WO2014073536A1

WO2014073536A1 - Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof

Info

Publication number: WO2014073536A1
Application number: PCT/JP2013/079920
Authority: WO
Inventors: 政隆中西; 一真井上; 篤彦長谷川
Original assignee: 日本化薬株式会社
Priority date: 2012-11-06
Filing date: 2013-11-05
Publication date: 2014-05-15
Also published as: KR102047681B1; KR20150082181A; JP6240613B2; JPWO2014073536A1; CN104781307B; TW201431901A; CN104781307A

Abstract

The objective of the present invention is to provide: a polyvalent phenylene ether novolac resin that provides a cured product having high heat resistance and superior dielectric properties; and an epoxy resin composition containing same. In the polyvalent phenylene ether novolac resin, a poly(phenylene ether) resin having a molecular weight of 400-8000 (weight average molecular weight; in terms of polystyrene) is bonded by means of an organic group.

Description

Polyvalent phenylene ether novolak resin, epoxy resin composition and cured product thereof

The present invention relates to a novolac resin, an epoxy resin composition, and a cured product thereof suitable for use in electrical and electronic materials that require heat resistance and electrical properties (dielectric properties, etc.).

Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment.

Japanese Laid-Open Patent Publication No. 2003-12796 Japanese Unexamined Patent Publication No. 2006-291178

In the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes complicated with thinning, stacking, systemization, and three-dimensionalization, and a very high level of heat resistance. Required characteristics such as stability and high fluidity are required. Furthermore, in order to realize high-speed communication, semiconductor peripheral materials are required to have excellent dielectric properties. If this dielectric property is poor, it is difficult to increase the speed of the electric signal due to delay of the electric signal and generation of noise.
In such a field, particularly in a network substrate such as a server, dielectric properties at high frequencies are required. In a network environment that continues to evolve year by year, low dielectric loss tangent is particularly important among dielectric properties. For such applications, poly (phenylene ether) resins are often used, and various studies have been made.
Poly (phenylene ether) resin is characterized by its very excellent dielectric properties, but in order to embody the dielectric properties, there are very few functional groups and its low heat resistance is a problem.
According to recent reports, studies such as adding a functional group (a) and bifunctional (b) have been made to deal with these problems. However, in (b), there is a slight improvement, but it is still insufficient.
In the face of these challenges, we have arrived at the present invention.
That is, the present invention provides a polyvalent phenylene ether novolak resin capable of giving a cured product having excellent heat resistance while maintaining excellent dielectric properties, an epoxy resin composition containing the same, and a cured product thereof. With the goal.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention

(1)
A polyvalent phenylene ether novolak resin in which a poly (phenylene ether) resin having a molecular weight of 400 to 8000 (weight average molecular weight in terms of polystyrene) is linked by an organic group,

(2)
The polyvalent phenylene novolak resin according to (1), wherein the organic group is represented by at least one of the following formula (1):

(In the formula, the * part is bonded to the benzene skeleton of the poly (phenylene ether) resin.)

(3)
The poly (phenylene ether) resin described in (1) or (2) is an oxidized polymer of biphenols or bisphenols and phenol compounds, (1) or a polyvalent phenylene ether novolak resin described in (2),

(4)
An epoxy resin composition containing at least one polyphenylene ene novolak resin according to any one of (1) to (3) above;
(5)
A cured product obtained by curing the epoxy resin composition according to item (4),
Is provided.

The cured product of the epoxy resin composition using the polyphenylene ether novolak resin of the present invention has not only high dielectric properties but also excellent heat resistance, and an insulating material for electrical and electronic parts and a laminate (print Wiring board, build-up board, etc.) and various composite materials including CFRP, adhesives, paints, etc. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.

The polyvalent phenylene ether novolak resin of the present invention has a structure in which a resin having a poly (phenylene ether) structure is bonded via an organic group such as an alkylene group (hereinafter also referred to as a linking group or a linking group). That is, the polyvalent phenylene ether novolak resin of the present invention is a resin having a poly (phenylene ether) structure resin and a novolac resin structure.

Specifically, the resin having a poly (phenylene ether) structure is a resin described in Patent Document 1 or Patent Document 2 described above, and an oxidized polymer of xylenol or trimethylphenol is generally used. Examples thereof include biphenols and oxidized polymers of phenol compounds such as bisphenols and 2,6-xylenol.
Here, as the bisphenols, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and bisphenol I can be used. Examples of commercially available products include PPO (registered trademark) manufactured by SABIC, and SA120, SA90-100 and the like are particularly preferable from the range of molecular weight. In particular, it is preferable to use a bifunctional compound such as SA90-100 in view of the degree of polyfunctionalization. Examples of the biphenols include compounds represented by the following formula.

