TWI460199B - Flame retardant phosphor-containing epoxy resin composition and cured article thereof - Google Patents

Description

Flame retardant phosphorus-containing epoxy resin composition and cured product thereof

The present invention relates to a resin composition for producing a flame-retardant epoxy resin composition, a resin composition for producing a copper-clad laminate used for an electronic circuit board, or a sealing material, a molding material, and a mold material for use in an electronic component. In the case of a resin composition for the production of a copper clad laminate, it is not only a flame retardant effect, but also a flame retardant laminate which is excellent in adhesion, heat resistance and moisture resistance. A phosphorus-containing epoxy resin composition.

The type of epoxy resin actually used has a liquid to solid shape, a varnish dissolved in a solvent, and the like. The liquid type is widely used for molding materials and adhesives, and the solid type is used for sealing materials and powder coatings. In addition, the varnish type is used for fiber-reinforced plastic materials and solvent-based coatings which are impregnated on glass substrates and carbon fibers. In particular, it is widely used in electrical and electronic materials because of its excellent adhesion and electrical properties (insulation).

Halogenated epoxy resins are commonly used because such electrical and electronic material parts are highly flame-retardant (UL: V-0) as represented by glass epoxy laminates or IC sealants. For example, in a glass epoxy laminate, the flame-retarded FR-4 grade is generally made up of a bromine-substituted epoxy resin as a main raw material component, in which an epoxy resin of various epoxy resins is mixed and blended. The epoxy resin is used as a hardener.

However, the use of such halogenated epoxy resins is not only one of the major causes of environmental problems represented by Dioxin in recent years, but also has a negative effect on the long-term reliability of electrical properties due to halogen dissociation in a high temperature environment. There is a strong demand to reduce the amount of halogen used, or to develop flame retardants or other flame retardant prescriptions that use other compounds that can replace halogens.

In the past, in order to replace the flame retardant formulation of such halogens, various techniques such as the use of a phosphate ester compound as an additive flame retardant have been reviewed, but these techniques all lead to heat resistance of the laminate. The decrease in water resistance and the like, the problem that the flame retardant will bleed out over time, and in particular, the adhesion of the use of the electric laminate will be drastically lowered. Then, various techniques for improving the performance of the laminated board by reacting an epoxy resin with a specific phosphorus compound are examined (Patent Documents 1 to 4). However, these techniques are based on the FR-4 rating in terms of heat resistance, and it is difficult to increase the heat resistance to the above. In general, in order to improve heat resistance, a method of using a polyfunctional epoxy resin such as cresol novolac epoxy resin is employed, but a decrease in flame retardancy and a decrease in adhesion are caused. Recently, in order to cope with lead-free soldering, in order to further improve the reliability at high temperatures, the water absorption rate of the cured product is lowered and the elasticity is lowered. In Patent Document 5, an epoxy resin having a naphthene aralkyl structure is reacted with a specific phosphorus compound to simultaneously achieve an improvement in flame retardancy and heat resistance, but the adhesion is lowered. Thus, it is difficult to maintain heat resistance while ensuring adhesion by maintaining the flame retardancy by the phosphorus-containing epoxy resin composition.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-288247

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-249540

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-123049

[Patent Document 4] Japanese Patent No. 3642403

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-214513

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2008-150495

[Patent Document 7] JP-A-61-268691

The problem to be solved by the present invention is to provide a flame-retardant phosphorus-containing epoxy resin composition excellent in heat resistance, moisture resistance, and flame retardancy, which is in a phosphorus-containing epoxy resin which imparts flame retardancy without using a halogen. , because the reliability at high temperatures is improved, and the decrease in adhesion is not caused.

That is, the gist of the present invention is a flame-retardant phosphorus-containing epoxy resin composition comprising a flame-retardant phosphorus-containing epoxy resin composition containing a phosphorus-containing epoxy resin (X) and a hardener (Y), The epoxy-containing epoxy resin (X) is an epoxy resin (a) having a bifunctional epoxy resin having a sulfur atom in a skeleton of 50% by weight to 100% by weight, and a chemical formula (1) The reaction of the phosphorus compound (b) in which the molar amount is mixed at a ratio of 0.06 mol or less in the chemical formula (2), and the flame-retardant phosphorus-containing epoxy resin composition is relative to the entire ring. The oxygen resin component has a phosphorus content of 0.5% by weight to less than 2.0% by weight, and further, the sulfur content is 2% by weight to 9% by weight or less.

When the flame retardant phosphorus-containing epoxy resin composition of the present invention is used, it is excellent in flame retardancy, adhesion, and heat resistance. Further, a cured product excellent in flame retardancy and high heat resistance and particularly excellent in adhesion to metals can be obtained at a phosphorus-containing ratio of 0.5% by weight to less than 2.0% by weight, by containing a 2-functional ring having a sulfur atom in the skeleton. Oxygen resin is an essential component, which further enhances the effect.

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

The epoxy resin (a) used in the present invention contains, as an essential component, 50% by weight to 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton. If it is less than 50% by weight, the heat resistance is not improved, and the flame retardancy is also lowered, and the composition which can be used for high heat resistance cannot be obtained.

The bifunctional epoxy resin having a sulfur atom in the skeleton may be any structure as long as it is a bifunctional epoxy resin containing a sulfur atom, but particularly preferably a bisphenol epoxy resin containing a sulfur atom. Specifically, bisphenol S type epoxy resin such as EPOTOHTO TX-0908 (made by Dongdu Chemical Co., Ltd., replacing bisphenol S type epoxy resin) or EPOTOHTO YSLV-120TE (made by Dongdu Chemical Co., Ltd., dimethyl dihydroxyl) Diphenyl sulfide (diphenyl sulfide) or EPOTOHTO YSLV-50TE (diphenyl sulfide, bis(diphenyl sulfide) epoxy resin (diphenyl sulfide) The epoxy resin or the like is not limited thereto, and two or more kinds thereof may be used in combination.

Further, although a bifunctional epoxy resin having no sulfur atom in the skeleton may be used in combination as the bifunctional epoxy resin, the bifunctional epoxy resin having a sulfur atom in the skeleton must be an epoxy resin (a). 50% by weight or more.

In order to improve the adhesion, a bifunctional epoxy resin having a sulfur atom in the skeleton and a bifunctional epoxy resin having no sulfur atom in the skeleton which is used in combination as needed are necessary. The amount is 50% by weight or more, preferably 65% by weight or more, and more preferably 80% by weight or more based on the epoxy resin (a). In this case, if it is less than 50% by weight, the adhesion is drastically lowered, and only a composition lacking in practicality can be obtained.

