TWI598371B - Phosphorus-containing epoxy resin and the epoxy resin as an essential component of the composition, hardened material - Google Patents

Description

Phosphorus-containing epoxy resin and composition and hardened material using the epoxy resin as an essential component

The present invention relates to a halogen-free flame-retardant epoxy resin containing a phosphorus atom in a molecular skeleton, an epoxy resin composition containing the epoxy resin as an essential component, and a hardening of the epoxy resin composition. The epoxy resin cured product provides a film material, a sealing material, a molding material, a casting material, an adhesive, an electrical insulating coating, which is suitable for use in a prepreg, a copper foil laminate or an electronic component used in an electronic circuit board. Epoxy resins such as flame retardant composites and powder coatings are required.

Regarding the incombustibility of the epoxy resin, it was previously carried out by halogenation as represented by a brominated epoxy resin using tetrabromobisphenol A as a raw material. However, in the case of using a halogenated epoxy resin, when a cured product is burned, problems such as generation of a highly toxic halide due to thermal decomposition reaction are observed. In this regard, in recent years, a phosphorus-containing epoxy resin or a phosphorus-containing phenol resin disclosed in Patent Documents 1 to 7 has been proposed.

The phosphorus-containing epoxy resin disclosed in Patent Document 1 and Patent Document 2 has a high adhesion strength, but the heat resistance represented by the glass transition temperature is not sufficient, and the glass transition temperature of the phosphorus-containing epoxy resin disclosed in Patent Document 3 is improved. But it is difficult to have both strengths. Further, the phosphorus-containing epoxy resin disclosed in Patent Document 4 is intended to improve high adhesion and high heat resistance by using a ruthenium compound. Further, in Patent Document 5, by using a specific bifunctional epoxy resin in combination, it is possible to further improve high adhesion and high heat resistance, and Patent Document 6 also studies the adhesion and high heat resistance of the disclosed phosphorus-containing epoxy resin. Improve. However, there are higher requirements regarding the glass transition temperature, maintaining the adhesion and seeking improvement.

In the phosphorus-containing epoxy resin obtained by the flame-retardant method of the phosphorus compound, it is difficult to achieve high heat resistance and high adhesion at the same time, and if the polyfunctionality is increased in order to improve heat resistance, the adhesion force is lowered, and in order to improve the adhesion force On the other hand, the bifunctionalization of the phosphorus compound lowers the heat resistance. On the other hand, Patent Document 5 proposes that the high heat resistance and the high adhesion force are further improved by using a specific bifunctional epoxy resin in the range of 20% to 45%.

Patent Document 1 Japanese Patent Publication No. 04-11662

Patent Document 2 Japanese Patent Laid-Open Publication No. 2000-309623

Patent Document 3 Japanese Patent Laid-Open No. Hei 11-166035

Patent Document 4 Japanese Patent Laid-Open No. Hei 11-279258

Patent Document 5 Japanese Patent No. 4588834

Patent Document 6 Japanese Patent Laid-Open Publication No. 2001-123049

Patent Document 7 Japanese Patent Laid-Open Publication No. 2003-040969

Recently, in order to increase the reflow temperature or ensure long-term reliability, an electronic circuit board or the like is required to further improve heat resistance, particularly glass transition temperature. An object of the present invention is to provide an epoxy resin having a property of maintaining an adhesive force and further improving heat resistance.

In order to solve the above problems, the present inventors have found that a phosphorus-containing epoxy resin obtained by using a novolac type epoxy resin having a specific molecular weight distribution and a phosphorus compound or a ruthenium compound in an epoxy resin can maintain high adhesion and improve heat resistance. Further, it was found that the flame retardancy was good, and the present invention was completed.

That is, the present invention is intended to (1) A phosphorus-containing epoxy resin (A) obtained by reacting a phosphorus compound represented by the formula (1), a ruthenium compound, and an epoxy resin (a) as essential components, and is characterized in that the ring The oxygen resin (a) is a novolac type epoxy resin, and the novolac type epoxy resin has a dinuclear group content of 15% by area or less in the measurement of gel permeation chromatography described below, and the trinuclear body contains The ratio is 15% by area to 60% by area, and has a molecular weight distribution with a number average molecular weight of 350 to 700;

(Metal conditions for gel permeation chromatography)

The TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL manufactured by Tosoh Co., Ltd. were used in series, and the column temperature was set to 40 ° C. Further, the elution solution was tetrahydrofuran (THF), the flow rate was set to 1 ml/min, and the detector was RI ( a differential refractometer detector; a sample for measurement is obtained by dissolving 0.1 g of a sample in 10 ml of THF; calculating a dinuclear content and a trinuclear content according to the obtained chromatogram, according to standard polystyrene The calibration curve determines the number average molecular weight;

(wherein R1 and R2 represent a hydrocarbon group, which may be the same or different, and R1 and R2 may form a cyclic structure together with a phosphorus atom; n represents 0 or 1)

(2) A phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin (A) of the above (1) And the hardener is an essential component, and is equivalent to 0.3 equivalent to 1.5 equivalents of the active group of the epoxy resin of the phosphorus-containing epoxy resin (A); (3) an epoxy resin cured product The phosphorus-containing epoxy resin composition of the above (2) is cured; (4) a prepreg obtained by impregnating the phosphorus-containing epoxy resin composition of the above (2) with a substrate; a laminated board obtained by hardening the phosphorus-containing epoxy resin composition of the above (2); (6) an electronic circuit board obtained by hardening the phosphorus-containing epoxy resin composition of the above (2) .

