TWI574984B - Method for manufacturing phosphorus-containing epoxy resin - Google Patents

Description

Method for producing phosphorus-containing epoxy resin

The present invention relates to a method for producing a phosphorus-containing epoxy resin which has both flame retardancy, low viscosity and high heat resistance, and a phosphorus-containing epoxy resin obtainable by the production method, which is regarded as an essential The epoxy resin composition of the component, and the cured product.

Since epoxy resin is excellent in adhesiveness, heat resistance, and moldability, it is widely used in laminated boards, sealants, automobile parts, FRP, sporting goods, etc. of electric/electronic equipment. In particular, in the case of a laminate used in an electric/electronic machine, in order to prevent combustion during a fire and control smoke generation, it is strongly required to impart flame retardancy. As a method for incombustizing a laminated resin, conventionally, a bromine-based flame retardant, a nitrogen-based flame retardant, and a phosphorus-based flame retardant are used alone or in combination with the flame retardant alone or in combination. The flame retardant system of flame retardant additives is the mainstream. However, in recent years, bromine-based flame retardants have been gradually avoided due to environmental problems. Further, when red phosphorus is used as the additive phosphorus-based flame retardant, safety is not sufficient; when a phosphate-based compound is used, there is a problem that bleed out on the surface of the cured product. Moreover, when a phosphate ester is used, there exists a problem that solder heat resistance and solvent resistance fall.

In view of the above problems, Patent Document 1 and Patent Document 2 disclose: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ, manufactured by Sanko Co., Ltd.) and epoxy resin The molar ratio reaction provides a thermosetting resin and a composition. Further, Patent Document 3 discloses that a resin having a bifunctional or higher epoxy group is reacted with Diphenylphosphinyl hydroquinone to form a phosphorus-containing epoxy resin. However, since the phosphorus-containing epoxy resin obtained by the reaction of such a phosphorus compound and an epoxy resin has a large molecular weight as the phosphorus content becomes high, a varnish of an epoxy resin which is sufficiently flame-retardant is obtained. The viscosity is high, and there is a problem that the impregnation property of the substrate such as workability and glass cloth is deteriorated. Further, since the molecular weight of the phosphorus-containing epoxy resin is increased, the crosslinking density of the cured product is lowered, so that it is difficult to obtain a high glass transition temperature.

Further, Patent Document 4 discloses that since only a phosphorus-containing epoxy resin cannot obtain sufficient flame retardancy, a phosphorus-containing compound is dissolved in a phosphorus-containing epoxy resin composition to increase the phosphorus content, but The use of a high boiling point solvent such as N,N-dimethylformamide in a solvent also has a problem that a phosphorus compound is easily precipitated. Patent Document 5 discloses a method of dispersing HCA-HQ into a resin varnish by finely pulverizing HCA-HQ into an average particle diameter of 10 μm and a maximum particle diameter of 40 μm, but the viscosity is likely to be dissolved by using a high-boiling solvent to dissolve a phosphorus compound. The time is higher, and there is a problem that the viscosity of the varnish cannot be lowered and sufficient flame retardancy cannot be obtained.

The present inventors have carefully studied the problem that the viscosity of the flame-retardant varnish is increased, which is a disadvantage of the phosphorus-containing epoxy resin, and as a result, it has been found that the epoxy resin obtained by the reaction between the epoxy resin and the phosphorus-containing compound is found. By coexisting an epoxy group and a phenolic hydroxyl group, a phosphorus-containing epoxy resin having a small molecular weight, a low varnish viscosity, and excellent workability can be obtained, and it is further known that an epoxy resin cured product which can be obtained and used with a conventional phosphorus-containing epoxy resin can be obtained. The application of Patent Document 6 is proposed in comparison with the high heat resistance characteristics.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 3092009

[Patent Document 2] Japanese Patent Publication No. 11-279258

[Patent Document 3] Japanese Patent Laid-Open No. Hei 5-214070

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-249540

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-011269

[Patent Document 6] Japan's Special Announcement No. 2011-036034

The present invention provides a method for producing a phosphorus-containing epoxy resin which is obtained by coexisting an epoxy group and a phenolic hydroxyl group in a phosphorus-containing epoxy resin, and which has a lower viscosity and no crystal precipitation stability, which is disclosed in Patent Document 6.