A bifunctional epoxy resin having no sulfur atom in the skeleton which can be used together with a bifunctional epoxy resin having a sulfur atom in the skeleton, and examples thereof include a hydroquinone type epoxy resin, a bisphenol type epoxy resin, and a combination. A phenolic epoxy resin or a naphthalenediol epoxy resin. Specifically, for example, EPOTOHTO YDC-1312, EPOTOHTO ZX-1027 (made by Dongdu Chemical Co., Ltd., hydroquinone type epoxy resin), EPOTOHTO ZX-1251 (made by Dongdu Chemical Co., Ltd., 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 (made by Dongdu Chemical Co., Ltd., bisphenol A epoxy resin), EPOTOHTO YDF -170,EPOTOHTO YDF-8170,EPOTOHTO YDF-870GS,EPOTOHTO YDF-2001 (made by Dongdu Chemical Co., Ltd., bisphenol P type epoxy resin), EPOTOHTO ZX-1201 (made by Dongdu Chemical Co., Ltd., bisphenol oxime epoxy) Resin), EPOTOHTO ZX-1355, EPOTOHTO ZX-1711 (manufactured by Tosho Kasei Co., Ltd., naphthalene glycol type epoxy resin), etc., but not limited thereto, or two or more types may be used in combination. Further, from the viewpoint of flame retardancy, it is preferred to use an epoxy resin having no alkyl substituent, such as a naphthalenediol type epoxy resin or a biphenyl type epoxy resin or a bisphenol F type epoxy. The resin is better.

When 50% by weight or more of a bifunctional epoxy resin having a sulfur atom in the skeleton is used, heat resistance and adhesion can be sufficiently satisfied, but in order to further improve flame retardancy, heat resistance and adhesion, it may not be reached. The range of 50% by weight includes an epoxy resin other than a bifunctional epoxy resin having a sulfur atom in the skeleton. However, from the viewpoint of flame retardancy, the aliphatic epoxy resin is not preferable, and it is preferable to use a bifunctional epoxy resin from the viewpoint of improving adhesion, but from the viewpoint of improving heat resistance A polyfunctional epoxy resin having an average number of functional groups of 2.1 or more is preferred.

Examples of the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and an aralkyl type epoxy resin. Specific examples include, for example, EPOTOHTO YDPN-638 (made by Dongdu Chemical Co., Ltd., phenol novolak type epoxy resin), EPOTOHTO YDCN-701, EPOTOHTO YDCN-702, EPOTOHTO YDCN-703, and EPOTOHTO YDCN-704 (made by Dongdu Chemical Co., Ltd.). O-cresol novolac type epoxy resin), EPOTOHTO ESN-175 (made by Dongdu Chemical Co., Ltd., β-naphthyl aralkyl type epoxy resin), EPOTOHTO ESN-475V, EPOTOHTO ESN-485 (made by Dongdu Chemical Co., Ltd.) Α-naphthyl aralkyl type epoxy resin), EPOTOHTO ESN-355, EPOTOHTO ESN-375 (made by Dongdu Chemical Co., Ltd., dinaphthyl aralkyl type epoxy resin), EPPN-501H, EPPN-502 (Japan Chemicals Co., Ltd., polyfunctional epoxy resin), NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), etc., but not limited thereto, or two or more types may be used in combination. . Further, from the viewpoint of flame retardancy, an epoxy resin having no alkyl substituent is preferred, and among these, a phenol novolak type epoxy resin or a naphthol aralkyl type epoxy resin is more preferable.

In Patent Document 1, although a phosphorus-containing epoxy resin obtained from an epoxy resin containing up to 45% by weight of a bifunctional epoxy resin having a sulfur atom in a skeleton is disclosed, since it is less than 50% by weight, The heat resistance is not sufficient. Patent Document 5 discloses that a phosphorus-containing epoxy resin obtained from a naphthyl aralkyl type epoxy resin has sufficient heat resistance, but since a bifunctional epoxy resin having a sulfur atom in a skeleton is not used, Then the sex is not good.

The phosphorus compound (b) used in the present invention is required to be a phosphorus compound in which a compound represented by the chemical formula (2) is mixed at a ratio of 0.06 mol or less to the compound 1 of the formula (1).

A representative example of the compound of the formula (1) is a compound of the formula (2), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-Dihydro-9) -oxa-10-phosphaphenanthrene-10-oxide) A phosphorus compound obtained by reaction with 1,4-naphthoquinone.

In the case of the phosphorus compound (b), the compound represented by the chemical formula (1) synthesized in advance may be used in combination with the compound represented by the chemical formula (2), or may be used before the reaction with the epoxy resin (a), relative to the chemical formula. (2) The compound 1 shown is a molar reaction of 1,4-naphthoquinone in a range of from 0.94 mol to 1.00 mol. When the compound of the formula (2) is reacted with 1,4-naphthoquinone before the reaction with the epoxy resin (a), the compound of the formula (2) is 1 mol, and the use is less than 1.00 mol. The 1,4-naphthoquinone is preferred. At this time, the reaction of the compound of the formula (2) with 1,4-naphthoquinone is carried out according to the theory, and the compound of the formula (1) is obtained, and the obtained phosphorus-containing epoxy resin (X) does not remain in the raw material. 1,4-naphthoquinone. The 1,4-naphthoquinone which remains in the phosphorus-containing epoxy resin (X) obtained by using 1,4-naphthoquinone of 1.00 mol or more with respect to the compound 1 molar represented by the chemical formula (2), However, the moisture resistance of the cured product is deteriorated, which is not preferable.