The present invention is a phosphorus-containing epoxy resin obtained by reacting a novolac type epoxy resin having a specific molecular weight distribution, a phosphorus compound and a cerium compound as an essential component, by using a novolac type epoxy having a specific molecular weight distribution. Resin, a phosphorus-containing epoxy resin which maintains the adhesion force and exhibits a hardening property of a high glass transition temperature is obtained. Further, the epoxy resin has a low viscosity, excellent workability and impregnation properties to the substrate, and good flame retardancy.

Fig. 1 is a gel permeation chromatography (GPC) chart showing a general-purpose phenol novolak type epoxy resin, i.e., YDPN-638. The dissolution time is indicated on the horizontal axis and the signal intensity is indicated on the left vertical axis. The number average molecular weight M is indicated by log on the right vertical axis. The measured value of the number average molecular weight of the standard substance to be used is plotted as a calibration curve by a black dot. The peak indicated by A indicates a dinuclear body, and the peak indicated by B indicates a trinuclear body.

Fig. 2 is a GPC chart showing the novolac type epoxy resin of Synthesis Example 2. The peak indicated by A indicates a dinuclear body, and the peak indicated by B indicates a trinuclear body.

Hereinafter, embodiments of the present invention will be described in detail.

The epoxy resin (a) used in the present invention is a reaction product of a phenol and an aldehyde, and is a polyfunctional novolac type epoxy obtained by reacting a novolak resin having a specific molecular weight distribution with an epihalohydrin. Resin. Examples of the phenol to be used include phenol, cresol, ethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, naphthalenediol, and bis. Examples of the aldehydes such as phenol A include fumarin, formaldehyde, hydroxybenzaldehyde, and salicylaldehyde. Further, in the present invention, the novolak resin also includes an aralkyl phenol system using aldehyde dimethyl dimethyl methoxide, benzodimethyl dichloride, bis chloromethyl naphthalene, bis chloromethyl biphenyl or the like instead of an aldehyde. Resin. A novolac type epoxy resin is obtained by epoxidation using epihalohydrin in the aforementioned novolac resin.

Specific examples of the conventional novolak-type epoxy resin include Epotohto YDPN-638 (Nippon Steel Chemical Co., Ltd. manufactures phenol novolak type epoxy resin), Epikote 152, and Epikote 154 (Mitsubishi Chemical Co., Ltd. manufactures phenol). Novolac type epoxy resin), EPICLON N-740, EPICLON N-770, EPICLON N-775 (a phenol novolak type epoxy resin manufactured by DIC Corporation), Epotohto YDCN-700 series (Nippon Steel Chemical Co., Ltd. Manufacture of cresol novolak type epoxy resin), EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-695 (cresol novolac type epoxy resin manufactured by DIC Corporation) , EOCN-1020, EOCN-102S, EOCN-104S (Nippon Chemical Co., Ltd. manufactures cresol novolac type epoxy resin), Epotohto ZX-1071T, ZX-1270, ZX-1342 (Nippon Steel Chemical Co., Ltd. Co., Ltd. manufactures alkyl novolac type epoxy resin), Epotohto ZX-1247, GK-5855 (Nippon Steel Chemical Co., Ltd. manufactures styrenated phenol novolac type epoxy resin), Epotohto ZX-1142L (Nippon Steel Chemical Co., Ltd. manufactures naphthol novolac type epoxy resin), ESN-155, ESN-185V, ESN-175 (Nagosone Chemical Co., Ltd. manufactures β-naphthol aralkyl type epoxy resin), ESN-300 Series of ESN-355, ESN-375 (Nippon Steel Chemical Co., Ltd. manufactures dinaphthol aralkyl type epoxy resin), ESN-400 series of ESN-475V, ESN-485 (Nippon Steel Chemical Co., Ltd. An α-naphthol aralkyl type epoxy resin) a bisphenol novolac type epoxy resin or the like is produced, but these epoxy resins do not have the specific molecular weight distribution of the present invention.

When the epoxy resin (a) having a specific molecular weight distribution used in the present invention is obtained, it can be obtained by adjusting the molar ratio of the phenol to the aldehyde and removing the low molecular weight component from the obtained novolak resin. Further, the novolac resin obtained by the production method shown in Patent Document 8 and Patent Document 9 can be epoxy-formed.

Patent Document 8 Japanese Patent Laid-Open Publication No. 2002-194041

Patent Document 9 Japanese Patent Laid-Open Publication No. 2007-126683

The molar ratio of phenols to aldehydes is expressed as a ratio of 1 or more to the molar ratio of phenols to aldehydes, but in the case where the molars are relatively large, a large number of dinuclear bodies are formed. The trinuclear body, when the mole is relatively small, generates a large amount of high molecular weight bodies, and the dinuclear body and the trinuclear body are reduced.

