KR102047681B1

KR102047681B1 - Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof

Info

Publication number: KR102047681B1
Application number: KR1020157007946A
Authority: KR
Inventors: 마사타카 나카니시; 카즈마 이노우에; 아츠히코 하세가와
Original assignee: 닛뽄 가야쿠 가부시키가이샤
Priority date: 2012-11-06
Filing date: 2013-11-05
Publication date: 2019-11-22
Also published as: WO2014073536A1; JP6240613B2; KR20150082181A; CN104781307B; CN104781307A; TW201431901A; JPWO2014073536A1

Abstract

An object of the present invention is to provide a polyhydric phenylene ether novolak resin and a epoxy resin composition comprising the same, which provide a cured product having high heat resistance and excellent dielectric properties. In polyhydric phenylene ether novolak resin of this invention, poly (phenylene ether) resin of the molecular weight 400-8000 (weight average molecular weight polystyrene conversion) is connected by the organic group.

Description

Polyhydric phenylene ether novolak resin, epoxy resin composition and its hardened | cured material {POLYVALENT PHENYLENE ETHER NOVOLAC RESIN, EPOXY RESIN COMPOSITION, AND CURED PRODUCT THEREOF}

TECHNICAL FIELD The present invention relates to a novolak resin, an epoxy resin composition, and a cured product thereof suitable for use in electric and electronic material applications requiring heat resistance and electrical properties (dielectric properties, etc.).

Epoxy resin compositions are widely used in the fields of electrical and electronic components, structural materials, adhesives, paints and the like due to their excellent workability and excellent cured product, such as electrical properties, heat resistance, adhesion, moisture resistance (water resistance), and the like.

However, in recent years, in the field of electric and electronics, the development of high purity resin composition, low viscosity for high moisture resistance, adhesiveness, dielectric properties, filler (inorganic or organic filler), and shortening molding cycle The improvement of various characteristics, such as the reaction up, is further requested | required. Moreover, as a structural material, the material which is lightweight and excellent in mechanical property is calculated | required for aerospace material, leisure, sports equipment use, etc.

Japanese Patent Publication No. 2003-12796 Japanese Patent Publication No. 2006-291178

In the field of semiconductor sealing and substrates (substrate itself or its surrounding materials), it is complicated by thinning, stacking, systemization, and three-dimensionality according to the change of the semiconductor, and the required characteristics made with very high level of heat resistance and high fluidity Is required. In addition, in order to realize high-speed communication, excellent dielectric properties are required for semiconductor peripheral materials. Due to the generation of delay and noise of the electric signal having poor dielectric properties, it is difficult to speed up the electric signal.

In these fields, especially in network boards such as servers, dielectric properties at high frequencies are required. In the evolving network environment year after year, especially low dielectric loss tangents become important. Many of these uses can mainly use a poly (phenylene ether) resin, and various studies have been made.

Poly (phenylene ether) resins are characterized by their very excellent dielectric properties, but in order to realize the dielectric properties, extremely low functional groups and low heat resistance have become a problem.

According to a recent report, such a problem has been examined such as a method of adding a functional group (a) or a bifunctional (b), but in (a), the introduction of the functional group is difficult and practically not practical. In (b) there is some improvement, but it is still insufficient.

In the face of this problem, we have come to the present invention.

That is, an object of this invention is to provide the polyhydric phenylene ether novolak resin which can provide the hardened | cured material excellent in heat resistance, maintaining the excellent dielectric property, the epoxy resin composition containing this, and its hardened | cured material.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in view of the above fact.

That is, the present invention

(1) polyhydric phenylene ether novolac resin, characterized in that 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 ether novolak resin according to (1), wherein the organic group is represented by at least one of the following formulas (1),

[Wherein, the * moiety is bonded to the benzene skeleton of the poly (phenylene ether) resin]

(3) The polyhydric phenylene ether novolak resin according to (1) or (2), wherein the poly (phenylene ether) resin is an oxidized polymer of biphenols or bisphenols and phenol compounds,

(4) At least 1 sort (s) of polyhydric phenylene ether novolak resin in any one of said (1)-(3), The epoxy resin composition characterized by the above-mentioned.

(5) It is obtained by hardening | curing the epoxy resin composition as described in said (4), It provides the hardened | cured material characterized by the above-mentioned.

(Effects of the Invention)

The cured product of the epoxy resin composition using the polyvalent phenylene ether novolac resin of the present invention not only has a high dielectric property, but also exhibits excellent heat resistance, and is used for insulating materials and laminates for printed electronic boards (printed wiring boards, build-up substrates). Etc.) and CFRP, and various composite materials, adhesives, paints, and the like. In particular, it is very useful for the semiconductor sealing material which protects a semiconductor element.