When the compound represented by the chemical formula (2) exceeds 0.06 mol, since the phosphorus content is easily adjusted, it is effective for improving flame retardancy and lowering the viscosity, but a compound having a monofunctional chemical formula (2) and an epoxy are often generated. The reaction of the base lowers the number of epoxy groups, resulting in a decrease in the adhesion of the cured product, a decrease in heat resistance and a decrease in moisture resistance, and a significant decrease in electrical insulation reliability for high heat-resistant applications. When the compound represented by the chemical formula (2) is not used, the compound represented by the chemical formula (1) must be produced in advance. The manufacture of this compound requires many steps, is not productive, and is not of industrial interest. Further, in the reaction with the epoxy resin (b), if the phosphorus content in the final phosphorus-containing epoxy resin composition is set to a high value, the molecular weight of the resulting phosphorus-containing epoxy resin is increased, and the resin viscosity is increased. It will rise excessively, and the impregnation with the glass cloth will be significantly deteriorated. Not only will it be unprofitable in the industry, but the physical properties of the laminated sheets obtained, especially the weld heat resistance, and the elastic modulus tend to become higher. The laminate is easy to become hard and brittle. Therefore, the molar ratio of the compound represented by the chemical formula (2) to the compound of the formula (1) is 0.06 mol or less, preferably 0.01 mol to 0.05 mol.

In Patent Document 4, a phosphorus-containing epoxy resin obtained from a bisphenol S-type epoxy resin is suggested, but it is not disclosed in the examples, and the compound represented by the chemical formula (2) remaining is not considered. In the examples, bisphenol A or bisphenol F is exemplified, but the compound 1 of the formula (1) is reacted with 0.92 mole of the compound represented by the formula (2), so the chemical formula (2) The compound is left to be present in a large amount, so that heat resistance is poor, and there is a problem in electrical insulation reliability for high heat-resistant use.

When the epoxy resin (a) used in the present invention is reacted with the phosphorus compound (b), a phenol compound having two or more functional groups other than the phosphorus compound (b) may be used. Examples of the phenolic compound having two or more functional groups include bisphenol A, bisphenol S, bisphenol F, naphthalenediol, biphenol, phenol novolac resin, cresol novolac resin, glyoxal tetraphenol resin, and bisphenol A phenol resin. , phenol aralkyl resin, naphthol aralkyl resin, biphenol aralkyl resin, and the like. In particular, from the viewpoint of flame retardancy, a phenol compound having no alkyl substituent is preferred, and among these, bisphenol S or naphthalenediol or biphenol is particularly preferred. The purpose of using a bifunctional or higher phenolic compound is to adjust the phosphorus content or sulfur content or softening point or epoxy equivalent when reacting the epoxy resin (a) with the phosphorus compound (b), or Adjust the elastic modulus of the laminate.

Further, the reaction of the epoxy resin (a) and the phosphorus compound (b) used in the present invention with a difunctional or higher phenol compound used as needed may be carried out by a known method, and the reaction temperature may be from 100 ° C to 200 ° C. More preferably, it is carried out under stirring at 120 ° C to 180 ° C. The reaction time can be determined by measuring the epoxy equivalent. The measurement of the epoxy equivalent can be carried out in accordance with the method of JIS K-7236. Since the epoxy resin (a) and the phosphorus compound (b) react with the phenol compound to increase the epoxy equivalent, the reaction end point can be determined in accordance with the comparison with the theoretical epoxy equivalent.

Further, when the reaction rate is slow, a catalyst may be used as needed to improve productivity. Specifically, a tertiary amine such as benzyldimethylamine, a quaternary ammonium salt such as tetramethylammonium chloride, triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine 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.

In the flame-retardant phosphorus-containing epoxy resin composition of the present invention, the phosphorus content must be from 0.5% by weight to less than 2.0% by weight based on the total epoxy resin component. If it is less than 0.5% by weight, sufficient flame retardancy cannot be imparted. When it is 2.0% by weight or more, the moisture resistance of the cured product is lowered by the influence of the phosphorus component in the phosphorus-containing epoxy resin, and the reliability of the high heat-resistant use is remarkably lowered.

In the flame-retardant phosphorus-containing epoxy resin composition, since the phosphorus content of the entire epoxy resin component is adjusted to 0.5% by weight to less than 2.0% by weight, it is relative to the phosphorus-containing epoxy resin (X). 100 parts by weight, 0 parts by weight to 50 parts by weight of the epoxy resin containing no phosphorus. When 50 parts by weight or more is blended, the phosphorus content of the phosphorus-containing epoxy resin (X) must be increased so that the flame retardancy is not impaired, and in this case, the heat resistance of the flame-retardant phosphorus-containing epoxy resin composition Will be greatly reduced. From the viewpoint of flame retardancy, the epoxy resin containing no phosphorus is poor in aliphatic epoxy resin, and from the viewpoint of heat resistance, the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more The class is preferred, and the above epoxy resins are preferred. In particular, when a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more is used as the epoxy resin containing no phosphorus, if it is 50 parts by weight or less, the present invention can be obtained without impairing heat resistance and flame retardancy. A flame retardant phosphorus-containing epoxy resin composition. More preferably, the epoxy resin containing no phosphorus is from 0 part by weight to 25 parts by weight relative to 100 parts by weight of the phosphorus-containing epoxy resin (X).

The phosphorus-containing ratio of the phosphorus-containing epoxy resin (X) of the present invention may be in the range of 0.5% by weight to 3.5% by weight, preferably 0.8% by weight to 3.0% by weight, and 1.2% by weight to 2.7% by weight. More preferably, it is particularly preferably from 1.5% by weight to 2.3% by weight. If the phosphorus content is less than 0.5% by weight, it is difficult to ensure flame retardancy. When it exceeds 3.5% by weight, the resin viscosity becomes high and it is difficult to synthesize, and the molecular weight of the resin increases, which adversely affects heat resistance, and the impregnation property of the glass cloth is also deteriorated, which is not industrially advantageous. The physical properties of the cured product, especially moisture resistance and solder heat resistance, are deteriorated. Further, when an epoxy resin other than the phosphorus-containing epoxy resin (X) is not used, the phosphorus-containing epoxy resin (X) must have a phosphorus content of 0.5% by weight to less than 2.0% by weight.

In the flame-retardant phosphorus-containing epoxy resin composition of the present invention, the sulfur content of the epoxy resin component must be 2% by weight to 9% by weight or less. If it is less than 2% by weight, sufficient heat resistance cannot be imparted. When it exceeds 9% by weight, the physical properties of the obtained cured product, particularly moisture resistance or solder heat resistance, are deteriorated by the influence of the sulfur component in the phosphorus-containing epoxy resin, and the reliability of the high heat-resistant use is remarkably lowered. It is preferably from 3% by weight to 8% by weight, more preferably from 4% by weight to 7% by weight. Further, when an epoxy resin other than the phosphorus-containing epoxy resin (X) is not used, the sulfur content of the phosphorus-containing epoxy resin (X) must be 2% by weight to 9% by weight or less.

