TWI537335B - Flame-retardant epoxy resin, composition containing such epoxy resin as a necessary component, and hardened substance thereof - Google Patents

Description

a flame retardant epoxy resin and a composition containing the epoxy resin as an essential component, and a cured product

The present invention relates to a film material, a sealing material, a molding material, a casting material, an adhesive, an electrical insulating coating, and a flame retardant which are suitable for a prepreg which can be used for an electronic circuit substrate, can be used for a copper clad laminate or an electronic component. Phosphorus-containing epoxy resin and composition, and hardened materials such as composite materials and powder coatings.

Epoxy resin is widely used in electronic parts, electric machines, automobile parts, FRP, sporting goods, etc., because of its excellent adhesion, heat resistance and formability. Among them, copper-clad laminates used in electronic parts and electric machines are used. In the case of a sealing material, a brominated epoxy resin is used for the purpose of preventing or delaying safety such as fire.

By introducing a halogen represented by bromine into an epoxy resin, it is possible to impart a flame retardancy and an excellent cured product due to high reactivity of an epoxy group. However, since harmful substances such as halogen compounds may be generated during combustion, the demand for epoxy resins which are flame retardant without using halogens is gradually increasing.

On the other hand, Patent Document 1 discloses a method of imparting flame retardancy by introducing a phosphorus atom into an epoxy resin skeleton. However, since this method reacts an epoxy group which provides a hardening reaction with a phosphorus compound, the crosslinking density at the time of hardening is reduced, and the physical property of a hardened material cannot be satisfied. Therefore, Patent Document 2 discloses a method of introducing an epoxy resin skeleton by reacting a phosphorus compound with a quinoline compound as a phosphorus-containing compound having two phenol groups and reacting with an epoxy resin. Although the method can obtain a dramatic increase in the physical properties of the hardened material, There is a high-quality copper-clad laminate, but since the step of reacting the phosphorus compound with the quinoline compound is required, the reaction time is prolonged and the productivity is deteriorated. Patent Document 3 discloses a phenolic epoxy resin having a number of cores of 3 to 8, but relates to heat resistance and impregnation, and does not show or teach any flame retardancy.

[Previous Technical Literature] [Patent Literature]

(Patent Document 1) Japanese Patent Laid-Open No. Hei 11-166035

(Patent Document 2) Japanese Patent Laid-Open No. Hei 11-279258

(Patent Document 3) Japanese Laid-Open Patent Publication No. 62-064821

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2002-194041

(Patent Document 5) Japanese Patent Laid-Open Publication No. 2007-126683

The present inventors have continually studied the phosphorus-containing epoxy resin, and as a result, completed the present invention, which is not only successful in rendering flame retardancy by reacting a phenolic epoxy resin having a specific molecular weight distribution with a specific phosphorus compound. The advantage of the productivity of Patent Document 1 can be maintained while the amount of the high-priced phosphorus compound is reduced, and the physical properties of the cured product close to Patent Document 2 can be achieved. The difunctional epoxy resin constituting the dinuclear component of the novolac type epoxy resin, although reacting with the phosphorus compound to form a reaction component having no epoxy group, is considered to be a phenolic epoxy resin used in the present invention. Since the content of the dinuclear component is reduced, the reaction component having no epoxy group can be reduced, and it is considered that the flame retardancy and physical properties can be improved. Furthermore, this is considered to be the invention The phenolic epoxy resin used can reduce the content of the high-molecular weight component having a tetranuclear or higher, and further improve the flame retardancy and physical properties of the phosphorus-containing epoxy resin. It is presumed that the reason is that when the high molecular weight component of the tetranuclear or higher body contained in the phenolic epoxy resin partially reacts with the phosphorus compound, it becomes a phosphorus-containing epoxy resin having a large portion in structure, and reacts with the epoxy group and the hardener. The hardening reactivity is significantly deteriorated due to steric hindrance. The present invention provides a film material, a sealing material, a molding material, a casting material, an adhesive, an electrical insulating coating, and a flame retardant which are suitable for a prepreg which can be used for an electronic circuit substrate, can be used for a copper clad laminate or an electronic component. A composite material, a powder coating, or the like, and is a low-cost and high-quality flame-retardant phosphorus-containing epoxy resin and the epoxy resin composition.

That is, the present invention is: (1) A phosphorus-containing epoxy resin having a dinuclear body content of 15% by area or less and a trinuclear group content of 15% by area to 60 areas as measured by gel permeation chromatography. % is obtained by reacting a phenolic epoxy resin (A) having a molecular weight distribution having a number average molecular weight of 350 to 700 with a compound represented by the general formula (1) as an essential component; (gel permeation chromatography measurement conditions) Using TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000HXL manufactured by Tosoh Co., Ltd. in series, the column temperature was 40 ° C; in addition, the eluent was used in tetrahydrofuran at a flow rate of 1 ml/min, and the detector was subjected to an RI (differential refractometer) tester. Determination of the number average molecular weight of the polyethylene calibration line; (wherein R1 and R2 are hydrogen or a hydrocarbon group, which may be the same or different, the phosphorus atom may have a cyclic structure with R1 and R2, n represents 0 or 1); (2) a phosphorus-containing epoxy resin composition, The phosphorus-containing epoxy resin of the above (1) and the hardener are formulated by using one epoxy group in the range of 0.3 to 1.5 active groups; (3) a prepreg containing the above (2) The phosphorus epoxy resin composition is impregnated into the substrate; (4) an epoxy resin cured product obtained by hardening the phosphorus-containing epoxy resin composition described in (2) above; (5) a laminated board It is obtained by hardening the phosphorus-containing epoxy resin composition of the above (2).