The polyhydric phenylene ether novolak resin of this invention has the structure which the resin of the poly (phenylene ether) structure couple | bonded through organic groups, such as an alkylene group (henceforth a coupling group or a coupling group). That is, the polyhydric phenylene ether novolak resin of this invention is resin which has the structure of resin of a poly (phenylene ether) structure, and novolak resin.

Resin of a poly (phenylene ether) structure is resin of the above-mentioned patent document 1, patent document 2 specifically, Although xylenol and the oxidation polymer of trimethylphenol are common, Biphenols like resin of patent document 2 are common. Oxidized polymers of phenolic compounds, such as a bisphenol and 2, 6- xylenol, etc. are mentioned.

As bisphenols, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and bisphenol I can be used. Commercially available products include PPO (registered trademark) manufactured by SABIC, and SA120, SA90-100, and the like are particularly preferable in the range of molecular weight. In addition, it is particularly preferable to use a bifunctional one such as SA90-100 in the degree of polyfunctionalization. As biphenols, the compound of the following formula is mentioned, for example.

[Wherein, R ¹ each represents an independent substituent, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aralkyl group, an aryl group, an alkoxy group, and t represents an integer of 1 to 4]

Examples of the phenol compounds are o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol and 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-fluorophenyl) phenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, and the like A monohydric phenol compound is mentioned.

As molecular weight of the poly (phenylene ether) resin to be used, it is 400-8000 (weight average molecular weight gel permeation chromatography polystyrene conversion), Preferably it is 500-4000.

When the molecular weight of the resin to be used is too high, it is unfavorable because it impairs compatibility with solvents or compatibility with other resins and is separated when blown into the cured product, resulting in poor curing and localization of properties. Moreover, when molecular weight is small, especially about 200, it is unpreferable since it cannot make a big difference in dielectric properties compared with general novolak resin.

As control of these molecular weights, not only can a molecule | numerator be connected simply, but the case where molecular weight control was possible by depolymerization by a radical is mentioned.

The polyhydric phenylene ether novolak resin of the present invention is connected to a phenylene structure with a linking group to form a novolak or similar form (all expressed as novolaks for convenience).

As a coupling group, it is preferable that it is a C1-C20 hydrocarbon group. Specific examples include methylene, ethylene, propylene, cyclohexane-diyl, phenylmethylene, phenylenebismethylene, bienylenebismethylene, phenylenebisethylene, phenylenebispropylene and the like.

Especially as a coupling group in this invention, the structure represented by following formula (1) is preferable.

As the bonding method of these linking groups, by using a raw material poly (phenylene ether) resin and bond forming compounds such as various aldehydes, ketones, benzyl methylene compounds, and compounds having a vinylbenzene structure, heating is performed under acidic or basic conditions in the presence of a solvent. Can be synthesized.

Here, specific examples of the bonding compound include aldehydes such as formaldehyde, acetaldehyde, glyoxal, propylaldehyde, isobaraldehyde, octylaldehyde, furfural, benzaldehyde, pyridinecarboxyaldehyde, acetone, methyl ethyl ketone, cyclopentanone, and the like. Ketones such as cyclohexanone, xylylene glycol, xylylenedihalide (halogen: chlorine, bromine and the like), bisalkoxymethylbenzene (xylylenebisalkyl ether, specifically bismethoxymethylbenzene, C1-C6 alkoxymethyl bodies, such as bisethoxymethylbenzene, bispropoxymethylbenzene, bisbutoxymethylbenzene, bisphenoxymethylbenzene, bisaryloxymethylbenzene, etc. Especially in this synthesis reaction, xylyl Lenglycol, xylylenedichloride, bismethoxymethylbenzene are preferred, and the arrangement of the substituents is either ortho, meta, or para. Although it does not matter, xylylene compounds, such as the balance of heat resistance and a mechanical characteristic, are especially preferable), biphenyl dimethanol, bishalogen methyl biphenyl (halogen: chlorine, bromine etc.), bisalkoxy Methyl biphenyl (specifically bismethoxymethylbiphenyl, bisethoxymethylbiphenyl, bispropoxymethylbiphenyl, bisbutoxymethylbiphenyl, bisphenoxymethylbiphenyl, bisaryloxymethylbiphenyl, etc. And a compound having a vinylbenzene structure, such as a benzyl methylene compound, such as biphenylbismethylene compounds, such as a C1-C6 alkoxy methyl body, and divinylbenzene.