(In the formula, each R ¹ represents an independent substituent, which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aralkyl group, an aryl group, or an alkoxy group, and t represents an integer of 1 to 4) .)

Phenol compounds include o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n -Propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n- Propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluoro Phenyl) phenol, 2-methyl-6-tolyl phenols, monohydric phenolic compounds such as 2,6-di-tolyl phenols.

The molecular weight of the poly (phenylene ether) resin used is 400 to 8000 (weight average molecular weight gel permeation chromatography in terms of polystyrene), preferably 500 to 4000.
If the molecular weight of the resin used is too high, it may cause problems with compatibility with solvents and compatibility with other resins, and may be separated when incorporated into a cured product, resulting in poor curing and uneven distribution of characteristics. Absent. Further, when the molecular weight is small, particularly about 200, it is not preferable because a large difference in dielectric characteristics cannot be obtained as compared with a general novolac resin.
Examples of the control of these molecular weights include not only simply connecting molecules but also examples in which molecular weight control is possible by depolymerization with radicals.

The polyvalent phenylene ether novolak resin of the present invention becomes a novolak or a similar form (all expressed as a novolak for convenience) by connecting the phenylene structure with a bonding group.
The linking group is preferably a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include methylene, ethylene, propylene, cyclohexane-diyl, phenylmethylene, phenylene bismethylene, bienylene bismethylene, phenylene bisethylene, phenylene bispropylene, and the like.
As the bonding group in the present invention, a structure represented by the following formula (1) is particularly preferable.

As a method for bonding these linking groups, a raw material poly (phenylene ether) resin and various aldehydes, ketones, benzylmethylene compounds, bond-forming compounds such as compounds having a vinylbenzene structure, etc. are used in the presence of a solvent. It can be synthesized by heating under basic conditions.

Here, as specific examples of the bond-forming compound, aldehydes such as formaldehyde, acetaldehyde, glyoxal, propyl aldehyde, isovaleraldehyde, octyl aldehyde, furfural, benzaldehyde, pyridinecarbaldehyde, acetone, methyl ethyl ketone, cyclopentanone, Ketones such as cyclohexanone, xylylene glycol, xylylene dihalide (halogen: chlorine, bromine, etc.), bisalkoxymethylbenzene (xylylene bisalkyl ether, specifically bismethoxymethylbenzene, bisethoxymethylbenzene) , Bispropoxymethylbenzene, bisbutoxymethylbenzene, bisphenoxymethylbenzene, bisallyloxymethylbenzene, etc. In this synthesis reaction, xylylene glycol, xylylene dichloride, and bismethoxymethylbenzene are particularly preferred, and the arrangement of substituents may be any of ortho, meta, and para, but there is a balance between heat resistance and mechanical properties. From xylylene compounds such as biphenyldimethanol, bishalogenomethylbiphenyl (halogen: chlorine, bromine, etc.), bisalkoxymethylbiphenyl (specifically bismethoxymethylbiphenyl, bis Biphenyl bis-methyleneation such as ethoxymethyl biphenyl, bispropoxymethyl biphenyl, bisbutoxymethyl biphenyl, bisphenoxymethyl biphenyl, bisallyloxymethyl biphenyl, etc. Benzyl methylene compounds of goods, and the like, compounds having a vinyl benzene structure such as divinylbenzene.
In this synthesis reaction, biphenyldimethanol, bischloromethylbiphenyl, and bismethoxymethylbiphenyl are particularly preferable.

The polyvalent phenylene ether novolak resin of the present invention can be obtained by heating a raw material poly (phenylene ether) resin and a bond-forming compound with a catalyst added to a solvent mixture as necessary.
Further, the bond-forming compound may be gradually added to a solution in which a raw material poly (phenylene ether) resin and a catalyst are dissolved as necessary. The reaction time is usually 3 to 150 hours, and the reaction temperature is usually 40 to 150 ° C. The polyvalent phenylene ether novolak resin thus obtained can be used without being purified depending on the use. Usually, after completion of the reaction, the reaction mixture is neutralized as necessary, and then the crystal It is refined by removing solvents under precipitation or heating under reduced pressure and used for various applications. In addition, since the average molecular weight of the polyvalent phenylene ether novolak resin obtained by the reaction is increased, the softening point of the resin becomes very high and it is difficult to take out from the reaction vessel. Therefore, the following (a) to (d) ) Method can be used.