The present invention enables a phosphorus-containing epoxy resin having a specific molecular weight distribution to react with a specific phosphorus compound, which can make the flame retardancy leap compared to the use of a phenolic epoxy resin having a conventional molecular weight distribution. The improvement and reduction of high-priced phosphorus compounds, as a result, can improve the physical properties of the hardened material, and by controlling the molecular weight distribution of the phenolic epoxy resin used, it is a resin having a specific molecular weight distribution, and can simultaneously achieve good flame retardancy and excellent The two objects of hardened physical properties.

The invention will be described in detail below.

The novolac type epoxy resin is a polyfunctional novolac type epoxy resin obtained by reacting a phenolic resin of a reaction product of a phenol and an aldehyde with an epihalohydrin. Examples of the phenol to be used include phenol, cresol, ethyl phenol, butyl phenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, Examples of the aldehydes such as naphthalenediol and bisphenol A include formalin, formaldehyde, hydroxybenzaldehyde, and salicylaldehyde. Further, an aralkyl phenol resin which is substituted for an aldehyde using xylene dimethanol, dichloroxylene, bischloromethyl naphthalene or bischloromethylbiphenyl is also included in the novolac phenol resin of the present invention. The novolac type phenol resin is epoxidized with an epihalohydrin to obtain a novolac type epoxy resin.

Specific examples of the phenolic epoxy resin include: EPOTOHTO YDPN-638 (Nippon Chemical Co., Ltd. phenol novolac type epoxy resin), EPIKOTE 152, EPIKOTE 154 (Mitsubishi Chemical Co., Ltd. phenol) Phenolic epoxy resin), EPICLON N-740, EPICLON N-770, EPICLON N-775 (phenolic phenolic epoxy resin manufactured by DIC Corporation) EPOTOHTO YDCN-700 series (Nippon Steel Chemical Co., Ltd. cresol Phenolic epoxy resin), EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-695 (cresol phenolic phenolic epoxy resin), ECON-1020, ECON-102S, ECON-104S (Nippon Chemical Pharmaceutical Co., Ltd. cresol novolac epoxy resin), EPOTOHTO ZX-1071T, ZX-1270, ZX-1342, (Nippon Steel Chemical Co., Ltd. alkylphenol type) Epoxy resin), EPETOHTO ZX-1247, GK-5855 (styrene-based phenolic novolac epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPOTOHTO ZX-1142L (naphthol phenolic epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN -155, ESN-185V, ESN-175 (beta-naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN-355 of ESN-300 series, ESN-375 (Nippon Steel Chemical Co., Ltd. Company's naphthalene diphenol aralkyl epoxy resin), ESN-400 series ESN-475V, ESN-485 (alpha naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) biphenol phenolic type Epoxy resins and the like, but such epoxy resins do not have a specific molecular weight distribution with respect to the present invention.

In order to obtain the phenolic epoxy resin having a specific molecular weight distribution used in the present invention, the phenol phenolic resin obtained by removing the low molecular weight component by adjusting the crude phenolic phenol resin obtained by adjusting the molar ratio of the phenol to the aldehyde can be epoxidized. Alternatively, the phenol phenol resin obtained by the production method shown in Patent Document 4 and Patent Document 5 may be epoxidized.

The molar ratio of the phenolic phenolic resin to the phenol and the aldehyde is produced at a ratio of 1 or more to 1 mole of aldehyde and phenol, but in the case of the molar ratio, a dinuclear is generated. In the case of a trinuclear body, a high molecular weight body is formed in a case where the molar ratio is small, and a dinuclear body and a trinuclear body are reduced.

The phenolic epoxy resin having a specific molecular weight distribution used in the present invention can be obtained by removing the dinuclear component and/or the tetranuclear component from the obtained crude phenol phenol resin by utilizing the difference in solubility of various solvents. It is obtained by a method of dissolving and removing a dinuclear body in an alkaline aqueous solution, etc., but other conventional separation methods can also be used.

A conventional epoxidation technique can be used for phenol resins of controlled molecular weight. A phenolic epoxy resin having a specific molecular weight distribution is obtained. Alternatively, the dinuclear epoxy resin component may be removed by various methods from a commercially available phenolic epoxy resin to obtain a phenolic epoxy resin having a specific molecular weight distribution. Other conventional separation methods can also be used.

The phenolic epoxy resin having a specific molecular weight distribution of the present invention has a dinuclear content of 15% by area or less, preferably 5% by area to 12% by area. Due to the small amount of the dinuclear body, the physical properties such as adhesion can be improved. The content of the trinuclear body is 15% by area to 60% by area, preferably 20% by area to 50% by area. The number average molecular weight is from 350 to 700, preferably from 380 to 600. The usable molecular weight dispersion (weight average molecular weight / number average molecular weight) is from 1.1 to 2.8, preferably in the range of from 1.2 to 2.5, more preferably from 1.2 to 2.3, and if the ratio is less than 1.1, the physical properties such as adhesion are poor, and the condition exceeds 2.8. There is a fear of reducing the flame retardancy and heat resistance.

Specific examples of the phosphorus compound represented by the formula (1) include dimethylphosphine, diethylphosphine, diphenylphosphine, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10. -Oxide (manufactured by HCA Sanko Chemical Co., Ltd.), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylphosphine Oxide, 1,5-cyclooctylphosphine oxide (manufactured by CPHO Nippon Chemical Industry Co., Ltd.), and the like. These phosphorus-containing compounds may be used singly or in combination of two or more kinds, but are not limited to the phosphorus compounds.