Especially in this synthesis reaction, biphenyl dimethanol, bischloromethyl biphenyl, bismethoxymethyl biphenyl is preferable.

The polyhydric phenylene ether novolak resin of this invention is obtained by adding a catalyst to a liquid mixture of a solvent, and adding a catalyst as needed, heating a raw material poly (phenylene ether) resin.

Moreover, you may add a bond formation compound gradually to raw material poly (phenylene ether) resin and the solution which melt | dissolved the catalyst as needed. The reaction time is usually 3 to 150 hours, and the reaction temperature is usually 40 to 150 ° C. The polyhydric phenylene ether novolak resin thus obtained may be used without purification depending on the application. However, after the completion of the reaction, the reaction mixture is neutralized, if necessary, and then the solvent is removed under crystallization or heating under reduced pressure. Purified and used for various purposes. Moreover, since the average molecular weight of the polyhydric phenylene ether novolak resin obtained by reaction becomes large, the softening point of resin becomes very high and it becomes difficult to take out from a reaction container, The method of (a)-(d) below can be used.

(a) A method of obtaining by reprecipitation as it is mixed with water after dilution in water-soluble solvents.

(b) A method of diluting with alcohols having 1 to 4 carbon atoms (methanol, ethanol, propanol, butanol and the like) to obtain a precipitate.

(c) After removing only water contained in a solvent after completion | finish of reaction and purification (heating pressure reduction etc.), it is taken out from the reaction container as a varnish of a solvent cut. (The resin concentration is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably 30 to 80% by weight.) In particular, the viscosity is often important, and from the fluidity, 25 The viscosity at 1000 ° C. is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. When the viscosity is too high, taking out and mixing with other resins may be difficult due to lack of fluidity at the time of use. In addition, the solvent which can be used is mentioned later (it is a solvent of the term of the curable resin composition varnish.).

(d) The method of mixing with another resin (resin of the term of the hardening | curing agent for curable resin compositions mentioned later), and taking out from a reaction container as a hardening | curing agent composition. (The mixing ratio is preferably 90:10 to 30:70, more preferably 80:20 to 30:70, in terms of the weight ratio of the other resin to the resin of the present invention. There is no significant improvement.)

Further, the reaction molar ratio (hydroxyl equivalent ratio) of the raw material 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 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 resulting polyvalent phenylene ether novolak resin becomes too large solubility in solvents. In addition, compatibility with other resins may be poor. In addition, when the raw material poly (phenylene ether) resin exceeds 20: 1, that is, the raw material poly (phenylene ether) resin exceeds 20 with respect to the bond-forming compound 1, the heat resistance may be poor.

As a solvent which can be used in the synthesis | combination of the polyhydric phenylene ether novolak resin of this invention, toluene, xylene, methyl isobutyl ketone, anone, cyclopentanone, methyl ethyl ketone, etc. are mentioned, It is not limited to these, It is independent You may use together 2 or more types. As a solvent which can be used together, it is added to each of the above, alcohols, such as methanol, ethanol, isopropanol, butanol, ketones, such as acetone, esters, such as ethyl acetate, butyl acetate, carbitol acetate, and propylene glycol monomethyl ether acetate, tetra Ethers such as hydrofuran and dioxane, nitrogen-containing solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. The usage-amount of a solvent is 5-500 weight part normally with respect to 100 weight part of total amounts of raw material poly (phenylene ether) resin and a bond formation compound, Preferably it is the range of 10-400 weight part.

As a catalyst, it is preferable to use an acidic catalyst fundamentally. In the case where the bond-forming compound is benzyl halide, the reaction can proceed smoothly even without addition of a catalyst, and it is preferable that the catalyst be formed without or almost without a catalyst from the viewpoint of easy purification. In the case of using a catalyst, specific examples of acidic catalysts 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, tin tin chloride, zinc chloride, ferric chloride, and the like, and other acidic catalysts commonly used for the production of novolak resins such as organic and inorganic acid salts exhibiting acidic properties. Can be. These catalysts are not limited to the above-mentioned substances and may be used alone or in combination of two or more. The amount of the catalyst to be used is usually 0.005 to 2.0 times mole, preferably 0.01 to 1.1 times mole, or 0.1 to 50 g relative to 100 g of the raw poly (phenylene ether) resin with respect to the raw poly (phenylene ether) resin. More preferably, it is 0.3-20 parts. If the amount of catalyst is small, the progress of the reaction is slowed down. In addition, problems such as the reaction not progressing to the end, requiring a reaction at a high temperature, are not preferable. In addition, when the amount of catalyst is too large, a great labor may be required in post-treatment such as neutralization and purification.