The epoxy equivalent of the phosphorus-containing epoxy resin (X) of the present invention is preferably from 200 g/eq to 900 g/eq, more preferably from 250 g/eq to 800 g/eq, particularly preferably from 300 g/eq to 600 g/eq. When the epoxy equivalent is less than 200 g/eq, the adhesion is poor, and when it exceeds 900 g/eq, the heat resistance is adversely affected, so it is preferably adjusted to 200 g/eq to 900 g/eq.

The hardener (Y) of the present invention may, for example, be a phenol novolac resin, an alkylphenol novolac resin, an aralkylphenol novolac resin, or a third Phenolic phenolic resin, biphenyl aralkyl phenol resin, aralkyl naphthalenediol resin, polyphenols such as triphenylmethane and tetraphenylethane, adipic dihydrazide, bismuth dioxime Isoindoles, imidazole compounds and their salts, dicyandiamide, aminobenzoic acid esters, di-ethyltriamine, tri-ethylidene tetraamine, tetraethylidene pentaamine, m-benzene An aliphatic amine such as m-xylylenediamine or isophorone diamine, an aromatic amine such as diaminodiphenylmethane, diaminodiphenylanthracene or diaminoethylbenzene; Anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrofurfuric anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl A known conventional curing agent such as an acid anhydride such as methylnadic acid anhydride, but is not limited thereto. These hardeners may be used alone or in combination of two or more. These hardeners are preferably used in an amount of from 0.3 to 1.5 equivalents, more preferably from 0.4 to 1.2 equivalents, per equivalent of the epoxy group in the epoxy resin to be used.

In addition, the flame-retardant phosphorus-containing epoxy resin composition of the present invention may also be combined with a phosphine, an imidazole compound, a quaternary phosphonium salt, a tertiary amine, a quaternary ammonium salt, and a boron trifluoride as needed. Species, 3-(3,4-dichlorodiphenyl)-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-phenyl- A hardening accelerator such as 1,1-dimethylurea. These hardening accelerators vary depending on the epoxy resin to be used, the type of the epoxy resin hardener to be used, the molding method, the curing temperature, and the required characteristics, but are 0.01 parts by weight to 20 parts by weight based on 100 parts by weight of the epoxy resin. The range of parts by weight is preferably from 0.1 part by weight to 10 parts by weight.

The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be formulated with a thermosetting resin or a thermoplastic resin other than the epoxy resin within a range that does not impair the properties. For example, a phenol resin, an acrylic resin, a petroleum resin, an anthraquinone resin, an indene coumarone resin, a phenoxy resin, a cyanate resin, a polyurethane, and a poly Ester, polyamide, polyimine, polyamidimide, polyetherimide, bismaleimide Resin, polyether oxime, polyfluorene ether, polyetheretherketone, polyphenylene sulfide, polyvinylformal, etc., but are not limited thereto.

The flame retardant phosphorus-containing epoxy resin composition of the present invention may be formulated with an inorganic filler or an organic filler as needed. Examples of the filler include, for example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium citrate, calcium hydroxide, magnesium carbonate, barium carbonate, sulfuric acid. Niobium, boron nitride, carbon, glass fiber, carbon fiber, alumina fiber, cerium oxide alumina fiber, strontium carbide fiber, polyester fiber, cellulose fiber, aramid fiber, and the like. These fillers are preferably from 1% by weight to 95% by weight of the total amount of the epoxy resin.

The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be further formulated with a decane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a shake imparting agent, a smoothing agent, a flame retardant, a pigment, and the like as needed. additive. These additives are preferably from 0.01% by weight to 20% by weight based on the total amount of the epoxy resin composition.

The flame-retardant phosphorus-containing epoxy resin composition of the present invention can be prepared by a known method of preparing a phosphorus-containing epoxy resin (X), a hardener (Y), a hardening accelerator as needed, various fillers, and various various components. Additives and the like are obtained by uniformly mixing.

The flame-retardant phosphorus-containing epoxy resin composition of the present invention can be molded, hardened, and easily formed into a cured product in accordance with a known method. The molding method and the hardening method can be the same as those of the known epoxy resin composition.

The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be in the form of a sealing material, an adhesive layer, a molded article, a laminate, or a film.

As a result of evaluating the characteristics of the laminate obtained by using the flame-retardant phosphorus-containing epoxy resin composition of the present invention, a cured product having high heat resistance, low water absorption, and high reliability at high temperatures can be obtained. It is understood that the flame-retardant phosphorus-containing epoxy resin composition and the cured product thereof are a resin composition for manufacturing a copper-clad laminate used for an electronic circuit board, or a sealing material, a molding material, a mold material for an electronic component, Subsequent materials, film materials, materials for electrical insulating coatings, and the like.

Hereinafter, the present invention will be specifically described based on Synthesis Examples, Examples, and Comparative Examples, but the technical scope of the present invention is not limited to the examples. In addition, the number of the components of the synthesis examples, the examples, and the comparative examples is a part by weight unless otherwise specified.

Further, the present invention uses the following analytical methods.

Epoxy equivalent: According to the method described in JIS K-7236. That is, the sample was dissolved in 10 mL of chloroform, and 10 mL of acetic anhydride 20 mL and 20% of a tetraethylammonium bromide solution were added thereto, and titrated with a 0.1 mol/L perchloric acid acetic acid standard solution using a potentiometric titration apparatus.

Softening point: The ringing method according to JIS K-7234. That is, the sample was melted and defoamed and injected into a ring, and measured in a glycerin bath.

Phosphorus content: based on the nitric acid-perchloric acid decomposition method. That is, sulfuric acid, nitric acid, and perchloric acid are added to the sample and thermally decomposed to make all the phosphorus become orthophosphoric acid, and then reacted with a 0.25% ammonium vanadate solution and a 5% ammonium molybdate solution in an acidic sulfuric acid solution to produce The chromonic color of the phosphorus-vanadium molybdate complex was measured for the absorbance at a wavelength of 420 nm, and the phosphorus content was determined by a calibration curve.

Sulfur content: A method according to the oxygen flask combustion method described in JIS K-6233-1. That is, the sample was completely decomposed in a combustion flask, and captured and absorbed in the form of sulfate ions in the solution, and then measured using an ion chromatograph.

Copper foil peeling strength: According to the method described in JIS C-6481 5.7. That is, the copper foil and the insulating sheet were peeled off at a speed of 50 mm/min in a right angle direction and measured.

