the viewpoint of releasability, the R / H (molar ratio) is preferably 0.0025 or more. More preferably, it is the range of 0.1 or more.
Here, as the alkyl group having 1 to 12 carbon atoms in R ² , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, a propargyl group, a butyl group, an n-amyl group, a sec-amyl group, Examples thereof include a tert-amyl group, a cyclohexyl group, a phenyl group, and a benzyl group, preferably a methyl group, an ethyl group, and an n-propyl group, and more preferably a methyl group.

In carrying out the reaction with the vinyl aromatic halomethyl compound, a polar solvent is preferably used. Preferred polar solvents include alcohols such as methanol, ethanol, propanol and butanol, dimethylformamide, dimethylacetamide, N- Amide solvents such as methyl pyrrolidone, ether solvents such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, 1,3-dimethoxypropane, 1,2-dimethoxyethane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone , Dimethyl sulfoxide, acetonitrile, or a mixed solvent thereof.

In carrying out the above reaction, an alkali metal hydroxide is preferably used for promoting the reaction, and preferred alkali metal hydroxides include sodium hydroxide, potassium hydroxide, or a mixture thereof. . The blending ratio of the alkali metal hydroxide is preferably in the range of 1.1 to 2.0 times in terms of an equivalent ratio with respect to the hydroxy group of the aromatic hydroxy compound.

The reaction temperature and reaction time of the above reaction may be appropriately selected depending on the reaction, but the reaction proceeds sufficiently if they are in the range of 30 to 100 ° C. and 0.5 to 20 hours, respectively.

As another reaction method, a naphthol aralkyl resin and a vinyl aromatic halomethyl compound are dehydrogenated in a mixture of water and an organic solvent in the presence of a phase transfer catalyst such as a quaternary ammonium salt. A poly (vinyl benzyl) ether compound is produced by reacting with a halogenated halide.

Since the reaction product is a crude poly (vinylbenzyl) ether compound containing the poly (vinylbenzyl) ether compound of the formula (1), it is purified to obtain the poly (vinylbenzyl) ether compound of the present invention. Although there is no restriction | limiting in the purification method, It is preferable to refine | purify by reprecipitation refinement | purification or recrystallization using a poor solvent.

As the poor solvent, those having low solubility of the poly (vinylbenzyl) ether compound and high solubility of the halogen compounds are suitable. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, ethylene glycol, water, or a mixed solvent thereof, preferably a mixed solvent of water and alcohols. Suitable as such a poor solvent is a polar solvent having a solubility parameter of 10 or more, more preferably a polar solvent having a solubility parameter of 11 or more. In particular, from the viewpoint of the purification efficiency for reducing the recovery yield of poly (vinylbenzyl) ether compound and the total halogen content to 600 ppm or less, and the peak area derived from vinyl aromatic halomethyl compounds to 1.0% or less, the solubility parameter The value of is most preferably in the range of 15-20.

In the purification, the total halogen content in the poly (vinylbenzyl) ether compound of the present invention is 600 ppm or less, and the peak area derived from the vinyl aromatic halomethyl compound in GPC measurement is poly (vinylbenzyl) of formula (1). ) The total peak area combined with the peak area of the ether compound is reduced to 1.0% or less, but this can be achieved by adjusting the recrystallization conditions and the number of times.

If the total halogen content exceeds 600 ppm, it is not preferable because the deterioration of dielectric properties after a long thermal history of 250 ° C. or more is increased. More preferably, the total halogen content is 450 ppm or less. Most preferably, the total halogen content is 200 ppm or less. When the halogen content is 600 ppm or less, it is preferable because an undesirable effect of avoiding molding defects such as warpage and transfer defects can be obtained. On the other hand, if the peak area derived from the vinyl aromatic halomethyl compound exceeds 1.0%, it is not preferable because the deterioration of dielectric properties after a long heat history of 250 ° C. or more is increased. More preferably, it is 0.5% or less. More preferably, it is 0.2% or less. 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.