Moreover, when corrosive gas is produced by reaction, it is preferable to discharge | emit from system inside by sending suction pressure or inert gas, such as nitrogen.

The polyhydric phenylene ether novolak resin obtained in this way is represented by the structural formula shown by following formula (A), and the specific example of this representative structural formula is demonstrated below.

The resulting polyhydric phenylene ether novolak resin is connected to the benzene skeleton of the poly (phenylene ether) resin exemplarily described in B below by a linker exemplarily described in A below, and the linker is poly ( The benzene skeletons in the same molecule of phenylene ether) resin or the benzene skeletons of the molecule | numerator of two or more poly (phenylene ether) resin are connected.

And the partial structure around a connector becomes a structure like following formula (A), for example. In addition, the following benzene skeleton has shown the benzene skeleton in a poly (phenylene ether) resin molecule.

[Wherein 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, and * is a hydrogen atom or the above X represents n represents an integer of 1 to 2]

Here, the residue of the poly (phenylene ether) resin may also be linked to the benzene skeleton in the poly (phenylene ether) resin molecule through X in a separate benzene skeleton.

The polyvalent phenylene ether novolak resin of the present invention thus obtained is brown resinous (or powder), soluble in an organic solvent, and becomes a resin which can also be treated as a varnish.

400-6000 are preferable and, as for the hydroxyl group equivalent of the polyhydric phenylene ether novolak resin of this invention obtained in this way, 500-5000 are especially preferable.

As a weight average molecular weight, 600-50000 are preferable and 700-25000 are especially preferable.

The polyvalent phenylene ether novolak resin of the present invention may be used as it is as a thermoplastic (or a raw material thereof), mixed with a thermoplastic plastic to improve properties, or used as a raw material of epoxy resin or a curing agent thereof.

Hereinafter, it describes about the epoxy resin composition (henceforth curable resin composition) of this invention containing the polyhydric phenylene ether novolak resin of this invention. In curable resin composition of this invention, an epoxy resin is used as an essential component.

In the curable resin composition of this invention, it is a composition which has an epoxy resin-hardening agent as an essential component, and polyhydric phenylene ether novolak resin is necessarily contained as a hardening | curing agent of an epoxy resin. Moreover, a hardening accelerator is contained as needed.

Specific examples of the epoxy resin that can be used in the curable resin composition of the present invention include novolak type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. have. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpendiphenol, 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, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxy Benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis ( Polycondensates such as methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, and modified substances thereof and tetrabromobisphenol A Such as halogenated bisphenols and alcohols Silsesquioxane-based epoxy resins such as glycidyl ether derivatives, alicyclic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins derived from Solid or liquid epoxy resins, such as glycidyl group and / or epoxycyclohexane structure, are mentioned to the siloxane structure of 2 or more types of mixed structure, It is not limited to these.

As a hardening | curing agent which the curable resin composition of this invention contains, other hardening agents other than the polyhydric phenylene ether novolak resin of the above-mentioned this invention can be used together. When using together, it can be used as a hardening | curing composition of the polyhydric phenylene ether novolak resin of this invention mentioned above, and another hardening | curing agent. When using together, 30 weight% or more is preferable and, as for the ratio to the whole epoxy resin composition of the polyhydric polyphenylene ether novolak resin of this invention, 40 weight% or more is especially preferable.

As a hardening | curing agent which can be used together, a phenol resin, a phenol type compound, an amine compound, an acid anhydride type compound, an amide type compound, a carboxylic acid type compound, etc. are mentioned, for example.

As a specific example of the hardening | curing agent which can be used, it is as follows.

Phenol resins, phenolic compounds; Bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 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, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p- Hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) Polycondensates such as -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, modified substances thereof, and tetrabromo bisphenol A Axis of halogenated bisphenols, terpenes and phenols Although polyphenols, such as a compound, are mentioned, It is not limited to these. These may be used independently and may use 2 or more types.

Preferable phenol resins include phenol aralkyl resins (resin having an aromatic alkylene structure) in terms of dielectric constant, and particularly preferably have a structure having at least one selected from phenol, naphthol and cresol, and the linker Resin (specifically, gyrox, naphthol gyroc, phenol biphenylene novolak resin, cresol biphenylene novolak resin) characterized by the alkylene part being at least 1 sort (s) chosen from a benzene structure, a biphenyl structure, and a naphthalene structure. And phenol-naphthalene novolac resins).

Amine compounds and amide compounds; Nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and diamides of linoleic acid and polyamide resins synthesized by ethylenediamine; Although it is mentioned, it is not limited to these. These may be used independently and may use 2 or more types.