When the epoxy resin (a) having a specific molecular weight distribution used in the present invention is obtained, the dinuclear body can be dissolved from the obtained novolac resin by utilizing the difference in solubility of various solvents. Obtained in an alkaline aqueous solution and removed, etc. Other known separation methods are utilized.

A novolac type epoxy resin having a specific molecular weight distribution can be obtained by using a known epoxidation method for a molecular weight controlled novolac resin. Alternatively, a novolac type epoxy resin having a specific molecular weight distribution can be obtained by removing a dinuclear component from a commercially available novolac type epoxy resin by various methods. Other known separation methods can also be utilized.

In the epoxy resin (a) having a specific molecular weight distribution used in the present invention, the dinuclear content is preferably 15% by area or less, more preferably 5% by area to 12% by area. By containing a small amount of the dinuclear body, physical properties such as adhesion can be improved. The trinuclear content is preferably from 15% by area to 60% by area, more preferably from 20% by area to 50% by area. When the content of the trinuclear body is less than 15% by area, heat resistance is likely to be deteriorated, and when it exceeds 60% by area, it tends to be poor in adhesion. Further, the range of the tetranuclear body and the penta-nuclear body is not particularly limited, but the total content of the trinuclear body and the tetranuclear body is preferably 30% by area to 70% by area. When the total content of the trinuclear body and the tetranuclear body is in the range of 30% by area to 70% by area, the flame retardancy can be further improved. The content of the nucleus or more is preferably 45 area% or less, more preferably 40 area% or less. When the content of the penta-nuclear body or more is 45 area% or less, a cured product having a higher adhesion force can be obtained. The number average molecular weight is preferably from 350 to 700, more preferably from 380 to 600. When the number average molecular weight exceeds 700, the viscosity of the obtained phosphorus-containing epoxy resin (A) becomes high, which may adversely affect workability or substrate impregnation. The reason why the flame retardancy of the phosphorus-containing epoxy resin (A) obtained by the above conditions is improved is generally considered to be that the carbon which is formed during combustion is lowered by the decrease in the modulus of elasticity of the obtained cured product. Stronger, with higher insulation, but not yet verified.

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

The oxime compound in the present invention may, for example, be benzoquinone, naphthoquinone, methyl benzoquinone, hydrazine or the like, or a substituent having a hydrocarbon group, and may be used singly or in combination of two or more kinds. Use is not limited to these. The molar ratio of the phosphorus compound represented by the formula (1) to the ruthenium compound is preferably a phosphorus compound: ruthenium compound = 1:1 or less, more preferably 1:0.99 to 0.2, more preferably 1:0.98 to 0.40. When the amount of the ruthenium compound is excessive, it remains in the phosphorus-containing epoxy resin (A) as an unreacted component, and thus the physical properties are liable to be lowered. When the ruthenium compound is less than 0.2, the heat resistance and flame retardancy are poor. The impact of the impact. Further, it is also possible to use a compound obtained by reacting a phosphorus compound with a ruthenium compound and then extracting only the reaction component by purification.

The phosphorus-containing epoxy resin (A) of the present invention is obtained by reacting a phosphorus compound represented by the formula (1) and a ruthenium compound with an epoxy resin (a) having a specific molecular weight distribution as an essential component, and can be obtained by the present invention. Other known conventional epoxy resins or modifiers are used in the range in which the effects are not affected.

The reaction of the phosphorus compound represented by the formula (1), the hydrazine compound, and the epoxy resin (a) having a specific molecular weight distribution is carried out by a known method. There is a method of reacting a phosphorus compound with a ruthenium compound and then reacting with the epoxy resin (a); reacting the phosphorus compound with the ruthenium compound in the epoxy resin (a) and then reacting with the epoxy resin (a) A method of generating a reaction; a method of reacting a phosphorus compound with a ruthenium compound and reacting it with an epoxy resin (a), and the like, and the reaction sequence is not particularly limited in the present invention.

The reaction temperature is usually a temperature set in the synthesis of the indirect epoxy resin, and is 100 ° C to 250 ° C, preferably 120 ° C to 200 ° C.

In the reaction, a catalyst may be used in order to shorten the time or lower the reaction temperature. The catalyst which can be used is not particularly limited, and a general user in the synthesis of an indirect epoxy resin can be used. For example, a tertiary amine such as benzyldimethylamine, a quaternary ammonium salt such as tetramethylammonium chloride, triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine, or the like can be used. Various catalysts such as phosphines, sulfonium salts such as ethyltriphenylphosphonium bromide, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole may be used alone or in combination of two or more. It is not limited to these. Moreover, it can also be divided and used in several times.

The amount of the catalyst is not particularly limited, and is 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% based on the total weight of the epoxy resin (a) or other commonly known conventional epoxy resins. Below mass%. When the amount of the catalyst is large, the self-polymerization reaction of the epoxy group proceeds depending on the case, and thus the viscosity of the resin becomes high, which is not preferable.