Next, the curable composition of this invention is demonstrated.
The curable composition of the present invention contains the poly (vinylbenzyl) ether compound of the present invention and a radical polymerization initiator (also referred to as a radical polymerization catalyst). 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 promoting the above, a radical polymerization initiator may be contained and used. The amount of the radical polymerization initiator used for this purpose is 0.1 to 10% by weight, preferably 0.1 to 8% by weight, based on the sum of the components (A) and (B). Since the radical polymerization initiator is a radical polymerization catalyst, it is represented below by a radical polymerization initiator.

Representative 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 Although there are peroxides such as (trimethylsilyl) peroxide and trimethylsilyltriphenylsilyl peroxide, they are not limited thereto. 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, the reaction proceeds well without inhibiting the curing reaction.

Further, if necessary, the poly (vinylbenzyl) ether compound-containing curable composition may be blended with another polymerizable monomer copolymerizable with the poly (vinylbenzyl) ether compound of the present invention and cured. .

Examples of copolymerizable monomers include styrene, styrene dimer, alphamethylstyrene, alphamethylstyrene dimer, divinylbenzene, vinyltoluene, t-butylstyrene, chlorostyrene, dibromostyrene, vinylnaphthalene, vinylbiphenyl, acenaphthylene, divinyl. Examples thereof include benzyl ether and allyl phenyl ether.

The curable resin composition containing the poly (vinyl benzyl) ether compound of the present invention includes known thermosetting resins such as vinyl ester resins, polyvinyl benzyl resins, unsaturated polyester resins, maleimide resins, epoxy resins, Polycyanate resins, phenol resins, etc., known thermoplastic resins such as polystyrene, polyphenylene ether, polyether imide, polyether sulfone, PPS resin, polycyclopentadiene resin, polycycloolefin resin, etc., or known heat Plastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene Isoprene Polymer etc. and or gums such as polybutadiene, may be blended with polyisoprene.

In the curable composition of the present invention, by using together an inorganic filler such as fused silica, crystalline silica, alumina, silicon nitride, aluminum nitride, a flame retardant imparting agent such as decabromodiphenylethane, brominated polystyrene, It can be used particularly effectively as an electrical or electronic component material that requires dielectric properties, flame retardancy, or heat resistance, especially as a semiconductor sealing material or circuit board varnish.

The varnish for circuit board material can be produced by dissolving the curable composition of the present invention in a solvent such as toluene, xylene, tetrahydrofuran, dioxolane and the like. Specific examples of the circuit board material include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

The cured product obtained by curing the curable 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, a cured product of a semiconductor sealing material is a cast or molded product. As a method for obtaining a cured product for such use, the compound is cast or molded using a transfer molding machine, an injection molding machine, or the like. Further, a cured product can be obtained by heating at 80 to 230 ° C. for 0.5 to 10 hours. Moreover, the hardened | cured material of the varnish for circuit boards is a laminated body, and as a method of obtaining this hardened | cured material, the varnish for circuit boards is used for base materials, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper. It is impregnated and dried by heating to obtain a prepreg, which can be obtained alone or laminated with a metal foil such as a copper foil and subjected to hot press molding.

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

Further, the curable composition of the present invention can be used by being bonded to a metal foil (meaning including a metal plate, hereinafter the same), as with the cured composite material described later.

Next, the curable composite material of the curable composition of the present invention and the cured product thereof will be described. A substrate is added to the curable composite material of the curable 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, and felt. , Carbon fiber cloth, kraft paper, cotton paper, natural cellulosic cloth such as paper-glass mixed paper, paper and the like are used alone 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 composite material can be 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 cured composite material 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 above-described curable composition of the present invention and a curable composite material obtained from a substrate and a metal foil are laminated in a layer configuration according to the purpose, and heated. An example is a method in which the respective layers are bonded together under pressure and thermally cured. In the laminate of the curable 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 bonding 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 of the present invention.