(A) A method obtained by reprecipitation by diluting with a water-soluble solvent and then mixing with water.
(B) A method obtained by diluting with an alcohol having 1 to 4 carbon atoms (methanol, ethanol, propanol, butanol, etc.) and reprecipitation.
(C) A method of removing only water contained in the solvent after completion of the reaction / purification (heating under reduced pressure, etc.) and then removing it from the reaction vessel as a solvent-cut varnish. (The resin concentration is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 30 to 80% by weight.) In particular, viscosity is often regarded as important, and its fluidity The viscosity at 25 ° C. is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. If the viscosity is too high, it may be difficult to take out or mix with other resins because it is not fluid during use. In addition, the solvent which can be used is mentioned later (it is a solvent as described in the term of the curable resin composition varnish).
(D) A method of mixing with other resin (the resin described in the section of curing agent for curable resin composition described later) and taking it out from the reaction vessel as a curing agent composition. (The mixing ratio is preferably 90:10 to 30:70, more preferably 80:20 to 30:70, by weight ratio of the other resin and the resin of the present invention. When the blending amount of the resin of the present invention is small, There is no significant improvement in characteristics.)

The reaction molar ratio (hydroxyl equivalent ratio) between the raw poly (phenylene ether) resin and the bond-forming compound is preferably 1.2: 1 to 20: 1, more preferably 1.5: 1 to 15: 1, particularly Preferably it is 1.5: 1 to 10: 1. When the reaction molar ratio is less than 1.2: 1, that is, when the raw material poly (phenylene ether) resin is less than 1.2 with respect to the bond-forming compound 1, the molecular weight of the polyvalent phenylene ether novolak resin to be formed becomes too large. Therefore, the solubility in a solvent and the compatibility with other resins may deteriorate. Moreover, when it exceeds 20: 1, ie, when the raw material poly (phenylene ether) resin exceeds 20 with respect to the bond-forming compound 1, heat resistance may be poor.

Solvents that can be used in the synthesis of the polyvalent phenylene ether novolak resin of the present invention include toluene, xylene, methyl isobutyl ketone, anone, cyclopentanone, methyl ethyl ketone, and the like. Two or more species may be used in combination. Solvents that can be used in combination, in addition to the above, alcohols such as methanol, ethanol, isopropanol, butanol, ketones such as acetone, esters such as ethyl acetate, butyl acetate, carbitol acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, Examples thereof include ethers such as dioxane, nitrogen-containing solvents such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. The amount of the solvent used is usually in the range of 5 to 500 parts by weight, preferably 10 to 400 parts by weight with respect to 100 parts by weight of the total amount of the raw material poly (phenylene ether) resin and the bond-forming compound.

As the catalyst, it is basically preferable to use an acidic catalyst. When the bond-forming compound is benzyl halide, the reaction can proceed smoothly without the addition of a catalyst. From the viewpoint of ease of subsequent purification, it is preferable to use no catalyst or hardly use it. When using the catalyst, specific examples of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acids, Examples include stannic chloride, zinc chloride, ferric chloride, and other acidic catalysts usually used for the production of novolak resins such as organic and inorganic acid salts showing acidity. These catalysts are not limited to those mentioned above, and may be used alone or in combination of two or more. The amount of the catalyst used is usually in the range of 0.005 to 2.0 moles, preferably 0.01 to 1.1 moles, or 100 g of the raw poly (phenylene ether) resin relative to the raw material poly (phenylene ether) resin. The amount is preferably 0.1 to 50 g, more preferably 0.3 to 20 parts. If the amount of catalyst is small, the progress of the reaction is slow. Moreover, problems such as the need for a reaction at a high temperature and the reaction not proceeding to the end are not preferable. Moreover, when there is too much catalyst amount, a great amount of labor may be applied in post-treatments such as neutralization and purification.
In addition, when corrosive gas produces | generates by reaction, it is preferable to make it exhaust from the inside of a system by sending inactive gas, such as drawing pressure or nitrogen.

The polyvalent phenylene ether novolak resin thus obtained is represented by a structural formula represented by the following formula (A), and specific examples of this representative structural formula will be described below.
The resulting polyvalent phenylene ether novolak resin is such that the benzene skeleton of the poly (phenylene ether) resin described in B below is connected by the connecting group described in A below, The groups connect the benzene skeletons in the same molecule of the poly (phenylene ether) resin or the benzene skeletons of two or more poly (phenylene ether) resin molecules.
And the partial structure around a coupling group becomes a structure like following formula (A), for example. The following benzene skeleton represents a benzene skeleton in a poly (phenylene ether) resin molecule.