The inventors of the present invention have carefully studied the production method of a phosphorus-containing epoxy resin in which an epoxy group and a phenolic hydroxyl group coexist, and as a result, it has been found that by using a specific reaction catalyst, a lower viscosity and no crystal precipitation can be obtained. The present invention is accomplished by a stable phosphorus-containing epoxy resin.

That is, the gist of the present invention is as follows.

(1) A method for producing a phosphorus-containing epoxy resin, wherein a phosphine-based catalyst represented by the formula (1) is used as an essential component to cause an epoxy resin (a) to react with an epoxy group The compound (b) having a reactive functional group, wherein the compound (b) having a reactive functional group is a phosphorus-containing phenol compound represented by the formula (2), is obtained as an essential component. The epoxy equivalent of the phosphorus epoxy resin is in the range of 60% to 90% of the theoretical epoxy equivalent obtained by the formula 1; (In the formula, R is hydrogen or a hydrocarbon group having 6 or less carbon atoms, and may contain oxygen. Further, at least one R in the formula may be a hydrocarbon group or may contain oxygen. R may be the same or different.)

(In the formula, A is a triyl group having a carbon number of 6 to 20, and n is 0 or 1. Further, in the formula, R ₁ and R ₂ are a hydrocarbon group having a carbon number of 1 to 6, which may be the same or different, and It can be ring-shaped together with the phosphorus atom.)

(2) The method for producing a phosphorus-containing epoxy resin according to the above (1), wherein the compound (b) having a reactive functional group is equivalent to 1 equivalent of the epoxy group of the epoxy resin (a) The reactive functional group is reacted in the range of 0.10 equivalents to 0.94 equivalents.

(3) A phosphorus-containing epoxy resin obtained by the production method according to (1) or (2) above.

(4) A phosphorus-containing epoxy resin composition which is equivalent to 1 equivalent of the epoxy group of the epoxy resin (c) containing the phosphorus-containing epoxy resin as described in the above (3) as an essential component. The reactive functional group of the oxy-resin hardener is formulated in a range of from 0.1 equivalent to 1.3 equivalents.

(5) A cured phosphorus-containing epoxy resin obtained by curing the phosphorus-containing epoxy resin composition according to (4) above.

In the method for producing a phosphorus-containing epoxy resin of the present invention, the epoxy resin (a) and the phosphorus represented by the general formula (2) are obtained by using a specific phosphine catalyst represented by the general formula (1). The compound (b) having a phenol compound as an essential component and having a reactive functional group reactive with an epoxy group is reacted to obtain a phosphorus-containing ring having a low molecular weight, a lower viscosity, and less crystal precipitation of the phosphorus-containing phenol compound. An epoxy resin can provide an epoxy resin excellent in impregnation workability.

Further, by using the production method of the present invention, the synthesis of the phosphorus-containing epoxy resin having the epoxy resin (a) having more than two epoxy groups in one molecule has been changed in the synthesis. It is easy to obtain higher heat resistance than the cured product of the conventional phosphorus-containing epoxy resin.