Interlaminar peel strength: According to JIS C-6481 5.7. That is, the peeling was performed at a speed of 50 mm/min in a right angle direction between one prepreg and the other three sheets.

Flame retardancy: It is measured according to the UL (Underwriters Laboratories) specification and the UL94 vertical test method, and is determined as the 4 level of V-0, V-1, V-2, and NG (non-flammability) based on the same specifications. (The more the latter, the worse the flame retardancy).

Glass transfer temperature: according to the TMA method. That is, TMA/SS120U manufactured by SII NanoTechnology Co., Ltd. was used as an analysis device, and the measurement was performed at a temperature increase rate of 10 ° C/min in accordance with thermomechanical analysis (TMA).

Linear thermal expansion coefficient: according to the TMA method. That is, the TMA/SS120U manufactured by SII NanoTechnology Co., Ltd. was used as an analysis device, and the displacement at 50 ° C to 150 ° C was determined by thermomechanical analysis (TMA) at a temperature increase rate of 10 ° C /min.

Water absorption rate: According to JIS C-6481 5.13. That is, using a test piece which has been cut into 50 mm × 50 mm, the dry weight after drying in an oven at 50 ° C for 24 hours is measured, and then the weight after boiling at 100 ° C for 2 hours is measured, based on the amount of increase from the dry weight. The moisture absorption rate was measured.

Solder heat resistance: According to JIS C-6481 5.5. That is, using a test piece which has been cut into 25 mm × 25 mm, the test piece which is boiled at 100 ° C for 2 hours is immersed in a solder bath of 288 ° C for 20 seconds at n = 5, when none of the five pieces expands and When peeling, it is ○, and even if only one sheet occurs, it is also ×.

Synthesis Example 1

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, HCA (phosphorus compound of the chemical formula (2) was fed (manufactured by Sanko Co., Ltd., phosphorus content: 14.2 weight) %) 64.0 g and 150 g of toluene were heated while stirring under a nitrogen atmosphere to completely dissolve. Then, 45.9 g of 1,4-naphthoquinone (manufactured by Kawasaki Kasei Kogyo Co., Ltd., 3% hydrated product) as an anthracene was placed in a divided manner. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.95. After the heating reaction, EPOTOHTO TX-0908 (epoxy equivalent: 219 g/eq) manufactured by Epoxy Chemical Co., Ltd. having a sulfur atom in the skeleton was fed, and 317.1 g of epoxy functional equivalent: 219 g/eq, and the number of average functional groups was 2.1 or more. EPOTOHTO YDPN-638 (manufactured by Toshiro Kasei Co., Ltd., phenol novolac type epoxy resin, epoxy equivalent: 176 g/eq) of 74.4 g of polyfunctional epoxy resin, stirred while introducing nitrogen gas, heated to 130 ° C and toluene Remove to the outside of the system. Then, 0.11 g of triphenylphosphine (manufactured by Kitagawa Chemical Co., Ltd., product name: TPP) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin A. . The obtained phosphorus-containing epoxy resin A had an epoxy equivalent of 392 g/eq, a phosphorus content of 1.8% by weight, a sulfur content of 5.2% by weight, and a softening point of 83 °C.

Synthesis Example 2

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 45.5 g of HCA (as described above) and 110 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 33.6 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.98. After heating the reaction, 420.7 g of EPOTOHTO TX-0908 (as described above) which is a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, and while stirring with nitrogen gas, the mixture was heated to 130 ° C and the toluene was removed to the outside of the system. Then, 0.08 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin B. The obtained phosphorus-containing epoxy resin B had an epoxy equivalent of 338 g/eq, a phosphorus content of 1.3% by weight, a sulfur content of 7.0% by weight, and a softening point of 76 °C.

Synthesis Example 3

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 64.5 g of HCA (as described above) and 150 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 47.2 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in a divided manner. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.97. After heating the reaction, 350.0 g of EPOTOHTO TX-0908 (as described above) having a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, and while stirring with nitrogen gas, the mixture was heated to 130 ° C and the toluene was removed to the outside of the system. Then, 0.11 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin C. The obtained phosphorus-containing epoxy resin C had an epoxy equivalent of 751 g/eq, a phosphorus content of 2.0% by weight, a sulfur content of 6.3% by weight, and a softening point of 120 °C.

Synthesis Example 4

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 75.0 g of HCA (as described above) and 175 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 55.9 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.99. After heating the reaction, 320.0 g of EPOTOHTO TX-0908 (as described above) as a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO ESN-485 as a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more were fed ( Manufactured by Dongdu Chemical Co., Ltd., α-naphthyl aralkyl type epoxy resin, epoxy equivalent: 269 g/eq) 30.0 g, and 4,4'-biphenol as a bisphenol or higher phenol compound (Nippon Steel Chemical Co., Ltd. The company's product, hydroxyl equivalent: 93 g/eq), 18.0 g, was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.15 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin D. The obtained phosphorus-containing epoxy resin D had an epoxy equivalent of 723 g/eq, a phosphorus content of 2.1% by weight, a sulfur content of 5.3% by weight, and a softening point of 125 °C.

Synthesis Example 5

In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, a 2,4-bisphenol S-type epoxy which is a bifunctional epoxy resin having a sulfur atom in the skeleton is fed. Resin (pre-synthesized according to the method described in Example 1 of Patent Document 6, epoxy equivalent: 220 g/eq) 340.0 g, and 9,10-dihydro-9-oxa compound as a phosphorus compound represented by Chemical Formula (1) -10-(2,7-dihydroxynaphthyl)-10-phosphaphenanthrene-10-oxide (previously synthesized according to the method described in Example 1 of Patent Document 7, hereinafter abbreviated as HCA-NQ) 64.8 g , Hg (as described above) of the phosphorus compound of the chemical formula (2) (1.1 g), and 4,4'-bisphenol S (a BPS-P (T) manufactured by Rihua Chemical Co., Ltd.) The hydroxyl group equivalent: 125 g/eq) 25.0 g was heated to 130 ° C while stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) was 0.03 mol based on the phosphorus compound 1 mol represented by the chemical formula (1). Then, 0.09 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin E. The obtained phosphorus-containing epoxy resin E had an epoxy equivalent of 441 g/eq, a phosphorus content of 1.2% by weight, a sulfur content of 7.8% by weight, and a softening point of 104 °C.