When the phosphorus compound or the ruthenium compound represented by the formula (1) is reacted with the epoxy resin (a) having a specific molecular weight distribution, it may be modified with various epoxy resins as needed within the range which does not impair the characteristics of the present invention. Agent. Examples of the modifier include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, methyl hydroquinone, dimethyl hydroquinone, and dibutyl. Hydroquinone, resorcinol, methyl resorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxyindole, phenol novolac resin, cresol novolac Varnish resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, indophenol resin, heavy oil modified phenol resin, brominated phenol novolac resin, etc. a polyphenol-based resin obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde or glyoxal, or aniline, phenylenediamine, toluidine, xylylamine, diethyl A Phenylenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone, diaminodiphenyl sulphide, diamine bis Phenylhydrazine, bis(aminophenyl)anthracene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzimidil, diaminobiphenyl, di Methyldiaminobiphenyl, biphenyltetramine, bisaminophenyl hydrazine, bisaminophenoxybenzene, bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisamine An amine compound such as phenoxyphenyl hydrazine, bisaminophenoxyphenylpropane or diaminonaphthalene is not limited thereto, and two or more kinds thereof may be used in combination.

When the phosphorus compound or the ruthenium compound represented by the formula (1) is reacted with the epoxy resin (a) having a specific molecular weight distribution, other various epoxy resins may be used as needed without impairing the characteristics of the present invention. Specific examples of the epoxy resin to be used include Epotohto YDC-1312, ZX-1027 (a hydroquinone-based epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), and YX-4000 (Mitsubishi Chemical Co., Ltd.) Manufacturing), ZX-1251 (Nippon Steel Chemical Co., Ltd. manufactures biphenol type epoxy resin), Epotohto YD-127, Epotohto YD-128, Epotohto YD-8125, Epotohto YD-825GS, Epotohto YD-011, Epotohto YD -900, Epotohto YD-901 (BNP-type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epotohto YDF-170, Epotohto YDF-8170, Epotohto YDF-870GS, Epotohto YDF-2001 (Nippon Steel Chemical Co., Ltd. Manufacture of BPF type epoxy resin), Epotohto YDPN-638 (Nippon Steel Chemical Co., Ltd. manufactures phenol novolak type epoxy resin), Epotohto YDCN-701 (Nippon Steel Chemical Co., Ltd. manufactures cresol novolac type epoxy Resin), ZX-1201 (Nippon Steel Chemical Co., Ltd. manufactures bisphenol oxime epoxy resin), NC-3000 (Nippon Chemical Pharmaceutical Co., Ltd. manufactures biphenyl aralkyl phenol epoxy resin), EPPN-501H , EPPN-502H (Japan Chemical Pharmaceutical Co., Ltd. Limited manufacture a polyfunctional epoxy Oxygen resin), ZX-1355 (Nippon Steel Chemical Co., Ltd. manufactures naphthalene diphenol type epoxy resin), ESN-155, ESN-185V, ESN-175 (Nippon Steel Chemical Co., Ltd. manufactures β-naphthol aralkyl Base type epoxy resin), ESN-355, ESN-375 (Nippon Steel Chemical Co., Ltd. manufactures dinaphthol aralkyl type epoxy resin), ESN-475V, ESN-485 (Nippon Steel Chemical Co., Ltd. An epoxy resin produced from a phenolic compound such as a polyphenol-based resin such as an α-naphthol aralkyl epoxy resin or an epihalohydrin, and Epotohto YH-434, Epotohto YH-434GS (Nippon Steel Chemical Co., Ltd.) An epoxy resin produced by an amine compound such as diamine diphenylmethanetetraglycidyl ether and epihalohydrin, and a carboxyl group such as YD-171 (manufactured by Nippon Steel Chemical Co., Ltd.) The epoxy resin produced by the acid and the epihalohydrin is not limited to these, and two or more types may be used in combination.

When the phosphorus compound or the ruthenium compound represented by the formula (1) is reacted with the epoxy resin (a) having a specific molecular weight distribution, an inert solvent may be used as needed. Specifically, it can be used: various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, etc. Ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, two Ethers such as alkane, methylfuran and tetrahydrofuran, methyl stilbene, methyl sarbuta acetate, ethyl celecoxib, serosu acetate, ethylene glycol isopropyl ether, diethylene Alcohol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl hydrazine, etc., but not limited thereto, and may be used in combination of two or more kinds. .

The phosphorus-containing epoxy resin (A) of the present invention can be formed into a curable phosphorus-containing epoxy resin composition by blending a curing agent. As the curing agent, various curing agents such as phenol resins or acid anhydrides, amines, hydrazines, and acid polyesters, which are generally used, and such curing agents can be used. It is also possible to use only one type or two or more types. Among these, the curing agent contained in the curable epoxy resin composition of the present invention is preferably a dicyandiamide or a phenolic curing agent. In the curable epoxy resin composition of the present invention, the curing agent is used in an amount of preferably from 0.4 to 2.0 equivalents, more preferably from 0.5 to 2.0 equivalents, based on the functional group of the epoxy resin, that is, the equivalent of the epoxy group. ~1.5 equivalents, particularly preferably 0.5 to 1.0 equivalents. When the amount of the hardener is less than 0.4 equivalents per equivalent of the epoxy group, or when it exceeds 2.0 equivalents, the hardening is incomplete and the good hardenability is not obtained.