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

In the method for producing a phosphorus-containing epoxy resin of the present invention, the epoxy resin (a) which can be used may, for example, be EPOTOHTO YD-128 or EPOTOHTO YD-8125 (bisphenol A type manufactured by Nippon Steel Chemical Co., Ltd.) Epoxy resin), EPOTOHTO YDF-170, EPOTOHTO YDF-8170 (Nippon Steel Chemical Co., Ltd. bisphenol F epoxy resin), YSLV-80XY (Nippon Steel Chemical Co., Ltd. tetramethyl bisphenol F Epoxy resin), EPOTOHTO YDC-1312 (hydroquinone epoxy resin), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), EPOTOHTO YDPN-638 (phenolic phenolic phenol manufactured by Nippon Steel Co., Ltd. Lacquer (phenol novolac) epoxy resin), EPOTOHTO YDCN-700-2, EPOTOHTO YDCN-700-3, EPOTOHTO YDCN-700-5, EPOTOHTO YDCN-700-7, EPOTOHTO YDCN-700-10, EPOTOHTO YDCN-704 (Nippon Steel Chemical Co., Ltd. cresol novolac type epoxy resin), EPOTOHTO ZX-1201 (bisphenol fluorene type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), TX -0710 (Nippon Steel Chemical Co., Ltd. made of bisphenol S type epoxy resin), EPICLON EXA-1515 (Daily Chemical Industry Co., Ltd. made of bisphenol S type epoxy resin), NC-3000 (biphenyl aralkyl phenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), EPOTOHTO ZX-1355, EPOTOHTO ZX-1711 (new Nippon Steel Chemical Co., Ltd. made naphthalene glycol type epoxy resin), EPOTOHTO ESN-155 (beta-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPOTOHTO ESN-355, EPOTOHTO ESN- 375 (Nippon Steel Chemical Co., Ltd. bisphthol aralkyl epoxy resin), EPOTOHTO ESN475V, EPOTOHTO ESN-485 (α-naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) , EPPN-501H (Nippon Chemical Pharmaceutical Co., Ltd. made phenylmethane type epoxy resin), Sumiepoxy TMH-574 (Sumitomo Chemical Co., Ltd. made phenylmethane type epoxy resin), YSLV-120TE (Nippon Steel Chemical Co., Ltd. made disulfide epoxy resin), EPOTOHTOZX-1684 (Nippon Steel Chemical Co., Ltd. made resorcinol epoxy resin), DENACOL EX-201 (Nagase ChemteX Co., Ltd. Phenolic epoxy resin), EPICLON HP -7200H (second ring made by DIC Corporation) Diene type epoxy resin), etc., epoxy resin produced from a phenolic compound of a polyhydric phenol resin and epihalohydrin; TX-0929, TX-0934, TX-1032 (alkane produced by Nippon Steel Chemical Co., Ltd.) Ethylene glycol epoxy resin) and other epoxy resins made from alcohol compounds and epihalohydrin; CELLQXIDE 2021 (aliphatic epoxy resin manufactured by DAICEL Chemical Industry Co., Ltd.), EPOTOHTOYH-434, (Nippon Steel Chemical Co., Ltd. Epoxy resin made from amine compound and epihalohydrin, such as diaminodiphenylmethanetetraglycidylamine, manufactured by Co., Ltd.; jER 630 (aminophenol-based epoxy resin manufactured by Mitsubishi Chemical Corporation) ), EPOOTO FX-289B, EPOTOHTO FX-305, TX-0932A (phosphorus epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), etc., which is obtained by reacting an epoxy resin with a modifier such as a phosphorus-containing phenol compound. Epoxy resin; amine ester modified epoxy resin, containing An epoxy resin such as an oxazolidone ring, but is not limited thereto. Further, these epoxy resins may be used singly or in combination of two or more types.

The compound (b) having a reactive functional group is a phosphorus-containing phenol compound represented by the formula (2) as an essential component. Specific examples of the phosphorus-containing phenol compound include 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA- manufactured by Sanko Co., Ltd.) HQ), 10-(1,4-dihydroxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA-NQ), diphenylphosphinylhydroquinone ( Beixing Chemical Industry Co., Ltd. trade name PPQ), diphenylphosphinyl-1,4-dihydroxynaphthalene, 1,4-cyclooctenephosphinyl-1,4-phenylene glycol (Japan Chemical Industry) Limited stock Phosphorus-containing phenols such as CPHO-HQ) and 1,5-cyclooctenephosphinyl-1,4-phenylene glycol (trade name CPHO-HQ, manufactured by Nippon Chemical Industry Co., Ltd.), but not Limited to this. Further, these phosphorus-containing phenol compounds may be used in combination of two or more types.

Wherein A is a tribasic group having a carbon number of from 6 to 20, and n is 0 or 1. In the formula, R ₁ and R ₂ are each a hydrocarbon group having a carbon number of from 1 to 6, which may be the same or may be the same. Different, it can also be ring-shaped together with the phosphorus atom.)

Further, these phosphorus-containing phenol compounds may be 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA manufactured by Sanko Co., Ltd.) or have direct binding to diphenyl. A phosphorus compound having an active hydrogen group of a phosphorus atom such as a phosphine is reacted with 1,4-benzoquinone or an anthracene such as 1,4-naphthoquinone. For the synthesis method, HCA-HQ is shown in Japanese Patent Laid-Open No. 60-126293, HCA-NQ is shown in Japanese Patent Laid-Open No. 61-236787, and PPQ is shown in zh. Obshch.kHim, 42(11), No. 2415- 2418 (1972), but it is not limited to this, and a well-known conventional method can be used.