Moreover, the curable 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 of the present invention is not particularly limited. For example, the curable composition and other components as required are uniformly dissolved in an aromatic solvent, a ketone solvent, or a mixed solvent thereof. Alternatively, a method of dispersing, applying to a resin film such as a PET film, and drying may be used. 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 composition of the present invention and the 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 composition and other components as necessary in an aromatic solvent, a ketone solvent or a mixed solvent thereof. A method of uniformly dissolving or dispersing, applying to a metal foil and then drying is exemplified. 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.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. 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 (vinylbenzyl) ether compound GPC (manufactured by Tosoh, HLC-8120GPC) was used for molecular weight and molecular weight distribution measurement, 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) Sample preparation and measurement of glass transition temperature (Tg) and softening temperature measurement After the curable 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) Bending toughness A test piece having a width of 5.0 mm and a length of 40 mm was prepared from a 2.0 mm thick flat plate obtained from the curable composition, and a bending test was performed using a bending test apparatus. It was. At this time, the bending toughness value (FD) calculated by the following formula was used to evaluate the bending toughness of the material.
FD = bending strength (MPa) / bending fracture strain (%)
FD was evaluated as 50 or more as D, less than 50, 40 or more as C, less than 40, 30 or more as B, and less than 30 as A.

5) Releasability Width: 3.0mm, Length: 20mm, Depth: 0.2mm Indentation of a flat plate using a mold containing 5 engravings at intervals of 3.0mm A 2.0 mm flat plate was cured and molded, and the shape of five rectangular portions on the cured flat plate was observed to evaluate the releasability. A rectangular shape with no defects such as cracks, chips, or shrinkage, and a rectangular shape with good reproducibility. A, rectangular shapes with cracks, chips, or shrinkage. There was no defect, but the corner part of the rectangular part was rounded B, the reproducibility of the rectangular part shape was good, but the rectangular part shape was cracked, chipped, closed, etc. Evaluated as C, where the molding failure was observed, and D, where the corner shape of the rectangular part was rounded, and the molding of the rectangular part was observed as cracking, chipping, or shrinkage. Went.

6) 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.

7) Dielectric constant and dielectric loss tangent In accordance with JIS C2565 standard, cured after storing in a room with 23 ° C and 50% humidity for 24 hours after drying completely using a cavity resonator method dielectric constant measuring device manufactured by ATE Co., Ltd. The dielectric constant and dielectric loss tangent at 2 GHz of the product film and the cured film after standing for 2 weeks at 85 ° C. and 85% relative humidity were measured.

6) Formability An uncured film of a curable composition is laminated on a blackened copper-clad laminate, and vacuum laminated at a temperature of 110 ° C. and a press pressure of 0.1 MPa using a vacuum laminator. And evaluated by the adhesion state of the blackened copper foil and the film. The evaluation is that the adhesion between the blackened copper foil and the film is good, the warp of the molded product is less than 1.0 mm, and the area is less than 1.0% in swelling, A, blackened The adhesion between the copper foil and the film is good, but the molded product has a warp of 1.0 mm or more and less than 2.0 mm, or a partial swelling of 1.0% or more and less than 5.0% in terms of area. B, a blackened copper foil and a film in an adhesive state where the film and the film can be easily peeled, or a molded product with a warp of 2.0 mm or more, or an area of 5.0% or more Those that produced a partial bulge were evaluated as C.

Explanation of abbreviations used in Examples and Synthesis Examples.
SN-485: 1-naphthol aralkyl resin (hydroxyl equivalent 214, softening point 88 ° C., melt viscosity 1.9 Pa · s (150 ° C.), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
SN495V: naphthol aralkyl resin (OH equivalent of phenolic hydroxyl group: 232 g / eq., Alkoxy modification rate of phenolic hydroxyl group: 2.7%, alkoxy group content derived from p-xylylene glycol dimethyl ether: ND Nippon Steel & Sumikin Chemical (Made by Co., Ltd.)
SN475N: naphthol aralkyl resin (OH equivalent of phenolic hydroxyl group 218 g / eq., Alkoxy modification amount of phenolic hydroxyl group: ND, alkoxy group content derived from p-xylylene glycol dimethyl ether: ND Nippon Steel & Sumikin Chemical (Made by Co., Ltd.)
CMS-AM: Chloromethylstyrene (manufactured by Seimi Chemical)