The reaction method of the phosphorus compound represented by the formula (1) and the novolac type epoxy resin having a specific molecular weight distribution can be carried out by a conventional method. The reaction is carried out under stirring at a reaction temperature of from 100 ° C to 200 ° C, more preferably from 120 ° C to 180 ° C. Active hydrogen directly bonded to a phosphorus atom of a phosphorus compound represented by the general formula (1) It reacts with the epoxy group of the epoxy resin. The end point of the reaction was confirmed by tracking the epoxy equivalent to a value of 99% or more of the theoretical epoxy equivalent. Alternatively, the method of confirming the end point of the reaction as the acid value of the epoxy resin as the acid value of the epoxy resin, or the analysis of the instrument represented by liquid chromatography or the like is used to trace the remaining general formula. (1) A method of a phosphorus compound or the like. Although any of the methods may be employed, it is necessary to completely react the epoxy resin with the phosphorus compound represented by the formula (1). The catalyst can be used as needed in consideration of the reaction rate. Specifically, a tertiary amine such as benzyldimethylamine, a quaternary ammonium salt such as tetramethylammonium chloride, or a phosphine such as triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine can be used. Various catalysts such as anthracene salts such as ethyltriphenylphosphonium bromide, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

When the phosphorus compound represented by the formula (1) is reacted with a phenolic epoxy resin having a specific molecular weight distribution, various epoxy resin modifiers may be used in combination as needed to the extent that the properties of the present invention are not impaired. The modifiers include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, isophthalene. Phenol, methyl resorcinol, bisphenol, tetramethylbisphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxystilbene, phenolic phenolic resin, cresol novolac resin, bisphenol A Various phenols such as phenolic resin, dicyclopentadiene phenolic resin, phenol aralkyl resin, naphthol phenolic resin, terpene phenolic resin, heavy oil modified phenolic resin, brominated phenol phenolic resin, or various phenols a polyphenol resin obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, or aniline, phenylenediamine, toluidine, xylyleneamine, diethyltoluenediamine Diaminodiphenylmethane, Diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone, diaminodiphenyl thioether, diaminodiphenyl hydrazine, bis(aminophenyl) fluorene , diaminodiethyl dimethyl diphenylmethane, diaminodiphenyl ether, diamino benzanilide, diaminobiphenyl, dimethyldiamine biphenyl, biphenyl tetra Amine, diaminophenyl hydrazine, diaminophenoxy benzene, diaminophenoxyphenyl ether, diaminophenoxybiphenyl, diaminophenoxyphenyl hydrazine, diamino benzene An amine compound such as oxyphenylpropane or diaminonaphthalene is not limited to the above-mentioned modifiers, and may be used in combination of two or more types.

When the phosphorus compound represented by the formula (1) is reacted with a novolac type epoxy resin having a specific molecular weight distribution, various epoxy resins can be used as needed without impairing the characteristics of the present invention. Specifically, YDC-1312, ZX-1027 (hydrogen oxime epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YX-4000 (manufactured by Mitsubishi Chemical Corporation), and ZX-1251 (Nippon Steel Chemical Co., Ltd.) Co., Ltd. Bisphenol type epoxy resin), EPOTOHTO YD-127, EPOTOHTO YD-128, EPOTOHTO YD-8125, EPOTOHTO YD-825GS, EPOTOHTO YD-011, EPOTOHTO YD-900, EPOTOHTO YD901 (Nippon Steel Chemical Co., Ltd. BPA epoxy resin, EPOTOHTO YDF-170, EPOTOHTO YDF-8170, EPOTOHTO YDF-870GS, EPOTOHTO YDF-2001 (BPF epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPOTOHTO YDPN-638 (new Nippon Steel Chemical Co., Ltd. phenolic phenolic epoxy resin), EPOTOHTO YDCN-701 (Nippon Steel Chemical Co., Ltd. cresol novolac epoxy resin), ZX-1201 (Nippon Steel Chemical Co., Ltd. double Phenolphthalein type epoxy resin), NC-3000 (biphenyl aralkyl phenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), EPPN-501H, EPPN-502H (Multifunctional epoxy resin manufactured by Nippon Kayaku Co., Ltd.), ZX-1355 (naphthalene glycol epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN-155, ESN-185V, ESN-175 (new Nippon Steel Chemical Co., Ltd. made β-naphthol aralkyl type epoxy resin), ESN-355, ESN-375 (Nippon Steel Chemical Co., Ltd. bisphthol aralkyl type epoxy resin), ESN-475V a phenolic compound such as a polyphenol resin such as ESN-485 (a naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.); an epoxy resin made of an epihalohydrin, EPOTOHTO YH-434, and EPOTOHTO Amine compounds such as YH-434GS (diamine diphenylmethane tetraglycidyl ether manufactured by Nippon Steel Chemical Co., Ltd.); epoxy resin manufactured from epihalohydrin, YD-171 (Nippon Steel Chemical Co., Ltd.) A carboxylic acid such as a dimer acid type epoxy resin, or an epoxy resin obtained by using a halogenated alcohol, but not limited to these resins, and may be used in combination of two or more types.

The phosphorus-containing epoxy resin composition of the present invention uses a phosphorus-containing epoxy resin having a specific molecular weight distribution of a phenolic epoxy resin as an essential component, and the hardener can be used for various phenol resins and anhydride acids, amines, anthracenes. A curing agent for an epoxy resin which is usually used, such as an acid polyester, may be used singly or in combination of two or more types.