As the compound (b) having a reactive functional group other than the phosphorus-containing phenol compound represented by the general formula (2), a modifier which is generally used as an epoxy resin can be used, and examples thereof include catechol (catechol). ), hydroxybenzenes such as resorcinol and hydroquinone; biphenols, binaphthols, phenols, bisphenol A, bisphenol F, bisphenol S, Shonol BRG-555 (Showa Denko) Co., Ltd. phenol novolac resin), cresol novolac resin, alkyl phenol novolac resin, aralkyl phenol novolac resin, containing three a phenol novolac resin, a biphenyl aralkyl phenol resin, a Resitop TPM-100 (a phenolic phenolic novolak resin made by Qunrong Chemical Industry Co., Ltd.), an aralkyl naphthalene diol resin, etc. a compound having two or more phenolic hydroxyl groups in the molecule; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA manufactured by Sanko Co., Ltd.) or having a direct bond a phosphorus compound such as an active hydrogen group of a phosphorus atom such as diphenylphosphine; an anthracene adipic acid; an anthracene azelate; an imidazole compound and a salt thereof; dicyandiamide ), an amine benzoate; an aliphatic amine such as divinyltriamine, trivinyltetramine, tetravinylpentamine, m-xylylenediamine, isophorone diamine; diaminodiphenyl An aromatic amine such as methane, diaminodiphenyl hydrazine or diaminoethyl benzene; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride (methyl An acid anhydride such as a nadic anhydride or a carboxylic acid obtained by ring-opening of an acid anhydride may be used in combination of two or more types. The compound is used in an amount of preferably 0.5 equivalent or less, more preferably 0.2 equivalent or less, based on 1 equivalent of the epoxy group in the epoxy resin to be used.

The catalyst used in the reaction is a phosphine catalyst represented by the formula (1). Specific examples thereof include: tertylyl phosphine, tris-dimethylphenylphosphine, ginseng (p-methoxyphenyl)phosphine (trade name: TPAP, manufactured by Kitagawa Chemical Co., Ltd.), and bis(dimethoxyphenyl). Phosphine, ginseng (tertiary butoxyphenyl) phosphine, diphenylphosphinostyrene (Beixing Chemical Industry Trade Name DPPST), and isomers of the above-mentioned catalyst, etc., but are not limited thereto. Further, these phosphine-based catalysts may be used in combination of two or more kinds, and a catalyst not represented by the formula (1) may be used in combination.

The amount of the reaction catalyst used is in the range of 0.005% to 1%, preferably 0.005% to 0.5%, relative to the compound (b) having a reactive functional group. More preferably, it is from 0.005% to 0.3%. When it is less than 0.005%, the reaction temperature becomes high and the reaction time needs to be prolonged, which is not preferable. On the other hand, when it is more than 1%, it is difficult to control the reaction, and not only a phosphorus-containing epoxy resin having a stable viscosity can be obtained, but also the storage stability of the epoxy resin is deteriorated.

The epoxy equivalent of the phosphorus-containing epoxy resin of the present invention is in the range of 60% to 90% of the theoretical epoxy equivalent obtained by the formula 1. When it is less than 60%, a phosphorus-containing phenol compound which is insoluble in a large amount remains, and it is precipitated without being dissolved in a solvent. When the amount is more than 90%, not only the effect of lowering the viscosity when the epoxy resin varnish is lowered is lowered, but also the glass transition temperature of the obtained cured product is lowered.

In the formula, the functional group equivalent of the compound (b) having a reactive functional group reactive with the epoxy group of the epoxy resin (a) is a phenolic hydroxyl equivalent in the case of a phenol compound, and is an anhydride. In the case of an acid anhydride equivalent, it is an active hydrogen equivalent in the case of an amine compound or a phosphorus compound having hydrogen directly bonded to a phosphorus atom.

Further, the phosphorus-containing epoxy resin obtained by the production method of the present invention is The reactive functional group of the compound (b) having a reactive functional group is reacted in an amount of from 0.10 equivalent to 0.94 equivalent, based on 1 equivalent of the epoxy group of the epoxy resin (a) represented by Formula 2. It is preferably from 0.20 equivalents to 0.70 equivalents, more preferably from 0.20 equivalents to 0.60 equivalents. When the compound (b) having a reactive functional group is less than 0.10 equivalent, the flame retardancy may become insufficient, and when the reaction is carried out in an amount exceeding 0.94 equivalent, the viscosity of the resulting phosphorus-containing epoxy resin becomes high, and This can result in poor workability.