Synthesis Example 6

In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, EPOTOHTO YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.), which is a bifunctional epoxy resin having a sulfur atom in the skeleton, is fed. , epoxy equivalent: 172 g/eq) 400.0 g, HCA-NQ (as described above) of the phosphorus compound represented by the chemical formula (1), 62.0 g, and 4,4'-biphenol as a bifunctional or higher phenol compound (for example) 40.0 g of the above) was heated to 130 ° C while stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, 0.1 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin F. The obtained phosphorus-containing epoxy resin F had an epoxy equivalent of 333 g/eq, a phosphorus content of 1.0% by weight, a sulfur content of 7.7% by weight, and a softening point of 96 °C.

Synthesis Example 7

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 75.0 g of HCA (as described above) and 175 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 55.9 g of 1,4-naphthoquinone (as described above) as an anthracene was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.99. After heating the reaction, 180.0 g of EPOTOHTO TX-0908 (as described above) having a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO ZX-1711 as a bifunctional epoxy resin (manufactured by Tohto Kasei Co., Ltd., 2 5-pentanediol type epoxy resin, epoxy equivalent: 146 g/eq) 175.0 g, stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.13 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin G. The obtained phosphorus-containing epoxy resin G had an epoxy equivalent of 371 g/eq, a phosphorus content of 2.2% by weight, a sulfur content of 3.0% by weight, and a softening point of 110 °C.

Synthesis Example 8

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 103.6 g of HCA (as described above) and 240 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 53.4 g of 1,4-naphthoquinone (as described above) as a hydrazine was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.68. After heating the reaction, EPOTOHTO TX-0908 (as described above) 226.4 g as a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO YDPN-638 as a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more were fed. 117.3 g (as described above) was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.16 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin H. The obtained phosphorus-containing epoxy resin H had an epoxy equivalent of 563 g/eq, a phosphorus content of 2.9% by weight, a sulfur content of 3.7% by weight, and a softening point of 110 °C.

Synthesis Example 9

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 70.0 g of HCA (as described above) and 160 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 46.4 g of 1,4-naphthoquinone (as described above) as a hydrazine was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.88. After heating the reaction, 172.8 g of EPOTOHTO TX-0908 (as described above) having a bifunctional epoxy resin having a sulfur atom in the skeleton, and EPOTOHTO YD-128 (available as Dongdu Chemical Co., Ltd.) as a bifunctional epoxy resin were fed. A phenol A type epoxy resin, epoxy equivalent: 187 g/eq) 211.2 g, stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.11 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin I. The obtained phosphorus-containing epoxy resin I had an epoxy equivalent of 384 g/eq, a phosphorus content of 2.0% by weight, a sulfur content of 3.0% by weight, and a softening point of 70 °C.

Synthesis Example 10

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 70.0 g of HCA (as described above) and 160 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 46.4 g of 1,4-naphthoquinone (as described above) as a hydrazine was introduced in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.88. After heating the reaction, 300.0 g of EPOTOHTO YSLV-50TE (as described above) which is a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, and the mixture was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. Then, 0.12 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin J. The obtained phosphorus-containing epoxy resin J had an epoxy equivalent of 370 g/eq, a phosphorus content of 2.4% by weight, a sulfur content of 7.1% by weight, and a softening point of 106 °C.

Synthesis Example 11

In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, EPOTOHTO TX-0908 (as described above) which is a bifunctional epoxy resin having a sulfur atom in the skeleton was fed, 315.8 g. Further, 181.8 g of HCA-NQ (as described above) as a phosphorus compound represented by the chemical formula (1) was heated to 130 ° C while stirring under a nitrogen atmosphere. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, 0.18 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 170 ° C to 190 ° C for 4 hours to obtain a phosphorus-containing epoxy resin K. The obtained phosphorus-containing epoxy resin K had an epoxy equivalent of 1,080 g/eq, a phosphorus content of 3.0% by weight, a sulfur content of 5.2% by weight, and a softening point of 140 ° C or more, which was impossible to measure.

Synthesis Example 12

In a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, EPOTOHTO YSLV-50TE (as described above) 332.0 g as a bifunctional epoxy resin having a sulfur atom in the skeleton was fed. And 96.3 g of 4,4′-bisphenol S (as described above) as a bifunctional or higher phenol compound, and 71.3 g of HCA-NQ (as described above) as a phosphorus compound represented by the chemical formula (1), under a nitrogen atmosphere Stir and heat to 130 °C. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, 0.17 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 170 ° C to 190 ° C for 4 hours to obtain a phosphorus-containing epoxy resin L. The obtained phosphorus-containing epoxy resin L had an epoxy equivalent of 651 g/eq, a phosphorus content of 1.2% by weight, a sulfur content of 9.1% by weight, and a softening point of 140 ° C or more, which could not be measured.

Synthesis Example 13

In a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 90.0 g of HCA (as described above) and 210 g of toluene were fed as a phosphorus compound represented by the chemical formula (2). Stir under a nitrogen atmosphere and heat to dissolve completely. Then, while paying attention to the temperature rise due to the heat of reaction, 67.0 g of 1,4-naphthoquinone (as described above) as a quinone was added in portions. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0.99. After heating the reaction, 324.6 g of EPOTOHTO YD-128 (as described above) as a bifunctional epoxy resin was fed, and the mixture was stirred while introducing nitrogen gas, heated to 130 ° C, and toluene was removed to the outside of the system. At this time, a bifunctional epoxy resin having a sulfur atom in the skeleton is not used. Then, 0.16 g of triphenylphosphine (as described above) as a catalyst was added, and the reaction temperature was maintained at 160 ° C to 165 ° C for 4 hours to obtain a phosphorus-containing epoxy resin M. The obtained phosphorus-containing epoxy resin M had an epoxy equivalent of 529 g/eq, a phosphorus content of 2.7% by weight, a sulfur content of 0% by weight, and a softening point of 104 °C.