(In the above formula, P is a residue of a poly (phenylene ether) resin, X is a linking group represented by the following formula (1), R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, * is Represents a hydrogen atom or the above X, and n represents an integer of 1 to 2.)

Here, the residue of the above poly (phenylene ether) resin can be further linked to the benzene skeleton in the poly (phenylene ether) resin molecule via X in another benzene skeleton.

The polyphenylene ether novolak resin of the present invention thus obtained is a brown resin (or powder), is soluble in an organic solvent, and can be handled as a varnish.
The thus obtained polyvalent phenylene ether novolak resin of the present invention preferably has a hydroxyl group equivalent of 400 to 6000, particularly preferably 500 to 5000.
The weight average molecular weight is preferably 600 to 50000, and particularly preferably 700 to 25000.

The polyvalent phenylene ether novolak resin of the present invention can be used as it is as a thermoplastic (or its raw material), mixed with a thermoplastic to improve its properties, or used as a raw material for an epoxy resin and its curing agent. You can also.

Hereinafter, the epoxy resin composition of the present invention containing the polyvalent phenylene ether novolak resin of the present invention (hereinafter also referred to as curable resin composition) will be described. In the curable resin composition of the present invention, an epoxy resin is used as an essential component.

The curable resin composition of the present invention is a composition containing an epoxy resin-curing agent as an essential component, and always contains a polyvalent phenylene ether novolak resin as a curing agent for the epoxy resin. Moreover, a hardening accelerator is contained as needed.

Specific examples of epoxy resins that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. It is done. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixed siloxane structure of at least two of them) such as a compound, alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, etc. Has glycidyl group and / or epoxycyclohexane structure Solid or liquid epoxy resin having an epoxy resin) and the like although not limited thereto.

As the curing agent contained in the curable resin composition of the present invention, other curing agents can be used in combination in addition to the above-described polyphenylene ether novolak resin of the present invention. When used in combination, it can be used as a curing agent composition of the above-described polyphenylene ether novolak resin of the present invention and another curing agent. When used together, the proportion of the polyvalent polyphenylene ether novolak resin of the present invention in the total epoxy resin composition is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Examples of the curing agent that can be used in combination include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound.
Specific examples of the curing agent that can be used are as follows.
Phenolic resins, phenolic compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hy Loxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, Polycondensates with 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, terpenes and phenols However, the present invention is not limited to these. These may be used alone or in combination of two or more.

Preferred phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure) in terms of dielectric constant, and particularly preferred is a structure having at least one selected from phenol, naphthol, and cresol, and serves as the linker. A resin characterized in that the alkylene part is at least one selected from a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene) And novolak resin.).

Amine compounds, amide compounds; diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine, It is not limited to these. These may be used alone or in combination of two or more.

Acid anhydride compounds, carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, etc .; by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides Although the obtained carboxylic acid resin is mentioned, it is not limited to these. These may be used alone or in combination of two or more.

Other examples of the curing agent that can be used in combination include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more.

In the curable resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents in terms of its functional group (hydroxyl group) equivalent to 1 equivalent of the epoxy group of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the curable resin composition of the present invention, a curing accelerator may be used in combination with a curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. And quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts, and the like. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When a curing accelerator is used, 0.01 to 5.0 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.

The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned. Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy may be insufficient, and if it is 0.6 or more, the hygroscopicity and dielectric properties of the cured product may deteriorate.

Furthermore, you may add antioxidant to the curable resin composition of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component in the curable resin composition of the present invention.

Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2,2 '-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzyl phosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl) calcium 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

Specific examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. The

Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite ; 9,10-dihydride -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- Examples thereof include oxaphosphaphenanthrene oxides such as 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

These antioxidants can be used alone, but two or more kinds may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-Pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Alternatively, two or more types may be used in combination.

Furthermore, a binder resin can be blended with the curable resin composition of the present invention as required. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

An inorganic filler can be added to the curable resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is used in an amount of 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

The curable resin composition of the present invention can be obtained by uniformly mixing each component. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the polyphenylene ether novolak resin and epoxy resin of the present invention and, if necessary, the curing accelerator, phosphorus-containing compound, binder resin, inorganic filler and compounding agent are made uniform using an extruder, kneader, roll or the like as necessary. Mix thoroughly until a curable resin composition is obtained, potting the curable resin composition, melting (without melting if liquid), molding using a casting or transfer molding machine, and 80- The cured product of the present invention can be obtained by heating at 200 ° C. for 2 to 10 hours.