The reaction temperature of the solventless production method of the present invention is in the temperature range of the well-known synthetic epoxy resin, specifically, higher than 130 ° C and less than 200 ° C. Further, it is preferably from 150 ° C to 180 ° C. When the temperature is lower than 130 ° C, the progress of the reaction is remarkably slow, and at 200 ° C or higher, the epoxy group and the phenolic hydroxyl group cannot be stably settled, and the epoxy equivalent is difficult to be in the range of 60% to 90% of the theoretical epoxy equivalent. .

The production method of the present invention may be carried out in the absence of a solvent or in a solvent, and the solventless reaction step and the solvent reaction step may be combined. However, when it is carried out in a solvent, it is preferably carried out in an aprotic solvent, and for example, it may be exemplified. : toluene, xylene, methanol, ethanol, 2-butoxyethanol, dialkyl ether, glycol ether, propylene glycol monomethyl ether, two The reaction temperature is preferably in the vicinity of the reflux temperature of the solvent, and the temperature range of 10 ° C or less from the reflux temperature is more preferable, and the heat source consumed by the reflux can be reduced. Further, these reaction solvents may be added during the reaction to adjust the reaction rate. Further, these reaction solvents may be used singly or in combination of two or more kinds. The reaction solvent is preferably used in an amount of 50% or less, preferably 30% or less, more preferably 10% or less based on the total mass of the reactants.

Further, in the production method of the present invention, by using the specific phosphine-based catalyst represented by the general formula (1), the epoxy equivalent can be made into the range of 60% to 90% of the theoretical epoxy equivalent, and adjustment can be employed. Reaction temperature, reaction time, and staged reaction A conventionally known production method such as a solvent to carry out a reaction, a stirring speed adjustment, and a loss of activity of a reaction catalyst is not limited thereto.

A phosphorus-containing epoxy resin composition can be obtained by using an epoxy resin curing agent in the epoxy resin (c) containing the phosphorus-containing epoxy resin obtained by the production method of the present invention as an essential component. As the epoxy resin curing agent, a known curing agent can be used, and examples thereof include a phenol curing agent such as a phenol novolak resin and an aralkyl phenol resin, and an amine curing agent such as dicyandiamide or diaminodiphenylmethane; An acid anhydride curing agent such as phthalic anhydride or maleic anhydride; an acidic polyester resin, an imidazole curing agent, and the like. Further, these curing agents may be used alone or in combination of two or more types.

The epoxy resin hardener is blended in an amount of from 0.1 equivalent to 1.3 equivalents based on the reactive functional group of the epoxy resin hardener, based on 1 equivalent of the epoxy group of the epoxy resin (c). When the general formulation of the epoxy resin is a phenolic hardener, the degree of phenolic hydroxyl equivalent of 1 equivalent to the epoxy group is adjusted, but the phosphorus-containing epoxy resin of the present invention still has a phenolic hydroxyl group, which is hardened. The phenolic hydroxyl group acts as a hardener, so the amount of blending hardening needs to be reduced. When the present invention is a phosphorus-containing epoxy resin, the phenolic hydroxyl group of the phenol curing agent is adjusted to 0.6 to 0.9 equivalents per equivalent of the epoxy group, and is optimally formulated in the same manner as the general formulation.

In addition to the above, the phosphorus-containing epoxy resin composition of the present invention may be an additive such as a curing accelerator, a flow regulator, a decane coupling agent, a filler, a pigment, or a colorant. Further, it may be impregnated into a substrate such as glass cloth or carbon cloth, and an organic solvent may also be used.

By hardening the phosphorus-containing epoxy resin composition of the present invention, a phosphorus-containing epoxy resin cured product can be obtained. As for the method of hardening, a well-known method of epoxy resin by heat hardening, photohardening, etc. can be performed, and can be cast by a mold or A well-known method such as lamination hardening and post-coating hardening is performed by hot pressing.

[Examples]

The following examples are illustrative of the invention, but the scope of the invention is not limited to such embodiments. Further, unless otherwise stated, "parts" means parts by weight, and "%" means percentage by weight. The analysis method and measurement method in the examples are as follows.

Epoxy equivalent: according to JIS K 7236.