Acid anhydride compounds and carboxylic acid compounds; Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylnadic acid, nadic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, butane tetra Carboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane Acid anhydrides such as -1,3,4-tricarboxylic acid-3,4-anhydride; Although the carboxylic acid resin obtained by addition reaction of various alcohol, carbinol modified silicone, and the above-mentioned acid anhydride is mentioned, It is not limited to these. These may be used independently and may use 2 or more types.

As other hardening | curing agent which can be used together, the compound of imidazole, a trifluoro borane amine complex, a guanidine derivative, etc. are mentioned, but it is not limited to these. These may be used independently and may use 2 or more types.

In the curable resin composition of this invention, 0.7-1.2 equivalent is preferable as the functional group (hydroxyl group) equivalent with respect to 1 equivalent of epoxy groups of all epoxy resins. When 0.7 equivalent is not satisfied with respect to 1 equivalent of epoxy groups, or when it exceeds 1.2 equivalent, hardening may become incomplete and it may not be able to obtain favorable hardened | cured material property.

In curable resin composition of this invention, you may use a hardening accelerator together with a hardening | curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8. Tertiary amines such as -diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethyl And quaternary phosphonium salts such as quaternary ammonium salts such as ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts and tetrabutylphosphonium salts. (The counter ions of the quaternary salts are not particularly specified, such as halogen, organic acid ions, hydroxide ions, but organic acid ions and hydroxide ions are particularly preferred.) Metal compounds such as octylic acid tin and the like can be given. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

Curable resin composition of this invention can also be made to contain a phosphorus containing compound as a flame retardance provision component. As a phosphorus containing compound, a reactive type or an additive type may be sufficient. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dicresyl phosphate and 1,3-phenylene bis (di Phosphoric acid esters such as cresyl phosphate), 1,4-phenylenebis (dicresyl phosphate), and 4,4'-biphenyl (dicresyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10- Phosphanes such as oxides; Although phosphorus containing epoxy compounds, red phosphorus, etc. which are obtained by making an epoxy resin react with the active hydrogen of the said phosphanes are mentioned, Phosphate esters, a phosphane, or a phosphorus containing epoxy compound are preferable, and 1, 3- phenylene bis (Dicre Silphosphates), 1,4-phenylenebis (dicresylphosphate), 4,4'-biphenyl (dicresylphosphate) or phosphorus-containing epoxy compounds are particularly preferred. As for content of a phosphorus containing compound, phosphorus containing compound / all the epoxy resin = 0.1-0.6 (weight ratio) are preferable. In 0.1 or less, flame retardance may become inadequate, and in 0.6 or more, the hygroscopicity and dielectric property of hardened | cured material may fall.

Moreover, you may add antioxidant to curable resin composition of this invention as needed. As antioxidant which can be used, a phenol type, sulfur type, phosphorus antioxidant can be mentioned. Antioxidants can be used individually or in combination of 2 or more types. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part of resin components in curable resin composition of this invention, Preferably it is 0.01-0.5 weight part.

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) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl monophenols such as] -o-cresol; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-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-hydrocinnamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydrate Hydroxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3 -t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl Bisphenols such as 4-hydroxybenzyl sulfonate) calcium; 1,1,3-tris (2-methyl-4-hydroxy-5-t-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'-t-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1, 3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc. Polymeric phenols of the above are illustrated.

Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate Etc. are illustrated.

Specific examples of phosphorus antioxidants include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di- t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (octadecyl) phosphite, cyclic neopentane tetrayl ratio (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl ratio ( 2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogenphosphite Phosphites such as these; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro- Oxaphosphopenan, such as 9-oxa-10-phosphafaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphafaphenanthrene-10-oxide Trenoxides, etc. are illustrated.

These antioxidants can be used alone, respectively, but may be used in combination of two or more thereof. Especially in this invention, phosphorus antioxidant is preferable.

Moreover, you may add a light stabilizer to curable resin composition of this invention as needed.

As a light stabilizer, a hindered amine light stabilizer, especially HALS etc. are preferable. Although it does not specifically limit as HALS, As a typical thing, a dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6- tetramethyl-4- piperidyl-1, Polycondensate of 6-hexamethylenediamine with N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl succinate dimethyl-1- (2-hydroxyethyl) -4-hydroxy- 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-piperidyl) [[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-butylmalonic acid ratio (1,2,2,6,6-pentamethyl-4-piperidyl) etc. One type of HALS may be used and two or more types may be used together.