Specific examples of the phenolic curing agent which can be used in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, and bisphenol S. Tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl- Bisphenols such as 6-t-butylphenol), catechol, resorcinol, methyl resorcinol, hydroquinone, monomethylhydroquinone, dimethyl-p-benzene Dihydroxybenzenes such as diphenol, trimethylhydroquinone, mono-t-butyl hydroquinone, di-tert-butyl hydroquinone, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxy Hydroxynaphthalenes such as methylnaphthalene and trihydroxynaphthalene, phenol novolac resin, DC-5 (Nippon Steel Chemical Co., Ltd. cresol novolak resin), naphthol novolac resin and other phenols and/or naphthols Condensate with aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical Co., Ltd.) and/or condensates of naphthols and benzenedimethyl glycol, phenols And/or a condensate of naphthol and isopropenylacetophenone, Phenol-based compound and / or a naphthol and dicyclopentadiene, the reactants, phenols and / or naphthols and biphenyl condensing agent of condensate.

In the above, examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Listed: 1-naphthol, 2-naphthol, and the like.

Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloroacetaldehyde, bromoacetaldehyde, glyoxal, malondialdehyde, succinaldehyde, and glutaraldehyde. , adipaldehyde, p-glyoxal, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, benzenedialdehyde, hydroxybenzaldehyde, and the like. Examples of the biphenyl condensing agent include bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl, and the like. .

Other known and commonly used curing agents which can be used in the curable epoxy resin composition of the present invention include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and pyromellitic dianhydride. Anhydrides such as phthalic anhydride, trimellitic anhydride, methylic acid anhydride, di-ethyltriamine, tri-ethylidenetetramine, m-xylylenediamine, isophoronediamine, diamine An amide which is a condensate of an acid such as diphenylmethane, diaminodiphenyl hydrazine, diaminodiphenyl ether, dicyandiamide or dimer acid, and a polyamine, that is, an amine compound such as polyamine.

Further, examples of the curing agent which hardens the polymerization of the epoxy group include a phosphine compound such as triphenylphosphine, a phosphonium salt such as tetraphenylphosphonium bromide, 2-methylimidazole or 2-phenylimidazole. Imidazoles such as 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, and the like with trimellitic acid, iso-cyanuric acid, boron Salts such as imidazolium salts, amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and quaternary ammonium salts such as trimethylammonium chloride, Azabicyclo compounds and such salts with phenols, phenol novolac resins, and the like, and complexes of boron trifluoride with amines, ether compounds, etc., aromatic or sulfonium salts. These hardeners may be used alone or in combination of two or more.

The blending ratio of the other known conventional epoxy resin hardener used in the epoxy resin composition of the present invention is 0.5 to 1.5 equivalents, preferably 0.8 to 1 equivalent per equivalent of the epoxy group. 1.2 equivalent ratio. Moreover, it causes hardening of the polymerization of the epoxy group to harden it. The blending ratio of the chemical agent is 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the epoxy resin.

In the flame retardant epoxy resin composition containing the phosphorus-containing epoxy resin (A) of the present invention, an organic solvent can also be used as the viscosity adjustment. The organic solvent to be used is not particularly limited, and examples thereof include decylamines such as N,N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, and ketones such as acetone and methyl ethyl ketone. An alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, or the like, or one or a plurality of such solvents may be mixed in an amount of 20 to 90% by mass based on the epoxy resin concentration. Blending.

A hardening accelerator can be used as needed in the composition of the present invention. Examples of the curing accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethyl). a tertiary amine such as phenol or 1,8-diazabicyclo(5,4,0)undecene-7; a phosphine such as triphenylphosphine, tricyclohexylphosphine or triphenylphosphine triphenylborane , metal compounds such as stannous octoate. The curing accelerator is used in an amount of 0.02 to 5.0 parts by mass, based on 100 parts by mass of the epoxy resin component in the epoxy resin composition of the present invention. By using a hardening accelerator, the hardening temperature can be lowered, or the hardening time can be shortened.

A filler may be used as needed in the composition of the present invention. Specific examples thereof include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, bauxite, titanium oxide, glass powder, and ruthenium balls, and pigments may be blended. Generally, as an reason for using an inorganic filler, the improvement of impact resistance is mentioned. Further, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it can function as a flame-retardant aid, and it is possible to ensure flame retardancy even when the phosphorus content is small. In particular, when the blending amount is not 10% by mass or more, the effect of impact resistance is small. However, if the blending amount exceeds 150% by mass, it is a necessary item for the use of the laminate, that is, the adhesion is lowered. low. Further, the resin composition may contain a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber, or an organic filler such as rubber fine particles or a thermoplastic elastomer.

The cured epoxy resin can be obtained by hardening the epoxy resin composition of the present invention. In the case of curing, for example, a resin sheet, a resin-attached copper foil, a prepreg or the like may be laminated and subjected to heat and pressure hardening to obtain a phosphorus-containing epoxy resin cured product as a laminate.