Synthesis example 1
Into a 1 L, 3-neck separable flask equipped with a stirrer, cooling tube, and nitrogen introducing tube, 500 g of SN-485, 50 g of methanol, and 5 g of p-toluenesulfonic acid were charged, heated while introducing nitrogen, and stirred while stirring. The temperature was raised at 0 ° C. and reacted for 5 hours. Thereafter, p-toluenesulfonic acid was removed by washing with water, and the temperature was raised to 200 ° C. under reduced pressure to remove unreacted methanol to obtain 507 g of naphthol aralkyl resin (naphthol aralkyl resin A). The obtained naphthol aralkyl resin A had a softening point of 82 ° C., a melt viscosity at 150 ° C. of 0.10 Pa · s, and a hydroxyl group equivalent of 335. The ratio of methoxy groups (methoxy modification ratio) to the total amount of hydroxyl groups and methoxy groups of the naphthalene ring determined from ¹ H-NMR spectrum was 28%.

Synthesis example 2
In a 2 L, 3-neck separable flask equipped with a stirrer, a condenser tube, and a nitrogen inlet tube, 600 g of 1-naphthol, 262 g of 1-methoxynaphthalene, 290 g of p-xylylene glycol dimethyl ether, and 5.8 g of p-toluenesulfonic acid were added. The mixture was heated and dissolved at 90 ° C. while introducing nitrogen. Then, it heated up at 150 degreeC, stirring, and was made to react for 5 hours. During this time, methanol produced by the reaction was removed out of the system. Thereafter, p-toluenesulfonic acid was removed by washing with water, and the temperature was raised to 200 ° C. under reduced pressure to remove unreacted 1-naphthol and 1-methoxynaphthalene to obtain 603 g of naphthol aralkyl resin (naphthol aralkyl resin). B). The obtained naphthol aralkyl resin B had a softening point of 84 ° C., a melt viscosity of 0.12 Pa · s, a hydroxyl group equivalent of 275, and a methoxy group modification rate of 15%.

Example 1
In a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel, 195 parts of SN495V (1.0 equivalent), 160.1 parts of CMS-AM (1.05 equivalents), tetra-n-butylammonium 9.6 parts of bromide, 0.152 parts of 2,4-dinitrophenol and 255 parts of methyl ethyl ketone were added and dissolved by stirring. The temperature of the liquid was adjusted to 75 ° C., and 160 parts (2.0 equivalents) of 50% aqueous sodium hydroxide solution was added for 20 minutes. Then, 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 with 1500 parts of water three times.

The obtained organic phase was distilled to concentrate until the organic phase became 500 parts, and 1,000 parts of methanol / water = 75/25 (v / v) 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 (VBESN 495V) as a poly (vinylbenzyl) ether compound which is a reaction product of SN495V and vinylbenzyl chloride.

When the product was confirmed by GPC and IR ¹ H-NMR, the peak derived from the raw material disappeared, a new peak was formed on the high molecular weight side, the phenolic hydroxyl group disappeared, The proton resonance lines derived from methylstyrene disappear, and instead, the proton resonance lines derived from the benzyl ether group around 5.02 ppm are derived from vinyl groups around 5.25 ppm, 5.77 ppm and 6.73 ppm. It was confirmed to have a proton resonance line, and it was confirmed that VBESN 495V was obtained. The alkoxy 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 GPC 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%.

Example 2
In a four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser and a dropping funnel, 195 parts of SN475N (1.0 equivalent), 160.1 parts of CMS-AM (1.05 equivalents), tetra-n-butylammonium 9.6 parts of bromide, 0.152 parts of 2,4-dinitrophenol and 255 parts of methyl ethyl ketone were added and dissolved by stirring. The temperature of the liquid was adjusted to 75 ° C., and 160 parts (2.0 equivalents) of 50% aqueous sodium hydroxide solution was added for 20 minutes. Then, 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 with 1500 parts of water three times.

The obtained organic phase was distilled and concentrated until the organic phase became 500 parts, and 1,000 parts of methanol / water = 75/25 (v / v) 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 (VBESN475N) which is a reaction product of SN475N and vinylbenzyl chloride.