Specific examples of the phenol resin in the above-mentioned curing agent include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, and tetramethyl bisphenol. F, tetramethyl bisphenol S, tetramethyl bisphenol Z, dihydroxy diphenyl sulfide, 4, 4 '-thiobis (3-methyl-6-tert-butylphenol) and other bisphenols Or catechol, resorcinol, methyl resorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, two First Dihydroxybenzenes such as tributylhydroquinone, hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene, phenolic phenolic resin, DC-5 (Nippon Steel Chemical Co., Ltd. cresol novolak type ring) Phenols such as oxy-resin and naphthol phenolic resin, and/or condensates of naphthols and aldehydes, phenols such as SN-160, SN-395, and SN-485 (manufactured by Nippon Steel Chemical Co., Ltd.) / or condensates of naphthols and xylylene alcohol, condensates of phenols and / or naphthols and cumene acetophenone, phenols and / or naphthols and dicyclopentadiene Phenolic compounds such as reactants, phenols and/or condensates of naphthols and biphenyl condensing agents

Examples of the phenols include phenol, cresol, xylenol, butylphenol, pentylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Naphthol, 2-naphthol, and the like.

Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, gly Dialdehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthaldehyde, hydroxybenzaldehyde, and the like. A biphenyl condensing agent is exemplified by bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxyethyl)biphenyl, bis(chloromethyl)biphenyl, and the like.

Specific examples of the acid anhydride hardener include, for example, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, and trimellitic anhydride. (trimellitic anhydride), an acid anhydride such as methyl nadic anhydride.

Specific examples of the amine hardener include, for example, di-ethyltriamine, tri-ethyltetramine, m-xylenediamine, isophorone diamine (isophorone). Polyamines of condensates of acids and polyamines such as diamine), diaminodiphenylmethane, diaminodiphenylphosphonium, diaminodiphenyl ether, dicyanodiamine, dimer acid - an amine compound such as an amine.

Further, the epoxy resin other than the phosphorus-containing epoxy resin of the present invention may be blended in the range which does not impair the characteristics of the present invention, and specific examples thereof include: EPOTOHTO YD-128, EPOTOHTO YD-8125 (manufactured by Nippon Steel Chemical Co., Ltd.) BPA type epoxy resin), EPOTOHTO YDF-170, EPOTOHTO YDF-8170 (BPF type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YSLV-80XY (tetramethyl bisphenol F manufactured by Nippon Steel Chemical Co., Ltd.) Epoxy resin), EPOTOHTO YDC-1312 (hydroquinone epoxy resin), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), EPOTOHTO YDPN-638 (phenolic phenolic phenol manufactured by Nippon Steel Co., Ltd. Epoxy resin), EPOTOHTO YDCN-701 (Nippon Steel Chemical Co., Ltd. cresol novolac epoxy resin), EPOTOHTO ZX-1201 (Nippon Steel Chemical Co., Ltd. bisphenol oxime epoxy resin), TX-0710 (Nippon Steel Chemical Co., Ltd. bisphenol S type epoxy resin), EPICLON EXA-1515 (Daily Chemical Industry Co., Ltd. bisphenol S type epoxy resin), NC-3000 (Nippon Chemical Copolymer styrene phenolic epoxy resin), EPOTOHTO ZX -1355, EPOTOHTO ZX-1711 (Naphthalenediol-type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPOTOHTO ESN-155, (beta-naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) , EPOTOHTO ESN-355, EPOTOHTO ESN-375 (Nippon Steel Chemical Co., Ltd. bisphthol aralkyl epoxy resin), EPOTOHTO ESN-475V, EPOTOHTO ESN-485 (Nippon Steel Chemical Co., Ltd. Naphthol aralkyl type epoxy resin) EPPN-501H (triphenylmethane type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), SUMIEPOXY TMH-574 (triphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.) An epoxy resin made of a phenolic compound of a polyphenolic phenolic ring and an epihalohydrin; an amine compound and the like by EPOTOHTO YH-434 (diamine diphenylmethanetetraglycidyl ether manufactured by Nippon Steel Chemical Co., Ltd.) Epoxy resin produced by halogenated alcohol; jER 630 (amino phenolic epoxy resin manufactured by Mitsubishi Chemical Corporation), EPOTOHTO FX-289B, EPOTOHTO FX-305, TX-0932A (Nippon Steel Chemical Co., Ltd. Epoxy resin and phosphorus-containing phenol compound Phosphorus-containing resin obtained by the modification of the modifier; YSLV-120TE (disulfide epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPOTOHTO ZX-1684 (Nippon Steel Chemical Co., Ltd. Phenol type epoxy resin), DENACOL EX-201 (resorcinol type epoxy resin manufactured by Nagase ChemteX Co., Ltd.), EPICLON HP-7200H (dicyclopentadiene type epoxy resin manufactured by DIC Corporation), amino group Ethyl formate modified epoxy resin, containing Epoxy resin of oxazolidone ring, TX-0929, TX-0934 (alkylene glycol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.).

The epoxy resin composition of the present invention has a phosphorus content of 0.8% to 7%, preferably 1% to 6%, more preferably 1.5% to 4%. When the amount is less than 0.8%, the flame retardancy is not obtained, and when it is more than 7%, the physical properties such as the decrease in heat resistance and the increase in hygroscopicity are deteriorated.

The composition of the present invention may be blended with a conventionally used epoxy resin hardening accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine or an imidazole as needed. Specifically, for example, a phosphine compound such as triphenylphosphine or a phosphonium salt such as tetraphenylphosphonium bromide or the like; Imidazoles such as imidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, and the like An imidazolium salt of a salt formed from benzenetricarboxylic acid, isocytric cyanide or boron; an amine such as benzyldimethylamine or 2,4,6-tris(dimethylaminomethyl)phenol; Tertiary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, and salts with such phenols and phenolic phenolic resins; boron trifluoride with amines, ether compounds, etc. a compound; an aromatic hydrazine or a hydrazine salt. These hardeners may be used singly or in combination of two or more types.