Examples 1 to 7 and Comparative Examples 1 to 6

Phosphorus-containing epoxy resin (X), hardener (Y), other epoxy resin, hardening accelerator, etc. are prepared according to the formulation shown in Table 1. Dissolving phosphorus-containing epoxy resin and other epoxy resin with methyl ethyl ketone, and adding dicyandiamide as a hardener (Y) predissolved in ethylene glycol cellosolve and dimethylformamide Amine (DICY, active hydrogen equivalent: 21.0 g/eq), and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) as a hardening accelerator to make the nonvolatile content 50% by weight The method is to modulate the resin varnish. Then, using the obtained resin varnish, glass cloth impregnated with the substrate (WEA 116E 106S 136, thickness 100 μm, manufactured by Nitto Denko Co., Ltd.), and the impregnated glass cloth was dried in a hot air circulating oven at 150 ° C for 8 minutes. Prepreg. Next, four pieces of the obtained prepreg were superposed on copper foil (3EC-III, thickness 35 μm, manufactured by Mitsui Mining Co., Ltd.), and heated at 130 ° C × 15 minutes and 190 ° C × 2.0 MPa × 70 minutes. Pressurized to obtain a 0.6 mm thick laminate. Each of the obtained laminated sheets was subjected to tests for physical properties such as copper foil peel strength, interlayer peel strength, flame retardancy, glass transition temperature, linear thermal expansion coefficient, water absorption ratio, and solder heat resistance. The results are shown in Table 2.

The phosphorus-containing epoxy resin (X) used in Example 1, Example 2, Example 3, Example 4, Example 7, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 6 was used. a phosphorus compound (b) obtained by reacting a compound represented by the chemical formula (2) with a 1,4-naphthoquinone before the reaction with the epoxy resin (a), and a reaction is carried out, and the phosphorus used in the embodiment 5 is used. The epoxy resin (X) is obtained by reacting a compound represented by the chemical formula (1) synthesized in advance with a compound represented by the chemical formula (2) as a phosphorus compound (b), and Example 6, Comparative Example 4, The phosphorus-containing epoxy resin (X) used in Comparative Example 5 was obtained by reacting only the phosphorus compound represented by the chemical formula (1) synthesized in advance. Further, in Example 3, Example 4, Example 5, Example 7, Comparative Example 3, and Comparative Example 6, a phosphorus-free epoxy resin other than the phosphorus-containing epoxy resin (X) was also used.

Comparative Example 1 used 66% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton when synthesizing the phosphorus-containing epoxy resin, but the compound of the chemical formula (2) was not related to the compound 1 of the chemical formula (1). The ear ratio is 0.46, that is, the compound of the chemical formula (2) is used in an amount of more than 0.06 mol, so the water absorption rate is as high as 1.7%, the moisture resistance is poor, and the solder heat resistance is also poor. Further, although a polyfunctional epoxy resin is often used, the glass transition temperature is 155 ° C, and heat resistance is difficult to be high. The interlaminar peel strength was also less than 1.0 kN/m, and it did not become a practical laminate. In Comparative Example 2, only 45% by weight (i.e., less than 50% by weight) of a bifunctional epoxy resin having a sulfur atom in the skeleton was used in synthesizing the phosphorus-containing epoxy resin, and, in contrast, the compound of the chemical formula (1) In the ear, the molar ratio of the compound of the formula (2) is 0.14, that is, the compound of the formula (2) is used in an amount of more than 0.06 mol, so that even if the phosphorus content is 2% by weight, flame retardancy cannot be obtained, and heat resistance is obtained. Low and high water absorption. In Comparative Example 3, although 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton was used in the synthesis of the phosphorus-containing epoxy resin, the compound of the chemical formula (2) was not related to the compound 1 of the chemical formula (1). The ear ratio is 0.14, that is, the compound of the chemical formula (2) is used in an amount of more than 0.06 mol, so the interlayer peel strength is less than 1.0 kN/m, and the solder heat resistance is also poor. In Comparative Example 4, although 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton was used in synthesizing the phosphorus-containing epoxy resin, and the compound of the chemical formula (2) was not used, since the phosphorus content was as high as 3% by weight, The softening point of the epoxy resin is as high as 140 ° C or more, which deteriorates the impregnation property of the glass cloth, and the interlayer peeling strength is less than 1.0 kN/m, and the solder heat resistance is not good. In Comparative Example 5, although 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton was used in synthesizing the phosphorus-containing epoxy resin, and the phosphorus compound of the chemical formula (2) was not used, the sulfur content was as high as 9.1% by weight. Therefore, the water absorption rate is as high as 2.2% by weight, and the moisture resistance is not good. Further, the softening point of the resin is as high as 140 ° C or more, so that the impregnation property to the glass cloth is deteriorated, and the interlayer peeling strength is less than 1.0 kN/m, and the solder heat resistance is not good. In Comparative Example 6, in the synthesis of the phosphorus-containing epoxy resin, since the bifunctional epoxy resin having a sulfur atom in the skeleton was not used, the glass transition temperature was also 138 ° C, the heat resistance was not high, and the phosphorus content was 2.07 wt% without difficulty. Flammability, has not become a practical laminate.