A phosphorus-containing epoxy resin composition using the phosphorus-containing epoxy resin (A) of the present invention is produced, and the phosphorus-containing epoxy resin cured product of the laminate is evaluated by heat curing, and as a result, a phosphorus compound or a ruthenium compound is obtained. The phosphorus-containing epoxy resin (A) obtained by reacting a compound with an epoxy resin (a) having a specific molecular weight distribution is compared with a previously known phosphorus-containing epoxy resin obtained from a phosphorus compound and an epoxy resin, not only It has low viscosity and good workability, and can have high heat resistance and high adhesion together, and can also improve flame retardancy.

[Examples]

The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means parts by mass, and "%" means mass%. The measurement methods were each measured by the following methods.

The measurement method is shown below.

Epoxy equivalent: according to JIS K7236.

Dinuclear content, trinuclear content, tetranuclear content, pentanucleoside content, number average molecular weight (Mn), weight average molecular weight (Mw), and dispersion (Mw/Mn): coagulation The molecular weight distribution was measured by gel permeation chromatography, and the dinuclear content, the trinuclear content, the tetranuclear content, and the pentanucleoside content were converted according to the area percentage of the peak. The average molecular weight, the weight average molecular weight, and the degree of dispersion are based on standard monodisperse polystyrene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F manufactured by Tosoh Co., Ltd.). -4, F-10, F-20, F-40) The calibration curve obtained is converted. Specifically, a column (TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL manufactured by Tosoh Co., Ltd.) was provided in series on the main body (HLC-8220GPC manufactured by Tosoh Co., Ltd.), and the column temperature was set to 40 °C. Further, tetrahydrofuran was used as the elution solution, and the flow rate was set to 1 ml/min, and the detector was an RI (differential refractometer) detector.

Phosphorus-containing rate: sulfuric acid, hydrochloric acid, and perchloric acid are added to the sample, and heating is performed to carry out wet ashing, so that all the phosphorus atoms become orthophosphoric acid. The metavanadate and the molybdate are reacted in an acidic solution of sulfuric acid, and the absorbance of the resulting phosphovanadomolybdic acid complex at 420 nm is measured, and the phosphorus atom is determined according to a calibration curve prepared by using potassium dihydrogen phosphate in advance. Contain rate, expressed in %. The phosphorus content of the laminate is expressed in terms of the content of the resin component relative to the laminate.

Copper foil peeling strength and interlayer adhesion: measured according to JIS C 6481, and the interlayer adhesion was peeled off between the seventh layer and the eighth layer and measured.

Flammability: According to UL94 (Safety Certification Specification of Underwriters Laboratories Inc.). Five test pieces were tested, and the total time of the flame combustion duration after the first and second contact flames (5 pieces of the contact flames for each of the two times) was expressed in seconds.

Glass transition temperature DSC: It is expressed by the temperature of the DSC extrapolation value measured by a differential scanning calorimeter (EXSTAR6000 DSC6200 manufactured by SII Nano Technology Co., Ltd.) under the temperature rise condition of 10 ° C /min.

Glass transfer temperature TMA: using a thermomechanical analysis device (EXSTAR6000 TMA/SS120U manufactured by SII Nano Technology Co., Ltd.) at 5 ° C / min The temperature of the TMA extrapolated value at the time of measurement under the temperature rise condition is expressed.

The epoxy resins used in the examples and comparative examples are shown below.

Epotohto YDPN-638 (Nippon Steel Chemical Co., Ltd. manufactures a general-purpose phenol novolac type epoxy resin, a dinuclear content of 22% by area, a trinuclear content of 15% by area, a trinuclear body and a tetranuclear content rate. The total amount is 25 area%, the content of the penta core or more is 53 area%, the number average molecular weight 528, the weight average molecular weight of 1127, the degree of dispersion of 2.13, and the epoxy equivalent of 176 g/eq (see Fig. 1).

Epotohto YDF-170 (manufactured by Nippon Steel Chemical Co., Ltd. Bisphenol F epoxy resin epoxy equivalent 170g/eq)

Synthesis Example 1 (Synthesis of Phenolic Novolak Resin)

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 added, and the mixture was stirred while introducing nitrogen gas, and heated to increase the temperature. 474.1 parts of 37.4% formalin was started to be added at 80 ° C, and the addition was completed in 30 minutes. Further, the reaction was carried out for 3 hours while maintaining the reaction temperature at 92 °C. While raising the temperature, the reaction-formed water was removed to the outside of the system and the temperature was raised to 110 °C. The residual phenol was recovered under reduced pressure at 160 ° C to obtain a phenol novolak resin. Further, the temperature is raised to recover a part of the dinuclear body. The dinuclear content and the trinuclear content of the obtained phenol novolak resin were 10 area% and 38 area% in the measurement by gel permeation chromatography, respectively.