Moreover, binder resin can also be mix | blended with curable resin composition of this invention as needed. Examples of the binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenolic resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. It is not limited to these. It is preferable that the compounding quantity of binder resin is a range which does not impair flame retardance and heat resistance of hardened | cured material, and is 0.05-50 weight part normally with respect to 100 weight part of resin components, Preferably 0.05-20 weight part is used as needed.

An inorganic filler can be added to curable resin composition of this invention as needed. As the inorganic filler, powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc or beads which spheroidized them Although these etc. are mentioned, it is not limited to these. These may be used independently and may use 2 or more types. The content of these inorganic fillers occupies 0 to 95 weight% in curable resin composition of this invention. In addition, to the curable resin composition of the present invention, release agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate, various compounding agents such as surfactants, dyes, pigments, ultraviolet absorbers, and various thermosetting resins can be added. Can be.

Curable resin composition of this invention is obtained by mixing each component uniformly. Curable resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler and a compounding agent may be used for the polyphenylene ether novolak resin and the epoxy resin arrangement of the present invention, if necessary, using an extruder, a kneader, a roll, or the like. The mixture is sufficiently mixed to obtain a curable resin composition, and the curable resin composition is potted and melted (melted in the case of liquid phase), and then molded using a mold or a transfer molding machine, and then at 80 to 200 ° C for 2 to 10 hours. The hardened | cured material of this invention can be obtained by heating.

Moreover, the curable resin composition of this invention is melt | dissolved in solvents, such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, as needed, and curable resin Cured product of the curable resin composition A of the present invention by impregnating a prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, or the like by heat drying as a composition varnish You can do The solvent at this time is 10 to 70 weight% normally in the mixture of curable resin composition of this invention and the said solvent, The quantity which preferably occupies 15 to 70 weight% is used. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material containing carbon fiber can also be obtained as it is, for example by RTM system.

Moreover, curable resin composition of this invention can be used also as a modifier of a film type composition. Specifically, it can be used when improving the flexibility and the like in the B-stage. Such a film type resin composition is obtained as a sheet-like adhesive agent by apply | coating curable resin composition of this invention on a peeling film as said curable resin composition varnish, removing a solvent under heating, and performing B stage forming. This sheet-like adhesive agent can be used as an interlayer insulation layer in a multilayer board | substrate.

The curable resin composition of this invention can mention the general use which an epoxy resin is used, For example, an adhesive agent, a paint, a coating agent, a molding material (including sheet | seat, a film, FRP, etc.), an insulating material (print board, an electric wire coating) And other additives other than the sealant. Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobiles, general office, and medical. Among them, as an adhesive for electronic materials, an adhesive for semiconductors such as an interlayer adhesive of a multilayer substrate such as a build-up substrate, a die bonding agent, an underfill, an underfill for BGA reinforcement, an anisotropic conductive film (ACF), an anisotropic conductive paste (ACP), etc. Mounting adhesives and the like.

As a sealant and a substrate, potting for condensers, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, potting seals made of IC, LSI type COB, COF, TAB, underfill for flip chips, QFP, etc. And sealing (including reinforcing underfill) when installing IC packages such as BGA and CSP, and a package substrate. Moreover, it is also suitable for the board | substrate application in which the functionality used as a network board | substrate or a module board | substrate is calculated | required.

(Example)

Next, although an Example demonstrates this invention further more concretely, a part is a weight part below unless there is particular notice. In addition, this invention is not limited to these Examples.

It describes about the various analysis methods used by the Example below.

Epoxy equivalent: According to JIS K 7236 (ISO 3001)

ICI melt viscosity: Complies with JIS K 7117-2 (ISO 3219)

Softening point: Complies with JIS K 7234

Total chlorine: conforms to JIS K 7243-3 (ISO 21672-3)

GPC:

Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)

The connecting eluent is tetrahydrofuran

Flow rate is 0.5ml / min

Column temperature is 40 ℃

Detection: Differential Refraction Detector (RI)

Hereinafter, an Example and a comparative example demonstrate this invention concretely.

(Example 1)

175 parts of polyphenylene ether resin (Mn = 2066, Mw = 3553, Mz = 5951 in the GPC chart while carrying out nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus); 9.6 parts of p-xylylene glycol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 300 parts of toluene (reagent manufactured by Junsei Chemical Co., Ltd.), paratoluenesulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) 2 parts of preparation reagents) were added, it was made to react at 100 degreeC for 2 hours, and it was made to reflux at 110-120 degreeC after that, and reaction was performed for 7 hours as it is.