An organic solvent for adjusting the viscosity can be used in the phosphorus-containing epoxy resin composition of the present invention. Examples of the organic solvent that can be used include decylamines such as N,N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, and methanol and ethanol. An aromatic hydrocarbon such as an alcohol, benzene or toluene. One or a plurality of such solvents may be blended so that the epoxy resin concentration is in the range of 30 to 80% by weight.

In addition, inorganic fillers such as ammonium hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, gibbsite, titanium dioxide, glass powder, silica balloon, and the like, microparticle rubber, thermoplastic elastomer, etc. may be used as needed. Organic filler materials, fibrous filler materials such as glass fiber, wood pulp fiber, synthetic fiber, ceramic fiber, reinforcing materials such as glass cloth, aramid cloth, carbon fiber, and the like.

As a result of evaluation of the laminate of the epoxy resin composition, a phosphorus-containing epoxy resin obtained by reacting a phenolic epoxy resin having a specific molecular weight distribution of an epoxy resin with a phosphorus compound represented by the general formula (1) , while maintaining productivity, it can achieve flame retardancy even if the phosphorus content is reduced, and The physical properties of the hardened material are not only suitable for the copper-clad laminate used in the electronic circuit substrate, but also suitable for the sealing materials, molding materials, casting materials, adhesives, electrical insulating coatings used in electronic components, and need to be flame-retardant. Composite of sex.

(Example)

The present invention will be specifically described below by way of examples and comparative examples, but the invention is not limited to the examples. Unless otherwise specified, "parts" means parts by weight, and "%" means % by weight. The measurement method was measured according to the following respective methods. Epoxy equivalent: Measured according to the method described in JIS K7236.

Dinuclear content, trinuclear content, number average molecular weight, weight average molecular weight: molecular weight distribution measured by gel permeation chromatography, dinuclear content, trinuclear content from peak area %, standard Single distribution polyethylene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40 made by Tosoh Co., Ltd.) The obtained calibration curve is converted into a number average molecular weight and a weight average molecular weight. Specifically, it was used for a tandem column (TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000HXL manufactured by Tosoh Corporation) on a main body (HLC-8220GPC manufactured by Tosoh Co., Ltd.), and the column temperature was 40 °C. Further, the eluent was tetrahydrofuran, the flow rate was 1 ml/min, and the detector was subjected to an RI (differential refractometer) tester.

Phosphorus content: sulfuric acid, hydrochloric acid, perchloric acid are added to the sample, heated and wet ashing to turn all phosphorus atoms into orthophosphoric acid. The metavanadate and the molybdate are reacted in an acidic solution of sulfuric acid, and the resulting ammonium phosphomolybdate (n-hydrate) is determined. The absorbance at 420 nm is determined by the amount of phosphorus atom contained in % by weight using a calibration curve prepared by using potassium dihydrogen phosphate in advance. The phosphorus content of the laminate is expressed in terms of the content of the resin component in the laminate.

Copper foil peeling strength and interlayer adhesion: measured by JIS C-6481, and the interlayer adhesion was measured by peeling between the seventh layer and the eighth layer. Flammability: Five test pieces were tested according to UL94 (Safety Certification Specification of Underwriters Laboratories Inc.), and the first and second flames were contacted in seconds (5 each for 2 times, for a total of 10 times) The total time of the subsequent flame burning duration.

Glass transition temperature DSC: DSC extrapolated temperature when measured by a differential scanning calorimeter (EXTRAR6000 DSC6200 manufactured by SII Nanotechnology Co., Ltd.) at a temperature rising condition of 10 ° C /min. Glass transition temperature TMA: TMA extrapolated temperature when measured by a thermomechanical analyzer (EXTRAR6000 TMA/SS120U, manufactured by SII Nanotechnology Co., Ltd.) at a temperature rise condition of 10 ° C/min.

Epoxy resin used:

YDF-170 (Nippon Steel Chemical Co., Ltd. bisphenol F-type epoxy resin, the ratio of dinuclear body by gel permeation chromatography is 81.9 area%, the content of trinuclear body is 5.3 area%, and the number average molecular weight 254, weight average molecular weight of 285, dispersion of 1.12, epoxy equivalent of 169 g / eq) YDPN-638 (Nippon Steel Chemical Co., Ltd. phenolic novolac type epoxy resin, two-core by gel permeation chromatography The volume fraction was 22.1 area%, the trinuclear body content was 10.7 area%, and the number average molecular weight was 463, and the weight average was YDCN-700-2, a molecular weight of 1003, a dispersion of 2.17, an epoxy equivalent of 176 g/eq (Nippon Steel Chemical Co., Ltd., a cresol novolac epoxy resin, for the determination of dinuclear bodies by gel permeation chromatography) The content rate was 10.5 area%, the trinuclear body content was 10.9 area%, the number average molecular weight was 633, the weight average molecular weight was 1187, the degree of dispersion was 1.88, and the epoxy equivalent was 200 g/eq.