Phenolic hydroxyl equivalent: The sample was dissolved in tetrahydrofuran (hereinafter referred to as THF) containing 4% methanol, 10% tetrabutylammonium hydroxide was added, and the absorbance at a wavelength of 400 nm to 250 nm was measured using an ultraviolet-visible spectrophotometer. The weight of the sample per hydroxy group of the phenolic hydroxyl group was determined from a standard curve obtained in advance by the same measurement method.

Non-volatile content: JIS K7235-1986

The number average molecular weight, the weight average molecular weight, and the dispersion: a gel permeation chromatography analyzer (HLC-8220GPC manufactured by Tosoh Corporation) in which G-2000HXL, G-3000HXL, and G-4000HXL were connected in series as a column. The THF as a solution was measured at a flow rate of 1.0 ml/min. The number average molecular weight and the weight average molecular weight were determined by a standard curve obtained from standard polystyrene. Dispersion is obtained by dividing the weight average molecular weight by the number average molecular weight.

Residual rate of phosphorus-containing phenol compound: Cadenza CD-C18 (150 × 4.6 mm Prod # CD005) using a high performance liquid chromatography (High Performance Liquid Chromatography; HP 1200, Agilent Technologies, Inc.), using an acidic solvent (water: acetic acid: Ammonium acetate = 395:5:1) and THF / acetonitrile solvent (1:1), flow rate of 0.7 ml / min, determination of THF / acetonitrile solvent in 0 minutes to 15 minutes concentration gradient from 40% to 80% of phosphorus-containing phenol % area of the compound and compounded by standard phosphorus-containing phenols The standard curve of the substance was measured to calculate the percentage in the sample.

Phosphorus-containing rate: sulfuric acid, hydrochloric acid, perchloric acid are added to the sample, heated and wet-ashed, and all phosphorus atoms are made into orthophosphoric acid. In the acidic solution of sulfuric acid, the metavanadate and the molybdate are reacted, and the absorbance of the resulting phosphovanadomolybdic acid complex at 420 nm is measured, and the sample is represented by the phosphorus atom content obtained by a standard curve prepared in advance. Percentage in .

Varnish viscosity: The viscosity at 25 ° C was measured using a rotary viscometer (Tokimec (current name: Tokyo Keiki) Co., Ltd.).

Solvent solubility: The resin solution obtained was visually confirmed, and it was indicated by crystallization or turbidity. Further, the resin solution was allowed to stand at 25 ° C for 7 days, and Δ indicates that crystals and turbidity appeared, and ○ indicates that crystals and turbidity did not occur, and it was shown in Table 1.

The phosphorus content of the composition is determined by calculating the phosphorus content of the phosphorus-containing epoxy resin to be formulated.

Tg: A differential scanning calorimeter (DSC6100 manufactured by SII Nano Technology Co., Ltd.) was used. The obtained cured product of the phosphorus-containing composition was measured at 10 ° C /min.

Flame retardancy test: Measured in accordance with UL94 specifications.

Peel strength: Measured in accordance with JIS K6854-1.

Example 1

In a four-port separable flask experimental apparatus equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction tube, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was placed ( Sanko Co., Ltd. trade name HCA, phosphorus content 14.2% by weight) 99 parts and 1,4-naphthoquinone (Kawasaki Chemicals Co., Ltd.) 71 copies, A 361 parts of benzene was stirred at 75 ° C for 30 minutes, and then the water in the system was removed while reacting at 110 ° C for 90 minutes. Thereafter, toluene was removed to obtain 10-(1,4-dihydroxynaphthalene)-10H-9-oxygen. Hetero-10-phosphaphenanthrene-10-oxide (HCA-NQ). 531 parts of a phenol novolac type epoxy resin (trade name YDPN-638, epoxide equivalent: 176 g/eq., manufactured by Nippon Steel Chemical Co., Ltd.) was added thereto as a catalyst (2.6-dimethoxyphenyl group). And 0.01 parts of phosphine (hereinafter referred to as DMPP), and after reacting at 165 ° C for 3 hours, 78 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) was added, and the reaction was carried out at reflux temperature for 2 hours or less. Thereafter, it was diluted with 179 parts of 43 parts of PGM and methyl ethyl ketone (hereinafter referred to as MEK), and the reaction was terminated after cooling to room temperature. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 1100 mPa. s, the actual measured epoxy equivalent was 297 g/eq., the phenolic hydroxyl equivalent was 2800 g/eq., the phosphorus content was 2.0%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 3514, the number average molecular weight was 825, and the dispersion was 4.26. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.29 equivalents based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 332 g/eq. The theoretical epoxy equivalent, the ratio of the actually determined epoxy equivalent is 89%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 2