The product was confirmed in the same manner as in Example 1, and it was confirmed that VBESN475N was obtained. The vinylbenzyl ether group content was 99.5% or more. On the other hand, alkoxy groups and phenolic hydroxyl groups in which the phenolic OH group of 1-naphthol was modified could not be detected. The total chlorine content is 178 ppm, and the peak area derived from chloromethylstyrene (chloromethylstyrene peak area ratio) is 0.05% of the total peak area totaled with the peak areas of VBESN475N and chloromethylstyrene. Met. Moreover, the melting peak derived from a crystal | crystallization was not observed, the thermal decomposition start temperature was 412.0 degreeC, and the carbide | carbonized_material production amount in 600 degreeC was 40.1 wt%. *

Examples 3-5
Vinylbenzylation was carried out by the same production method as in Example 1 except that SN-485, naphthol aralkyl resin A obtained in Synthesis Example 1 or naphthol aralkyl resin B obtained in Synthesis Example 2 was used as the naphthol aralkyl resin. Naphthol aralkyl resins (VBE-A to VBE-C) were synthesized. The evaluation results of the obtained vinylbenzylated naphthol aralkyl resin are shown in Table 1. ND means not detected. The vinyl benzyl ether group (%), the phenolic OH group (%) and the alkoxy group (%) are the ratio in R ² of the formula (1). Chloromethylstyrene (%) is the chloromethylstyrene peak area ratio.

Example 6
The organic phase obtained by reacting, neutralizing and washing under the same conditions as in Example 2 was concentrated by distillation until the organic phase was 500 parts, and methanol / water = 75/25 (v / v). 1,000 parts are added to reprecipitate the product, and the resulting resin precipitate is filtered and dried, and a vinylbenzylated naphthol aralkyl resin (VBE-D) 275, which is a reaction product of SN475N and vinylbenzyl chloride. .3 parts were obtained.

Example 7
The organic phase obtained by reacting, neutralizing and washing under the same conditions as in Example 2 was distilled and concentrated until the organic phase was 500 parts, methanol / water = 75/25 (v / v ) 1,000 parts were added to reprecipitate the product, and reprecipitation under the same conditions was repeated once more. The resulting resin precipitate was filtered and dried to obtain 252.8 parts of vinylbenzylated naphthol aralkyl resin (VBE-E) which is a reaction product of SN475N and vinylbenzyl chloride.

Comparative Example 1
The organic phase obtained by reacting, neutralizing and washing under the same conditions as in Example 2 was distilled and concentrated until distillation of the solvent was completed. Reprecipitation was not performed. 326.8 parts of vinylbenzylated naphthol aralkyl resin (VBE-F) which is a reaction product of SN475N and vinylbenzyl chloride was obtained.

Example 8
The organic phase obtained by reacting, neutralizing and washing under the same conditions as in Example 2 was concentrated by distillation until the organic phase was 500 parts, and 1,000 parts of methanol (100%) was added. The product was reprecipitated and reprecipitation under the same conditions was repeated two more times. The resulting resin precipitate was filtered and dried to obtain 89.3 parts of a vinylbenzylated naphthol aralkyl resin (VBE-G) which is a reaction product of SN475N and vinylbenzyl chloride.

The product was confirmed in the same manner as in Example 1, and it was confirmed that VBE-G was obtained. The vinylbenzyl ether group content was 99.5% or more, and the alkoxy group and phenolic hydroxyl group in which the phenolic OH group of 1-naphthol was modified were not detected. The total chlorine content was 18.0 ppm, and no peak derived from chloromethylstyrene was detected. Moreover, the melting peak derived from a crystal | crystallization was not observed, but thermal decomposition start temperature: 389.7 degreeC, and the carbide | carbonized_material production amount in 600 degreeC was.

The products obtained in Examples 6 to 8 and Comparative Example 1 were confirmed in the same manner as in Example 1, and it was confirmed that VBE-D, VBE-E, VBE-F and VBE-G were obtained. did.
The vinyl benzyl ether group content was 99.5% or more for all of VBE-D, VBE-E, VBE-F and VBE-G.
None of VBE-D, VBE-E, VBE-F and VBE-G were detected for the alkoxy group and the phenolic hydroxyl group in which the phenolic OH group of 1-naphthol was modified.
None of VBE-D, VBE-E, VBE-F and VBE-G were observed as melting peaks derived from crystals.