Synthesis Example 1

In a four-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 2,500 parts of phenol and 7.5 parts of oxalic acid dihydrate were placed, and while stirring, nitrogen gas was introduced, and the temperature was raised by heating. 474.1 parts of 37.4% marinar was added dropwise at 80 ° C, and the dropwise addition was completed at 30 minutes. The reaction temperature was further maintained at 92 ° C for 3 hours to carry out a reaction. The temperature was raised to 110 ° C while removing the water generated by the temperature rising reaction to the outside of the system. The residual phenol was recovered under reduced pressure at 160 ° C to obtain a phenol phenol resin. Further, the temperature is raised to recover a part of the dinuclear body. The dinucleotide content of the obtained phenol novolac resin was measured by gel permeation chromatography to be 10 area%.

Synthesis Example 2

The phenol novolac resin obtained in Synthesis Example 1 was dissolved in MIBK, and washed with a 5% sodium hydroxide solution. After removing the remaining sodium hydroxide by washing with water, MIBK was recovered under reduced pressure. The dinucleotide content of the obtained phenol novolac resin was measured by gel permeation chromatography to be 6 area%.

Synthesis Example 3

The same operation as in Synthesis Example 1 was carried out except that the amount of 37.4% of fumarin used in Synthesis Example 1 was changed to 711.1 parts. Gel permeation chromatography The dinucleotide content of the obtained phenol novolac resin was 10 area%.

Synthesis Example 4

665.8 parts of the phenol novolac resin of Synthesis Example 1, 2110.8 parts of epichlorohydrin, and 17 parts of water were placed in the same apparatus as in Synthesis Example 1, and the temperature was raised to 50 ° C while stirring. 14.2 parts of a 49% aqueous sodium hydroxide solution was charged and the reaction was carried out for 3 hours. The temperature was raised to 64 ° C, and the pressure was reduced to the extent that water was refluxed, and 457.7 parts of 49% sodium hydroxide was added dropwise over 3 hours to cause a reaction. The temperature was raised to 70 ° C to carry out dehydration, and the temperature was set to 135 ° C to recover the residual epichlorohydrin. Return to atmospheric pressure and add 1232 parts of MIBK to dissolve. 1200 parts of ion-exchanged water was added, and the mixture was stirred and dissolved in water to remove the by-product salt. Then, 37.4 parts of a 49% aqueous sodium hydroxide solution was charged, and the reaction was stirred at 80 ° C for 90 minutes to carry out a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain a novolac type epoxy resin. The dinuclear body content measured by gel permeation chromatography was 9 area%, the trinuclear body content was 37.0 area%, the number average molecular weight was 440, the weight average molecular weight was 605, the degree of dispersion was 1.38, and the epoxy equivalent was 176. g/eq.

Synthesis Example 5

The same procedure as in Synthesis Example 4 was carried out except that the phenol novolac resin of Synthesis Example 2 was used instead of the phenol novolac resin of Synthesis Example 1 used in Synthesis Example 4 to obtain a novolac type epoxy resin. The dinucleotide content determined by gel permeation chromatography was 5.5 area%, the trinuclear body content was 34.6 area%, the number average molecular weight was 485, the weight average molecular weight was 684, the dispersion was 1.41, and the epoxy equivalent was 176. g/eq.

Synthesis Example 6

The same procedure as in Synthesis Example 4 was carried out except that the phenol novolac resin of Synthesis Example 3 was used instead of the phenol novolac resin of Synthesis Example 1 used in Synthesis Example 4 to obtain a novolac type epoxy resin. The dinucleotide content determined by gel permeation chromatography was 9.1 area%, the trinuclear body content was 24.2 area%, the number average molecular weight was 593, the weight average molecular weight was 954, the degree of dispersion was 1.61, and the epoxy equivalent was 177 g. /eq.

Synthesis Example 7

In place of phenol phenolic aldehyde of Synthesis Example 1 used in Synthesis Example 4, except that LV-70S (phenolic phenolic aldehyde epoxy resin manufactured by Qunrong Chemical Industry Co., Ltd., 2% dinuclear component and 75% trinuclear component) was used. The same procedure as in Synthesis Example 4 was carried out except for the resin to obtain a novolac type epoxy resin. The dinucleotide content determined by gel permeation chromatography was 1.4 area%, the trinuclear body content was 56.1 area%, the number average molecular weight was 486, the weight average molecular weight was 617, the degree of dispersion was 1.27, and the epoxy equivalent was 176 g. /eq.

Synthesis Example 8

In addition to TRI-002 (a triphenylmethane type phenolic resin manufactured by Showa Denko Co., Ltd., a dinuclear component of 4.6%, a trinuclear component of 29.7%), 2326.5 parts, and 4,4-methylene xylenol 173.6 parts. The phenolic epoxy resin was obtained in the same manner as in Synthesis Example 4 except that the phenol novolac resin of Synthesis Example 1 used in Synthesis Example 4 was used. The dinuclear body content measured by gel permeation chromatography was 9.2 area%, the trinuclear body content was 21.8 area%, the number average molecular weight was 640, the weight average molecular weight was 1109, the degree of dispersion was 1.80, and the epoxy equivalent was 177 g. /eq.

Synthesis Example 9

The phenol phenolic aldehyde of Synthesis Example 1 used in Synthesis Example 4 was replaced by BRG-558 (phenolic phenolic epoxy resin manufactured by Qunrong Chemical Industry Co., Ltd., having a dinuclear component of 12.0% and a trinuclear component of 10.0%). The same procedure as in Synthesis Example 4 was carried out except for the resin to obtain a novolac type epoxy resin. The dinuclear body content measured by gel permeation chromatography was 10.4 area%, the trinuclear body content was 5.8 area%, the number average molecular weight was 818, the weight average molecular weight was 2436, the degree of dispersion was 2.98, and the epoxy equivalent was 177 g. /eq.