After completion of the reaction, 200 parts of methyl isobutyl ketone was added and water washing was repeated to confirm that the aqueous layer became neutral, and then the solvents under reduced pressure were distilled off from the oil layer using a rotary evaporator to thereby obtain the polyvalent phenylene ether furnace of the present invention. 179 parts of volac resins (P-1) were obtained. (In addition, in the GPC chart of polyphenylene ether resin which is a raw material, Mn = 2091, Mw = 4215, Mz = 7774.)

(Example 2)

75 parts of polyphenylene ether resin (MX90-100 made by SABIC) and p-xylylene glycol (Tokyo Chemical Industry Co., Ltd. make) while nitrogen purging to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. 5 parts of reagents), 130 parts of toluene (Junsei Chemical Co., Ltd. reagent), 1 part of paratoluene sulfonic acid monohydrate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and it was made to react at 100 degreeC for 2 hours, Thereafter, the reaction was carried out at 110-120 ° C. under reflux for 10 hours as it was.

After completion of the reaction, 100 parts of methyl isobutyl ketone was added and water washing was repeated to confirm that the aqueous layer became neutral, and then the solvents under reduced pressure were gradually removed from the oil layer using a rotary evaporator to confirm that no water was released. Methyl isobutyl ketone was added to adjust the resin concentration to 50%. This obtained 143 parts of polyhydric phenylene ether novolak resin varnishes (V-1) of this invention. In the chart of GPC, Mn = 2111, Mw = 4345 and Mz = 7932.

(Example 3)

87.5 parts of polyphenylene ether resin (MX90-100 made by SABIC) and p-xylylene glycol (Tokyo Chemical Industry Co., Ltd. make) while carrying out nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. Reagent) 4.8 parts, methyl isobutyl ketone (Junsei Chemical Co., Ltd. Reagent) 138 parts, paratoluene sulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd. Reagent) was added and reacted at 100 ° C for 2 hours. The reaction was carried out for 7 hours as it was at reflux at 110-120 ° C after that.

After completion of the reaction, 100 parts of methyl isobutyl ketone was added and water washing was repeated to confirm that the aqueous layer became neutral, and then the solvents under reduced pressure were gradually removed from the oil layer using a rotary evaporator to confirm that no water was released. Methyl isobutyl ketone was added to adjust the resin concentration to 60%.

After adding 50 parts of polyvalent phenylene ether novolak resin varnishes (V-2) of this invention obtained and 70 parts of phenol biphenylene novolaks (KAYAHARD GPH-65 by Nippon Kayaku Co., Ltd.), and dissolving, rotary EVA The solvents were distilled off under reduced pressure in the porator, and the hardening | curing agent composition (H-1) containing 30% of the polyhydric phenylene ether novolak resin of this invention was obtained. The softening point was 121 ° C.

(Example 4)

Except having changed 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 by Nippon Kayaku Co., Ltd.) into 30 parts in Example 3, operation was performed similarly and the hardening | curing agent composition (H-2) of this invention was obtained. .

(Example 5)

In Example 3, operation was performed similarly except having changed 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 by Nippon Kayaku Co., Ltd.) to 20 parts, and the polyhydric phenylene ether novolak resin of this invention is 60 % Contained curing agent composition (H-3) was obtained. The softening point was 130 ° C.

(Example 6)

100 parts of polyphenylene ether resin (Mn = 2960, Mw = 6863, Mz = 11851) in the flask equipped with the stirrer, the reflux condenser, and the stirring device while purging with nitrogen, while measuring SAPC-100 manufactured by SABIC and SA120-100, 10 parts of p-xylylene glycol (Tokyo Chemical Industry Co., Ltd. reagent), 140 parts of toluene (Junsei Chemical Co., Ltd. reagent), paratoluene sulfonic acid monohydrate (Tokyo Chemical Industry Co., Ltd.) 2.0 parts of preparation reagents) were added, it was made to react at 100 degreeC for 2 hours, and it was made to reflux at 110-120 degreeC after that, and reaction was performed for 7 hours as it is.

After completion of the reaction, 100 parts of methyl ethyl ketone was added, and gradually dropwise added to a vessel containing 1000 parts of methanol, and reprecipitation was carried out. After filtering the obtained resin powder, it wash | cleaned with methanol: water = 1: 1100 parts, and wash | cleaned 5 times with 100 parts of water. This obtained 89 parts of polyhydric phenylene ether novolak resin (P-3) of this invention. In the chart of GPC, Mn = 3683, Mw = 7356 and Mz = 11860. Furthermore, after mixing KAYAHARD GPH-65 using 20 parts and 50 parts of toluene with respect to 30 parts of obtained (P-3), the solvents under reduced pressure were distilled off in a rotary evaporator, and hardening | curing agent composition (H-4) was carried out, Got it.