Synthesis Example 2 (Synthesis of Phenolic Novolak Type Epoxy Resin)

In the same apparatus as in Synthesis Example 1, 665.8 parts of phenol novolak resin of Synthesis Example 1, 2110.8 parts of epichlorohydrin, and 17 parts of water were added, and the temperature was raised to 50 ° C while stirring. 14.2 parts of a 49% aqueous sodium hydroxide solution was added and the reaction was carried out for 3 hours. Warm up to 64 ° C, pump down to the water The degree of reflux was carried out by dropwise addition of 457.7 parts of a 49% aqueous sodium hydroxide solution over 3 hours. The temperature was raised to 70 ° C to carry out dehydration, and the temperature was set to 135 ° C to recover the remaining epichlorohydrin. Return to normal pressure, add 1232 parts of MIBK and dissolve. 1200 parts of ion-exchanged water was added, and the stirring was allowed to stand, and the by-produced salt was dissolved in water and removed. Then, 37.4 parts of a 49% aqueous sodium hydroxide solution was added, 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 is 9 area%, the trinuclear body content is 36 area%, the total content of the trinuclear body and the tetranuclear body is 53 area%, and the content above the penta core is 38 area%, and the number average molecular weight is It was 513, had a weight average molecular weight of 713, a degree of dispersion of 1.39, and an epoxy equivalent of 174 g/eq. (Refer to Figure 2)

Example 1

Into the same apparatus as in Synthesis Example 1, HCA (manufactured by Sanko Co., Ltd., 9,10% of 1,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) was added with 127 parts of toluene 270. The mixture was heated and dissolved. Then, while paying attention to heat, 70 parts of 1,4-naphthoquinone (manufactured by Tokyo Chemical Industry Co., Ltd., purity: 98% or more) was added, and the temperature was maintained at 90 ° C or lower for 30 minutes. Further, the temperature was gradually raised and maintained at the reflux temperature for 2 hours. After recovering a part of toluene, 804 parts of the phenol novolak type epoxy resin of Synthesis Example 2 was added, and while stirring with nitrogen gas, the temperature was raised to 130 °C. 0.20 parts of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 3 hours. The epoxy resin obtained had an epoxy equivalent of 276 g/eq and a phosphorus content of 1.8%. The results are summarized in Table 1.

Example 2

The same operation as in Example 1 was carried out except that 141 parts of HCA, 77 parts of 1,4-naphthoquinone, 782 parts of phenol novolac type epoxy resin of Synthesis Example 2, and 0.22 parts of triphenylphosphine were used. Obtained The epoxy resin had an epoxy equivalent of 294 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 1.

Example 3

The same operation as in Example 1 was carried out except that 155 parts of HCA, 85 parts of 1,4-naphthoquinone, 760 parts of phenol novolac type epoxy resin of Synthesis Example 2, and 0.24 parts of triphenylphosphine were used. The epoxy resin obtained had an epoxy equivalent of 317 g/eq and a phosphorus content of 2.2%. The results are summarized in Table 1.

Example 4

141 parts of HCA, 83 parts of 1,4-naphthoquinone, 726 parts of phenol novolak type epoxy resin of Synthesis Example 2, 0.22 parts of triphenylphosphine, and 50 parts of YDF-170B and phenol novolac type epoxy The same operation as in Example 1 was carried out except that the resin was simultaneously blended. The obtained epoxy resin had an epoxy equivalent of 297 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 1.

Example 5

155 parts of HCA, 57 parts of 1,4-naphthoquinone, 638 parts of phenol novolac type epoxy resin of Synthesis Example 2, 0.21 part of triphenylphosphine, and further, YDF-170150 parts and phenol novolak type epoxy resin The same operation as in Example 1 was carried out except that the mixture was simultaneously blended. The epoxy resin obtained had an epoxy equivalent of 286 g/eq and a phosphorus content of 2.2%. The results are summarized in Table 1.

Example 6

155 parts of HCA, 34 parts of 1,4-naphthoquinone, 777 parts of phenol novolac type epoxy resin of Synthesis Example 2, and 0.19 parts of triphenylphosphine, and further, BRG-555 (produced by phenol phenolic phenolic resin) The same operation as in Example 1 was carried out, except that 34 parts of the varnish resin were blended together with the phenol novolac type epoxy resin. The epoxy resin obtained had an epoxy equivalent of 310 g/eq and a phosphorus content of 2.2%. The results are summarized in Table 1.

Example 7

155 parts of HCA, 23 parts of 1,4-naphthoquinone, 779 parts of phenol novolac type epoxy resin of Synthesis Example 2, 0.18 parts of triphenylphosphine, and 43 parts of BRG-555 and phenol novolak type ring The same operation as in Example 1 was carried out except that the oxygen resin was simultaneously blended. The epoxy resin obtained had an epoxy equivalent of 310 g/eq and a phosphorus content of 2.2%. The results are summarized in Table 1.

Comparative example 1

In the same apparatus as in Synthesis Example 1, 824 parts of YDPN-638 and 176 parts of HCA were added, and while stirring with nitrogen gas, heating was carried out to raise the temperature. 0.18 parts of triphenylphosphine was added as a catalyst at 130 ° C, and the reaction was carried out at 160 ° C for 3 hours. The epoxy resin obtained had an epoxy equivalent of 263 g/eq and a phosphorus content of 2.5%. The results are summarized in Table 1.