Further, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary to obtain a curable resin composition varnish. A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating is subjected to hot press molding, whereby the curable resin composition A of the present invention is prepared. It can be a cured product. In this case, the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material containing a carbon fiber can also be obtained as it is, for example with a RTM system.

The curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The curable resin composition of the present invention includes general uses in which an epoxy resin is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (prints) In addition to a sealing agent, an additive to other resins and the like are included. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

As sealing agent and substrate, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use as which a functionality, such as a network board | substrate and a module board, is calculated | required.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) GPC:
Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(Example 1)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 175 parts of polyphenylene ether resin (MX90-100, manufactured by Subic, Mn = 2066, Mw = 3553, Mz = 5951 on the GPC chart) while purging with nitrogen, p- Add 9.6 parts of xylylene glycol (reagent made by Tokyo Kasei), 300 parts of toluene (reagent made by Junsei Kagaku), 2 parts of paratoluenesulfonic acid monohydrate (reagent made by Tokyo Chemical Industry), and react at 100 ° C. for 2 hours. Thereafter, the mixture was refluxed at 110-120 ° C. and reacted for 7 hours.
After completion of the reaction, 200 parts of methyl isobutyl ketone was added, washing with water was repeated, and after confirming that the aqueous layer became neutral, the solvent was distilled off from the oil layer under reduced pressure using a rotary evaporator. 179 parts of a polyphenylene ether novolak resin (P-1) was obtained. (In the GPC chart of the raw material polyphenylene ether resin, Mn = 2091, Mw = 4215, and Mz = 7774.)

(Example 2)
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, while 75 parts of polyphenylene ether resin (MX90-100 made by Subic), 5 parts of p-xylylene glycol (reagent made by Tokyo Chemical Industry), toluene (genuine) 130 parts of chemical reagent) and 1 part of p-toluenesulfonic acid monohydrate (reagent made by Tokyo Kasei) were reacted at 100 ° C for 2 hours, and then refluxed at 110-120 ° C for 10 hours. It was.
After completion of the reaction, 100 parts of methyl isobutyl ketone was added, washing with water was repeated, and after confirming that the aqueous layer became neutral, the solvents were gradually removed from the oil layer under reduced pressure using a rotary evaporator. After confirming that the outflow disappeared, methyl isobutylkenton was added to adjust the resin concentration to 50%. As a result, 143 parts of the polyvalent phenylene ether novolak resin varnish (V-1) of the present invention was obtained. In the GPC chart, Mn = 2111, Mw = 4345, and Mz = 7932.

(Example 3)
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 87.5 parts of a polyphenylene ether resin (MX90-100, manufactured by Savic) and 4.8 parts of p-xylylene glycol (a reagent manufactured by Tokyo Chemical Industry). , 138 parts of methyl isobutyl ketone (reagent manufactured by Junsei Kagaku), 1 part of paratoluenesulfonic acid monohydrate (reagent manufactured by Tokyo Chemical Industry), reacted at 100 ° C. for 2 hours, and then brought to reflux at 110-120 ° C. The reaction was carried out for 7 hours.
After completion of the reaction, 100 parts of methyl isobutyl ketone was added, washing with water was repeated, and after confirming that the aqueous layer became neutral, the solvents were gradually removed from the oil layer under reduced pressure using a rotary evaporator. After confirming that the outflow disappeared, methylisobutylkenton was added to adjust the resin concentration to 60%.
After adding 50 parts of the obtained polyphenylene ether novolak resin varnish (V-2) of the present invention and 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) Then, a curing agent composition (H-1) containing 30% of the polyvalent phenylene ether novolak resin of the present invention was obtained. The softening point was 121 ° C.,

Example 4
In Example 3, the same operation was performed except that 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was changed to 30 parts, to obtain a curing agent composition (H-2) of the present invention.
(Example 5)
In Example 3, the same operation was performed except that 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was changed to 20 parts, and 60% of the polyvalent phenylene ether novolac resin of the present invention was contained. A curing agent composition (H-3) was obtained. The softening point was 130 ° C.