On the other hand, in the synthesis of the phosphorus-containing epoxy resin of Example 1, 81% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton and 19% by weight of a polyfunctional ring having an average number of functional groups of 2.1 or more were used. Oxygen resin, and the molar ratio of the compound of the formula (2) is 0.05 with respect to the compound 1 of the formula (1), that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, so the water absorption rate is 1.0. % is low, moisture resistance is good, phosphorus content is 1.8% by weight, and less than 2% by weight, and flame retardancy is also good. Moreover, the glass transition temperature is also as high as 165 ° C, the solder heat resistance is good, and the interlayer peel strength is also 1.1 kN/m, which is a laminate having a very high practicality. In the synthesis of the phosphorus-containing epoxy resin, Example 2 uses 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and is a molar compound of the compound of the formula (1) with respect to the compound 1 of the formula (1). The ratio of 0.02, that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the phosphorus content is 1.3% by weight, and the sulfur content is 7 wt%, so that the laminate is excellent in moisture resistance and adhesion. . Since the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more was not used at all, the flame retardancy was V-0, but the time until the flameout was slightly longer than that of Examples 1 and 4. The transfer temperature was also 161 ° C and although it was inferior to those of Example 1 and Example 4, it was a laminate which can be sufficiently used for heat-resistant use. In the synthesis of the phosphorus-containing epoxy resin, Example 3 uses 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and is a molar compound of the compound of the formula (1) with respect to the compound 1 of the formula (1). The ratio is 0.03, that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is 4.2% by weight, so the phosphorus content is 1.3% by weight and less than 2% by weight, and the flame retardancy is good. Moreover, it is a laminated board excellent in moisture resistance, heat resistance, and adhesion. In the synthesis of the phosphorus-containing epoxy resin, in Example 4, 91% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton and 9 wt% of a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more were used. And the molar ratio of the compound of the formula (2) is 0.01 with respect to the compound 1 of the formula (1), that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is 4.2% by weight. Therefore, the phosphorus content is 1.7% by weight and less than 2% by weight, and it is excellent in flame retardancy, and is a laminate having excellent moisture resistance, heat resistance, and adhesion. In the synthesis of the phosphorus-containing epoxy resin, Example 5 uses 100% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and is a molar compound of the compound of the formula (1) with respect to the compound 1 of the formula (1). The ratio is 0.03, that is, the compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is 5.9% by weight, so the phosphorus content is 0.9% by weight and less than 1% by weight, and the flame retardancy is good. Moreover, it is a laminated board excellent in moisture resistance, heat resistance, and adhesion. In the synthesis of the phosphorus-containing epoxy resin, Example 6 uses 100% by weight of a bifunctional epoxy resin having a sulfur atom in the skeleton, and the phosphorus compound of the formula (2) is not used, and only the phosphorus compound of the chemical formula (1) is used. Further, since the phosphorus content is 1.0% by weight and the sulfur content is 7.7% by weight, it is a laminate having excellent moisture resistance and adhesion. Since the polyfunctional epoxy resin having an average number of functional groups of 2.1 or more was not used at all, although the flame retardancy was V-0, the time until the flameout was slightly longer than that of Examples 1 and 4. The glass transition temperature was also 160 ° C and although it was inferior to those of Example 1 and Example 4, it was a laminate which can be sufficiently used for heat-resistant use. In the synthesis of the phosphorus-containing epoxy resin, Example 7 uses 51% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and 49% by weight of a 2-functional epoxy resin having no sulfur atom in the skeleton, and Compared with the phosphorus compound 1 of the formula (1), the molar ratio of the phosphorus compound of the formula (2) is 0.01, that is, the phosphorus compound of the formula (2) is used in an amount of less than 0.06 mol, and the sulfur content is Since it is 2.4% by weight, the phosphorus content is 1.8% by weight and is less than 2% by weight, and it is excellent in flame retardancy and is a laminate having excellent moisture resistance, heat resistance and adhesion.

Thus, in the examples, the compound represented by the formula (1) is a compound represented by the formula (2), and the compound represented by the formula (2) is 0.06 mol or less, and 50% by weight or more of a bifunctional epoxy resin having a sulfur atom in the skeleton is used. A phosphorus-containing epoxy resin is synthesized, and the phosphorus-containing epoxy resin is used as an essential component, so that the phosphorus content of the epoxy resin is from 0.5% by weight to less than 2.0% by weight, and the sulfur content is from 2% by weight to 9%. % by weight, in these examples, excellent in flame retardancy, adhesion, heat resistance, and moisture resistance. In particular, by adjusting the phosphorus content of the epoxy resin to 0.5% by weight to less than 2.0% by weight, and adjusting the sulfur content to 2% by weight to 9% by weight, the heat resistance can be maintained while reducing the water absorption rate. And the solder heat resistance is improved. Further, as shown in Example 5 or Example 6, even if the phosphorus content is 1% by weight or less, the flame retardancy can be satisfied, and thus a laminated board excellent in moisture resistance can be obtained. Further, as shown in Example 3, Example 4, Example 5, and Example 7, a phosphorus-free epoxy resin may be used in combination, especially by using a polyfunctional epoxy having an average number of functional groups of 2.1 or more. In the resin, an epoxy resin composition excellent in adhesion and flame retardancy can be obtained while obtaining high heat resistance.

(industrial availability)

The present invention is most suitable as an electrical insulating material typified by a copper-clad laminate for use in an electronic circuit board, and is also suitable as a sealing material, a molding material, a molding material, an adhesive, and a film material for electronic components, and is also effective as Materials for electrical insulation coatings.

Claims (11)

A flame-retardant phosphorus-containing epoxy resin composition comprising a phosphorus-containing epoxy resin (X) and a hardener (Y) flame retardant phosphorus-containing epoxy resin composition, characterized in that: the phosphorus-containing epoxy The resin (X) is an epoxy resin (a) having a bifunctional epoxy resin having a sulfur atom in a skeleton of 50% by weight to 100% by weight, and a chemical formula relative to the chemical formula (1) (2) A phosphorus compound (b) mixed at a ratio of 0.06 mol or less is reacted as an essential component, and the flame retardant phosphorus-containing epoxy resin composition is contained with respect to all epoxy resin components. The phosphorus ratio is 0.5% by weight to 1.8% by weight, and the sulfur content is 2% by weight to 9% by weight or less; The flame-retardant phosphorus-containing epoxy resin composition according to claim 1, wherein the phosphorus-containing epoxy resin (X) is obtained from the epoxy resin (a), and the epoxy resin (a) is Containing 50% by weight to 95% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, respectively, and 5 weights From % to less than 20% by weight, a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more is an essential component. The flame-retardant phosphorus-containing epoxy resin composition according to claim 1, wherein the phosphorus-containing epoxy resin (X) is obtained from the epoxy resin (a), and the epoxy resin (a) is It contains 50% by weight to 95% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and contains 5% by weight to less than 20% by weight of a phenol novolac type epoxy resin. The flame-retardant phosphorus-containing epoxy resin composition according to claim 1, wherein the phosphorus-containing epoxy resin (X) is obtained from the epoxy resin (a), and the epoxy resin (a) is It contains 50% by weight to 95% by weight of a 2-functional epoxy resin having a sulfur atom in the skeleton, and contains 5% by weight to less than 20% by weight of an aralkyl type epoxy resin. The flame-retardant phosphorus-containing epoxy resin composition according to any one of the items 1 to 4, wherein the composition contains 50 parts by weight or less based on 100 parts by weight of the phosphorus-containing epoxy resin (X). Phosphorus-containing epoxy resins are essential components. A prepreg characterized by using a flame retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5. An insulating back sheet characterized by using the flame retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5. An epoxy resin laminated board characterized by using the flame retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5. An epoxy resin sealing material, which uses the first item of the patent application scope to A flame retardant phosphorus-containing epoxy resin composition according to any one of the items 5. An epoxy resin mold material obtained by using the flame retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5. A flame-retardant phosphorus-containing epoxy resin cured product obtained by hardening a flame-retardant phosphorus-containing epoxy resin composition according to any one of claims 1 to 5.