Example 1

824 parts of the phenol novolac type epoxy resin of Synthesis Example 4, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide manufactured by Sanko Co., Ltd.), and the phosphorus content was 14.2 by weight. 176 parts were placed in the same apparatus as in Synthesis Example 1, stirred while introducing nitrogen gas, and heated to increase the temperature. 0.18 parts of triphenylphosphine as a catalyst was added at 130 ° C, and the reaction was carried out at 160 ° C for 3 hours. The epoxy resin obtained had an epoxy equivalent of 266 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 1.

Example 2

The same operation as in Example 1 was carried out except that the amount of the phenol novolak type epoxy resin of Synthesis Example 4 was changed to 838 parts and the amount of HCA used was changed to 162 parts. The epoxy resin obtained had an epoxy equivalent of 256 g/eq and a phosphorus content of 2.3%. The results are summarized in Table 1.

Example 3

The same operation as in Example 1 was carried out except that the amount of the phenol novolak type epoxy resin of Synthesis Example 4 was changed to 880 parts and the amount of HCA used was changed to 120 parts. The obtained epoxy resin has an epoxy equivalent of 226 g/eq and a phosphorus content. 1.7%. The results are summarized in Table 1.

Example 4

The same operation as in Example 1 was carried out except that 824 parts of the phenol novolak type epoxy resin of Synthesis Example 5 and 176 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy resin obtained had an epoxy equivalent of 264 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 1.

Example 5

The same operation as in Example 1 was carried out except that 824 parts of the phenol novolak type epoxy resin of Synthesis Example 6 and 176 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy resin obtained had an epoxy equivalent of 256 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 1.

Example 6

The same operation as in Example 1 was carried out except that 711.9 parts of the phenol novolak type epoxy resin of Synthesis Example 7 and 112.1 parts of YDF-170C were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy resin used had a dinuclear group content of 11.9 area% and a trinuclear body content of 49.0 area%. The obtained epoxy resin had an epoxy equivalent of 257 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 1.

Example 7

804 parts of the phenol novolak type epoxy resin of the synthesis example 4 and 55 parts of bisphenol F (made by Honshu Chemical Co., Ltd.) were put, and it heated at 120 degreeC. 0.06 part of triphenylphosphine was added and reacted at 150 ° C for 2.5 hours. Further, 141 parts of HCA was added, and 0.14 part of triphenylphosphine was added, and the reaction was carried out at 160 ° C for 3 hours. The epoxy resin obtained had an epoxy equivalent of 301 g/eq and a phosphorus content of 2.0%. The results are consolidated in Table 1. in.

Example 8

The same operation as in Example 7 was carried out except that the amount of the phenol novolak type epoxy resin of Synthesis Example 4 of Example 7 was changed to 799 parts, and bisphenol F was replaced with 60 parts of bisphenol A. The epoxy resin obtained had an epoxy equivalent of 295 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 1.

Example 9

The same operation as in Example 1 was carried out except that 824 parts of the phenol novolak type epoxy resin of Synthesis Example 8 was used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy resin obtained had an epoxy equivalent of 260 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 1.

Comparative example 1

The same operation as in Example 1 was carried out except that 810 parts of YDPN-638 and 190 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. Place The epoxy equivalent of the epoxy resin was 271 g/eq, and the phosphorus content was 2.7%. The results are summarized in Table 2.

Comparative example 2

The same operation as in Example 1 was carried out except that the phenol novolac type epoxy resin of Synthesis Example 4 was replaced with 824 parts of YDPN-638. The epoxy resin obtained had an epoxy equivalent of 251 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 2.

Comparative example 3

The same operation as in Example 1 was carried out except that YDPN-638 838 parts and HCA 162 parts were substituted for the phenol novolac type epoxy resin of Synthesis Example 4. The epoxy resin obtained had an epoxy equivalent of 255 g/eq and a phosphorus content of 2.3%. The results are summarized in Table 2.

Comparative example 4

The same operation as in Example 7 was carried out except that 804 parts of YDPN-638 were used instead of the phenol novolak type epoxy resin of Synthesis Example 7 of Example 7. The epoxy resin obtained had an epoxy equivalent of 306 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 2.

Comparative Example 5

The same operation as in Example 7 was carried out except that 771 parts of YDPN-638 were used instead of the phenol novolak type epoxy resin of Synthesis Example 8 of Example 8. The epoxy resin obtained had an epoxy equivalent of 308 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 2.

Comparative Example 6

In addition to 824 parts of the phenolic novolac type epoxy resin of Synthesis Example 9, instead of synthesis The same operation as in Example 1 was carried out except for the phenol novolak type epoxy resin of Example 4. The epoxy resin obtained had an epoxy equivalent of 256 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 2.

Comparative Example 7

The same operation as in Example 1 was carried out except that the phenol novolac type epoxy resin of Synthesis Example 4 was replaced with YDPN-700-2 824 parts. The epoxy resin obtained had an epoxy equivalent of 303 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 2.

Comparative Example 8

141 parts of HCA and 330 parts of toluene were charged into the same apparatus as in Example 1 and dissolved by heating. Thereafter, while taking care of the temperature rise due to the heat of reaction, 87.5 parts of 1,4-naphthoquinone was added in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.85. After maintaining at 85 ° C for 30 minutes, the temperature was raised to reflux temperature for 2 hours. Further, the temperature was further raised, 200 parts of toluene was recovered, and 771.5 parts of YDPN-638 was charged, and while stirring with nitrogen, the mixture was heated to 120 °C. After adding 0.23 parts by weight of triphenylphosphine, the mixture was reacted at 165 ° C for 4 hours. The epoxy resin obtained had an epoxy equivalent of 327 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 2.