(Comparative Example 1)

30 parts of polyphenylene ether resin (MX90-100 manufactured by SABIC) and 70 parts of phenolbiphenylene novolac (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved in methyl isobutyl ketone. The solvents were distilled off under reduced pressure in the porator to obtain a comparative curing agent composition (H'-1).

(Comparative Example 2)

30 parts of polyphenylene ether resin (MX90-100 manufactured by SABIC) and 20 parts of phenolbiphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved in methyl isobutyl ketone. The solvents were distilled off under reduced pressure in the porator to obtain a comparative curing agent composition (H'-2).

Examples 7-8 and Comparative Example 3

Dielectric constant and dielectric loss tangent test

The hardening | curing agent composition obtained above, an epoxy resin, etc. were mix | blended in the ratio (weight part) of Table 1, and it mixed uniformly and knead | mixed using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was grind | pulverized with the mixer and also tableted by the tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and further hardened | cured on the conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours after demolding, and the test piece for evaluation was obtained.

In addition, the physical property of hardened | cured material was measured with the following method.

Dielectric constant and dielectric tangent: cavity resonance technique

Equipment Kanto Electric Application Development Joint Resonator 1GHz

Reference Teflon®

Example 9 and Comparative Example 4

The hardening | curing agent composition obtained above, epoxy resin, etc. were mix | blended in the ratio (weight part) of Table 2, and it mixed uniformly and knead | mixed using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was grind | pulverized with the mixer and also tableted by the tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and after demolding, it hardened | cured on conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours, and obtained the test piece for evaluation.

Dielectric constant and dielectric tangent: cavity resonance technique

Equipment Kanto Electric Application Development Joint Resonator 1GHz

Reference Teflon®

Heat resistance (TMA): Measured in accordance with JIS K 7244.

Example 10 and Comparative Example 5

The hardening | curing agent composition obtained above, an epoxy resin, etc. were mix | blended in the ratio (weight part) of Table 3, it mixed uniformly and kneaded using the mixing roll, and obtained the epoxy resin composition for sealing. This epoxy resin composition was grind | pulverized with the mixer and also tableted by the tablet machine. This tablet-ized epoxy resin composition was transfer-molded (175 degreeC x 60 second), and further hardened | cured on the conditions of 160 degreeC x 2 hours + 180 degreeC x 6 hours after demolding, and the test piece for evaluation was obtained.

Dielectric constant and dielectric tangent: cavity resonance technique

Equipment Kanto Electric Application Development Joint Resonator 1GHz

Reference Teflon®

Heat resistance (DMA)

Dynamic Viscoelasticity Meter: TA-instruments, DMA-2980

Measuring temperature range: -30 to 280 ° C

Temperature rise rate: 2 ℃ / min

Test piece size: The crop cut out to 5 mm x 50 mm was used (thickness about 800 micrometers).

Tg: The peak point of Tan-δ was made into Tg.

Heat resistance (TMA): Measured in accordance with JIS K 7244.

From the above result, it is clear that curable resin composition of this invention is excellent also in heat resistance compared with the use of H'-1 and H'-2 which have a similar structure as a hardening | curing agent (composition), and the dielectric constant compared with using another hardening | curing agent It was confirmed that the dielectric tangent was good and had excellent dielectric properties.

Although this invention was demonstrated in detail with reference to the specific aspect, it was clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

In addition, this application is based on the JP Patent application (patent application 2012-244309) of an application on November 6, 2012, The whole is taken in into consideration. Also, all references cited herein are incorporated in their entirety.

The polyphenylene ether novolak resin of the present invention is useful as a curing agent for epoxy resins, and the epoxy resin composition comprising the polyphenylene ether novolak resin as a curing agent is used as an insulating material for electrical and electronic components and a laminated board (printed wiring board, bill). It is useful for various composite materials, adhesives, paints, etc., such as a grader board | substrate etc.) and CFRP.

Claims

A poly (phenylene ether) resin having a molecular weight of 400 to 8000 (weight average molecular weight polystyrene equivalent), a polyhydric phenylene ether novolak resin, wherein a biphenol or bisphenol and an oxidized polymer of a phenol compound are connected by an organic group. .

The method of claim 1,
The organic group is represented by at least one of following formula (1), The polyhydric phenylene ether novolak resin characterized by the above-mentioned.

At least 1 type of polyhydric phenylene ether novolak resin of Claim 1 or 2 is contained, The epoxy resin composition characterized by the above-mentioned.

It is obtained by hardening the epoxy resin composition of Claim 3, The hardened | cured material characterized by the above-mentioned.

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