・ The total chlorine content was as follows.
VBE-D: 578ppm
VBE-E: 382ppm
VBE-F: 1,680 ppm
VBE-G: 18.0ppm
-The chloromethylstyrene peak area ratio was as follows.
VBE-D: 0.96%
VBE-E: 0.52%
VBE-F: 2.7%
VBE-G: Peak nondetection / thermal decomposition start temperature was as follows.
VBE-D: 378.3 ° C
VBE-E: 392.4 ° C
VBE-F: 317.6 ° C
VBE-G: 389.7 ° C
-The amount of carbide generation at 600 ° C was as follows.
VBE-D: 37.5wt%
VBE-E: 39.1wt%
VBE-F: 28.5wt%
VBE-G: 37.3wt%

Synthesis example 3
While purging a flask equipped with a thermometer, condenser, and 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. Then, the naphthalene ring of the formula (4) was a benzene ring, and 310 parts of a phenol aralkyl resin (P) in which R ¹ was a hydrogen atom and n was 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 softening point of the obtained poly (vinylbenzyl) ether compound was 54 ° C., and the absorption due to the phenolic hydroxyl group of the raw material disappeared. The total chlorine content was 980 ppm, and the chloromethylstyrene peak area ratio was 1.8%. Moreover, the melting peak derived from a crystal | crystallization was not observed, the thermal decomposition start temperature was 376 degreeC, and the carbide | carbonized_material production amount in 600 degreeC was 31.8 wt%.

Example 9
70 g of VBESN 495V obtained in Example 1 and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (trade name: Perhexa 25B, manufactured by NOF Corporation) as a polymerization initiator 7 g was dissolved in 30 g of toluene to obtain a curable 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 250 ° 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 by these measurements are shown in Table 2.

Comparative Example 2
70 g of VB1 obtained in Synthesis Example 3 and 0.7 g of perhexa 25B as a polymerization initiator were dissolved in 30 g of toluene to obtain a curable 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 250 ° 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 by these measurements are shown in Table 2.

VBESN 495V obtained in Example 1, VBESN 475N obtained in Example 2, VBE-A to VBE-C obtained in Examples 3 to 5, VBE-E obtained in Example 7, VBE-E obtained in Example 8 G, A curable composition was obtained in the same manner as described above for VBE-F obtained in Comparative Example 1, and a 2.0 mm-thick plate cured product was prepared therefrom to evaluate the bending toughness. Moreover, the mold release property was evaluated using this curable composition (without solvent). The evaluation results are as follows. Figures in parentheses are bending toughness and releasability.
VBESN 495V: (bending toughness A, releasability A), VBESN 475N (B, B), VBE-A (B, B), VBE-B (A, A), VBE-C (A, A), VBE-E (B, B), VBE-G (B, B), VBE-F (C, C).

Example 10
30 g of VBESN 495V obtained in Example 1, 20 g of a hydrogenated styrene butadiene block copolymer (manufactured by Kraton Polymer Japan Co., Ltd., trade name: KRATON A1535) as a thermoplastic elastomer, and 0.25 g of Perhexa 25B as a polymerization initiator in toluene It melt | dissolved in 150 g and obtained the curable composition (varnish C).

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 250 ° 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 solution viscosity was measured at 25 ° C. using an E-type viscometer. The results obtained by these measurements are shown in Table 3.

Comparative Example 3
30 g of VB1 obtained in Synthesis Example 3, 20 g of KRATON A1535 as a thermoplastic elastomer and 0.25 g of perhexa 25B as a polymerization initiator were dissolved in 150 g of toluene to obtain a curable composition (varnish D).

Using the prepared varnish D, a film was obtained in the same manner as in Example 10, and evaluated in the same manner. The results are shown in Table 3.

Example 11
Glass cloth (E glass, weight per unit area: 71 g / m ² ) was immersed in the varnish C obtained in Example 10 for impregnation, and dried in an air oven at 50 ° C. for 30 minutes. The resin content (RC) of the obtained prepreg was 55%.
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 12
Varnish C obtained in Example 10 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.

Example 13, Comparative Example 4
The test was performed under the same conditions as in Example 9, except that VBE-D obtained in Example 6 and VBE-F obtained in Comparative Example 1 were used. The results obtained from the tests are shown in Table 4.