Example 10 to Example 18

An epoxy resin composition was produced using the phosphorus-containing epoxy resin of Examples 1 to 9 and a diaminodiguanamine (manufactured by Nippon Carbide Co., Ltd.) as a curing agent. The formulation of the solid component is shown in Table 3. When blending, the epoxy resin is dissolved in methyl ethyl ketone and used. DICY is used after being dissolved in methoxypropanol or DMF. 2E4MZ is used after methoxypropanol. After the formulation, the non-volatile content in methyl ethyl ketone and methoxypropanol was adjusted to 50%, and it was used as a uniform solution.

The obtained resin varnish was impregnated into a glass cloth WEA 7628 XS13 (manufactured by Nitto Bose Co., Ltd., 0.18 mm thick), and the impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C for 8 minutes to obtain a prepreg. The prepreg obtained by stacking 8 sheets was superposed on the copper foil (3EC, manufactured by Mitsui Mining Co., Ltd.), heated at 130 ° C for 15 minutes and 170 ° C × 20 kg / cm ² × 70 minutes, and pressurized. Laminated board. The physical properties of the laminated sheets are shown in Table 3.

Comparative Example 9 to Comparative Example 16

In the same manner as in Example 10 to Example 18, a laminated plate was produced using the phosphorus-containing epoxy resin of Comparative Example 1 to Comparative Example 8. The formulation of the formulated formula and the physical properties of the laminate are shown in Table 4.

A phosphorus-containing epoxy resin obtained by reacting a phenol novolac epoxy resin having a specific molecular weight distribution with a specific phosphorus compound may have flame retardancy even if the phosphorus content is 1.7% (Example 12), and the phosphorus content is increased to 2.3%. In the case of 2.5% (Examples 10 and 11), the flame retardancy was good from the shortening of the residual flame time. On the other hand, the phosphorus-containing epoxy resin obtained by reacting a conventional phenol novolac epoxy resin with a specific phosphorus compound does not have flame retardancy and hard acid property if the phosphorus content is less than 2.6% (Comparative Example 1). It is also worse. In Comparative Example 2 and Comparative Example 3 in which the phosphorus content was 2.5% and 2.3%, although the physical properties of the cured product were improved, the flame retardancy was not obtained. In Example 6, Example 7, and Example 8, other epoxy resin or epoxy resin modifier can be used to improve the adhesion, but it is used in Comparative Example 4 and Comparative Example 5 using a conventional phenol novolac resin. In the case of an epoxy resin modifier, the result of extremely deteriorated flame retardancy is obtained.

In addition, the reaction time of the phosphorus-containing epoxy resin is from 3 hours to 5 hours. However, Comparative Example 8 in which the flame retardancy and the hardened physical properties were good required 9 hours, and was also good in productivity.

(industrial availability)

The phosphorus-containing epoxy resin of the present invention can improve the flame retardancy while reducing the use amount of the high-valent phosphorus compound by controlling the molecular weight distribution of the raw material phenol novolac type epoxy resin, thereby improving the productivity and improving the physical properties of the hardened material. A film material, a sealing material, a molding material, a casting material, an adhesive, an electrical insulating coating, a composite material requiring flame retardancy, used for a prepreg, a copper clad laminate, or an electronic component used in an electronic circuit substrate. , powder coatings, etc.

Fig. 1 is a GPC chart showing a phenol novolak type epoxy resin YDPN-638 having a conventional molecular weight distribution. The horizontal axis represents the dissolution time, the left vertical axis represents the detection intensity, and the right horizontal axis represents the number average molecular weight expressed in log (common logarithm). The measured value of the number average molecular weight of the standard substance is used as a calibration curve with a black dot mark. The peak represented by A is a dinuclear body, and the peak represented by B is a trinuclear body.

Fig. 2 shows a GPC chart of Synthesis Example 4. The peak represented by A is a dinuclear body, and the peak represented by B is a trinuclear body.

Since the figure in this case is the result data of the test compound, it is not a representative figure of this case. Therefore, there is no designated representative map in this case.

Claims (5)

A phosphorus-containing epoxy resin having a dinuclear body content of 15% by area or less and a trinuclear body content of 15% by area to 60% by volume by gel permeation chromatography, having a number average molecular weight of 350 to 700 A phenolic epoxy resin having a molecular weight distribution (excluding a cresol novolak type epoxy resin) (A) is reacted with a compound represented by the formula (1) as an essential component; (for gel permeation chromatography measurement conditions) TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000HXL manufactured by Tosoh Co., Ltd. in series, the column temperature was 40 ° C; in addition, the eluent was used in tetrahydrofuran at a flow rate of 1 ml/min, and the detector was subjected to RI (differential refractometer) test with 10 ml of THF. Dissolving 0.1 g of the sample, and determining the number average molecular weight by a standard polyethylene calibration line; (wherein R1 and R2 are hydrogen or a hydrocarbon group, and may be the same or different, and the phosphorus atom may have a cyclic structure with R1 and R2, and n represents 0 or 1). A phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin and the hardener as described in claim 1 as an essential component, and an epoxy group of the phosphorus-containing epoxy resin to be 0.3 to 1.5 hardened. The range of active groups of the agent is formulated. A prepreg obtained by impregnating a phosphorus-containing epoxy resin composition described in claim 2 of the patent application with a substrate. An epoxy resin cured product obtained by hardening a phosphorus-containing epoxy resin composition as described in claim 2 of the patent application. A laminated board obtained by hardening a phosphorus-containing epoxy resin composition as described in claim 2 of the patent application.