Comparative example 2

The same operation as in Comparative Example 1 was carried out except that 824 parts of the phenol novolak type epoxy resin of Synthesis Example 2 and 176 parts of HCA were used. 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.

Comparative example 3

The same operation as in Example 1 was carried out except that 141 parts of HCA, 77 parts of 1,4-naphthoquinone, 782 parts of YDPN-638, and 0.22 parts of triphenylphosphine were used. The epoxy resin obtained had an epoxy equivalent of 303 g/eq and a phosphorus content of 2.0%. The results are summarized in Table 1.

Comparative example 4

155 parts of HCA, 80 parts of 1,4-naphthoquinone, 465 parts of YDPN-638, and 0.23 parts of triphenylphosphine, and further, 300 parts of YDF-170 and phenol novolak type epoxy resin were blended at the same time. The same operation as in Example 1 was carried out. The epoxy resin obtained had an epoxy equivalent of 311 g/eq and a phosphorus content of 2.2%. The results are summarized in Table 1.

Example 8 to Example 14 and Comparative Example 5 to Comparative Example 8

The epoxy resins of Examples 1 to 7 and Comparative Examples 1 to 4 were blended with dicyandiamide as a curing agent according to the formulation of Table 2, and dissolved in methyl ethyl ketone and propylene glycol. An epoxy resin composition varnish was obtained by adjusting methyl ether and N,N-dimethylformamide in a mixed solvent.

The obtained resin composition varnish was impregnated with glass cloth WEA 7628 XS13 (manufactured by Nitto Textile Co., Ltd., 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C to obtain a prepreg. The prepreg obtained by the 8 pieces was combined and filled, and the copper foil (3EC manufactured by Mitsui Mining & Mining Co., Ltd.) was superposed on the top and bottom, and heated and pressurized at 130 ° C × 15 minutes and 170 ° C × 20 kg / cm ² × 70 minutes. Get a laminate. The results of the glass transition temperature, copper foil peel strength, interlayer adhesion, and flame retardancy test of the laminates of TMA, DSC, and DMS are summarized in Table 2.

As shown in Table 1 and Table 2, the phosphorus-containing epoxy resin (A) obtained by reacting the phosphorus compound represented by the formula (1) and the ruthenium compound with the epoxy resin (a) having a specific molecular weight distribution Compared with the case of using an epoxy resin which does not react with a ruthenium compound or a phenol novolak type epoxy resin which does not have a specific molecular weight distribution, the viscosity is low and the glass transition temperature and the adhesion force are high, and are lower. The phosphorus content is difficult to ignite.

[Industrial availability]

The present invention is a phosphorus-containing epoxy resin (A) obtained by reacting a specific phosphorus compound, a ruthenium compound and an epoxy resin (a) having a specific molecular weight distribution as an essential component, and can be used as a flame retardancy, heat resistance, and adhesion. Excellent epoxy resin for electronic circuit boards.

Claims (6)

A phosphorus-containing epoxy resin (A) obtained by reacting a phosphorus compound represented by the formula (1), a ruthenium compound and an epoxy resin (a) as an essential component, and is characterized in that an epoxy resin ( a) is a novolac type epoxy resin, and the novolac type epoxy resin has a dinuclear group content of 15% by area or less and a trinuclear group content of 15% by area to 60 in the measurement of gel permeation chromatography. The area %, the total content of the trinuclear body and the tetranuclear body is 30% by area to 70% by area, the content of the penta core or more is 45 area% or less, and the molecular weight distribution having a number average molecular weight of 350 to 600; The conditions of the gel permeation chromatography were as follows: TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL manufactured by Tosoh Co., Ltd. were used in tandem, and the column temperature was set to 40 ° C; and the eluent was tetrahydrofuran, and the flow rate was set to 1 ml/min. The detector is an RI (differential refractometer) detector; the measurement sample is obtained by dissolving 0.1 g of the sample in 10 ml of THF; calculating the dinuclear content, the trinuclear content, and the fourth according to the obtained chromatogram. Nuclear body content and content above the nucleus, according to the standard a quasi-polystyrene calibration curve for determining the number average molecular weight; (wherein R1 and R2 represent a hydrocarbon group, which may be the same or different, and R1 and R2 may form a cyclic structure together with a phosphorus atom; n represents 0 or 1). A phosphorus-containing epoxy resin composition which is an essential component of the phosphorus-containing epoxy resin (A) and a hardener according to claim 1 of the patent application, and 1 equivalent to the epoxy group of the phosphorus-containing epoxy resin (A) It is formed by blending the active group of the hardener with 0.3 equivalent to 1.5 equivalents. An epoxy resin cured product which is a phosphorus-containing epoxy resin of claim 2 The composition is hardened. A prepreg obtained by impregnating a substrate with a phosphorus-containing epoxy resin composition according to item 2 of the patent application. A laminated board which is obtained by hardening a phosphorus-containing epoxy resin composition of the second claim. An electronic circuit substrate obtained by hardening a phosphorus-containing epoxy resin composition of the second claim.