Industrial applicability

The curable composition of the present invention exhibits excellent chemical resistance, dielectric properties, low water absorption, heat resistance, flame retardancy, mechanical properties after curing, and is a dielectric material in the fields of electrical industry, space / aircraft industry, etc. It can be used for insulating materials, heat-resistant materials, structural materials, and the like. In particular, it can be used as a single-sided, double-sided, multilayer printed board, flexible printed board, build-up board or the like.

Claims

A poly (vinylbenzyl) ether compound represented by the following formula (1) obtained by reacting a naphthol aralkyl resin with a vinyl aromatic halomethyl compound, having a total halogen content of 600 ppm (wt) or less and gel permeation Poly (vinyl) characterized in that the peak area derived from the vinyl aromatic halomethyl compound in chromatographic measurement is 1.0% or less with respect to the total peak area totaled with the peak area of the poly (vinylbenzyl) ether compound. (Benzyl) ether compound.

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 represents an aryl group having 6 to 50 carbon atoms. , R 2 each 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. However, m + r does not exceed 8.
The poly (vinylbenzyl) ether compound according to claim 1, wherein the proportion of the alkyl group in R 2 of the formula (1) is 0.1 to 40 mol%.
A curable composition comprising the poly (vinylbenzyl) ether compound according to claim 1 and a radical polymerization initiator.
Hardened | cured material formed by hardening | curing the curable composition of Claim 3.
A curable composite material comprising the curable composition according to claim 3 and a substrate.
A cured composite material obtained by curing the curable composite material according to claim 5.
A laminate comprising the layer of cured composite material according to claim 6 and a metal foil layer.
A metal foil with a resin, comprising a film formed from the curable composition according to claim 3 on one side of the metal foil.
A hydroxynaphthalene represented by the following formula (2) and an aromatic compound represented by the following formula (3) are condensed to obtain a naphthol aralkyl resin, and the naphthol aralkyl resin and the vinyl aromatic halomethyl compound are 2. A reaction product containing a poly (vinylbenzyl) ether compound is obtained by reacting in the presence of an alkali metal hydroxide, which is purified with a mixed solvent comprising water and alcohols. The manufacturing method of the poly (vinyl benzyl) ether compound as described in 1 above.

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, m is a number from 1 to 6, and r is a number from 1 to 3. . However, m + r does not exceed 8.

Here, Ar 1 represents an aryl group having 6 to 50 carbon atoms, and X represents a fluorine atom, a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group.
The naphthol aralkyl resin to be reacted with a vinyl aromatic halomethyl compound is a partially modified naphthol aralkyl resin in which a part of the OH group of the naphthol aralkyl resin is an OR group (R is an alkyl group having 1 to 12 carbon atoms). 9. A process for producing a poly (vinylbenzyl) ether compound according to 9.
The method for producing a poly (vinylbenzyl) ether compound according to claim 10, wherein the partially modified naphthol aralkyl resin is a partially modified naphthol aralkyl resin obtained by alkoxylating a part of the OH group of the naphthol aralkyl resin. .
Partially modified naphthol aralkyl resin synthesizes naphthol aralkyl resin by condensing hydroxy naphthalene represented by formula (2) and aromatic compound represented by formula (3) wherein X is methoxy group or ethoxy group In this process, methanol or ethanol by-produced by the reaction is refluxed in the reaction system, whereby a part of the OH group of the naphthol aralkyl resin is alkoxylated to obtain an OR group. The manufacturing method of the poly (vinyl benzyl) ether compound as described in 1 above.
In the partially modified naphthol aralkyl resin, the hydroxy naphthalenes represented by the formula (2) and a part or all of the OH groups of the formula (2) are OR groups (R is an alkyl group having 1 to 12 carbon atoms). A mixture of hydroxynaphthalenes including alkoxynaphthalene or a hydroxynaphthalene in which a part of the OH group of formula (2) is an OR group (R is an alkyl group having 1 to 12 carbon atoms) is represented by the formula (3 The method for producing a poly (vinylbenzyl) ether compound according to claim 10, which is obtained by condensing the aromatic compound represented by