(Example 6)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 100 parts of polyphenylene ether resin (SA120-100 manufactured by Subic, Mn = 2960, Mw = 6863, Mz = 11851 in GPC measurement) while purging with nitrogen, p- Add 10 parts of xylylene glycol (reagent made by Tokyo Kasei), 140 parts of toluene (reagent made by Junsei Kagaku), 2.0 parts of paratoluenesulfonic acid monohydrate (reagent made by Tokyo Chemical Industry), and react at 100 ° C. for 2 hours. Thereafter, the mixture was refluxed at 110-120 ° C. and reacted for 7 hours.
After completion of the reaction, 100 parts of methyl ethyl ketone was added, and the mixture was gradually added dropwise to a container containing 1000 parts of methanol, and reprecipitation was performed. The obtained resin powder was filtered, washed with 100 parts of methanol: water = 1: 1, and then washed 5 times with 100 parts of water. As a result, 89 parts of the polyvalent phenylene ether novolak resin (P-3) of the present invention was obtained. In the GPC chart, Mn = 3683, Mw = 7356, and Mz = 1860. Also, 20 parts of KAYAHARD GPH-65 and 50 parts of toluene were mixed with 30 parts of the obtained (P-3), and after mixing, the solvents were distilled off under reduced pressure using a rotary evaporator. A product (H-4) was obtained.

(Comparative Example 1)
Add 30 parts of polyphenylene ether resin (MX90-100 from Savic) and 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 from Nippon Kayaku), dissolve in methyl isobutyl ketone, and then remove the solvents under reduced pressure using a rotary evaporator. Then, a comparative curing agent composition (H′-1) was obtained.
(Comparative Example 2)
Add 30 parts of polyphenylene ether resin (MX90-100 from Savic) and 20 parts of phenol biphenylene novolak (KAYAHARD GPH-65 from Nippon Kayaku), dissolve in methyl isobutyl ketone, and then remove the solvents under reduced pressure using a rotary evaporator. Then, a comparative curing agent composition (H′-2) was obtained.

Examples 7 to 8 and Comparative Example 3
<Dielectric constant and dielectric loss tangent test>
The curing agent composition and epoxy resin obtained above were blended in the proportions (parts by weight) shown in Table 1, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Dielectric constant / dielectric loss tangent: Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz
Reference Teflon (registered trademark)

Example 9 and Comparative Example 4
<Dielectric property test and heat resistance test>
The curing agent composition and the epoxy resin obtained as described above were blended in the proportions (parts by weight) shown in Table 2, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Dielectric constant / dielectric loss tangent: Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz
Reference Teflon (registered trademark)
Heat resistance (TMA): Measured according to JIS K 7244.

Example 10 and Comparative Example 5
<Heat resistance test / dielectric property test>
The curing agent composition and the epoxy resin obtained above were blended in the proportions (parts by weight) shown in Table 3, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Dielectric constant / dielectric loss tangent: Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz
Reference Teflon (registered trademark)
・ Heat resistance (DMA)
Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm)
Tg: Tan-δ peak point was Tg. Heat resistance (TMA): Measured in accordance with JIS K 7244.

From the above results, the curable resin composition of the present invention is excellent in heat resistance as compared with those using H'-1 and H'-2 having a similar structure as a curing agent (composition). It was clear that the dielectric constant and dielectric loss tangent were good as compared with those using other curing agents, and it was confirmed that they have excellent dielectric properties.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on November 6, 2012 (Japanese Patent Application No. 2012-244309), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

The polyphenylene ether novolak resin of the present invention is useful as a curing agent for an epoxy resin, and the epoxy resin composition containing the polyphenylene ether novolak resin as a curing agent includes an insulating material for electrical and electronic parts and a laminate (printed wiring board, It is useful for various composite materials such as build-up substrates) and CFRP, adhesives, paints and the like.

Claims

Polyvalent phenylene ether novolak resin in which poly (phenylene ether) resin having a molecular weight of 400 to 8000 (weight average molecular weight in terms of polystyrene) is linked by an organic group.
The polyvalent phenylene ether novolak resin according to claim 1, wherein the organic group is represented by at least one of the following formulas (1).

(In the formula, the * part is bonded to the benzene skeleton of the poly (phenylene ether) resin.)
3. The polyvalent phenylene ether novolak resin according to claim 1, wherein the poly (phenylene ether) resin is an oxidized polymer of biphenols or bisphenols and phenol compounds.
An epoxy resin composition comprising at least one polyphenylene ether novolak resin according to any one of claims 1 to 3.
A cured product obtained by curing the epoxy resin composition according to claim 4.