In addition to 123 parts of HCA, 88 parts of 1,4-naphthoquinone, 488 parts of YDPN-638, and 0.02 parts of DMPP as a catalyst, the reaction was carried out at 165 ° C for 3.5 hours, and the reaction time after the addition of PGM was 3 hours. The operation was carried out in the same manner as in the first embodiment. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 3700 mPa. s, the actual measured epoxy equivalent was 359 g/eq., the phenolic hydroxyl equivalent was 2100 g/eq., the phosphorus content was 2.5%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 6986, the number average molecular weight was 1017, and the dispersion was 6.87. Again With respect to 1 equivalent of the epoxy group of the epoxy resin (a), the functional group equivalent of the compound (b) having a reactive functional group is 0.40 equivalent, and the theoretical epoxy equivalent is 432 g/eq., relative to the theoretical epoxy equivalent. The ratio of the actually determined epoxy equivalent was 83%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1. For the storage stability test, the obtained resin was stored in an oven at 50 ° C for 150 days, and the molecular weight change was observed to obtain a weight average molecular weight of 7016, a number average molecular weight of 1020, and a dispersion of 6.88.

Example 3

99 parts of HCA and 71 parts of 1,4-naphthoquinone were placed, and the other reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 531 parts of a phenylene-methane type epoxy resin (trade name EPPN-501H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 165.2 g/eq.), 37 parts of PGM, and 0.01 part of DMPP as a catalyst were added thereto. After reacting at 165 ° C for 3 hours, 41 parts of PGM was added, and the reaction was carried out for 3 hours at a reflux temperature or lower. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and after cooling to room temperature, the reaction was terminated. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 1800 mPa. s, the actual measured epoxy equivalent weight was 268 g/eq., the phenolic hydroxyl equivalent was 2200 g/eq., the phosphorus content was 2.0%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 2,497, the number average molecular weight was 863, and the dispersion was 2.89. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.28 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 305 g/eq. The ratio of the epoxy equivalent to the actually determined epoxy equivalent was 88%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 4

74 parts of HCA and 55 parts of 1,4-naphthoquinone were placed, and the other reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. Adding a dinaphthol aralkyl group thereto 571 parts of epoxy resin (ESN-375, manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 167 g/eq.), 0.01 parts of DMPP as a catalyst, and reacted at 165 ° C for 3 hours, and then added 78 parts of PGM. The reaction was carried out for 3 hours below the reflux temperature. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 600 mPa. s, the actual measured epoxy equivalent was 218 g/eq., the phenolic hydroxyl equivalent was 1500 g/eq., the phosphorus content was 1.5%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 1995, the number average molecular weight was 692, and the dispersion was 2.88. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.20 equivalent, and the theoretical epoxy equivalent is 254 g/eq., relative to 1 equivalent of the epoxy group of the epoxy resin (a). The theoretical epoxy equivalent, the ratio of the actually determined epoxy equivalent is 86%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 5

In the same manner as in Example 1, 74 parts of HCA and 53 parts of 1,4-naphthoquinone were placed, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 573 parts of a naphthol aralkyl type epoxy resin (trade name ESN-485, epoxide equivalent 294 g/eq.), 37 parts of PGM, and 0.01 parts of DMPP as a catalyst were added thereto. After reacting at 165 ° C for 2.5 hours, 41 parts of PGM was added, and the reaction was carried out for 2 hours at a reflux temperature or lower. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 880 mPa. s, the actual measured epoxy equivalent was 463 g/eq., the phenolic hydroxyl equivalent was 2900 g/eq., the phosphorus content was 1.5%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 1515, the number average molecular weight was 753, and the dispersion was 2.01. Further, it has an inverse with respect to 1 equivalent of the epoxy group of the epoxy resin (a) The functional group equivalent of the compound (b) having a functional group is 0.34 equivalent, the theoretical epoxy equivalent is 551 g/eq., and the ratio of the actually determined epoxy equivalent is 84% with respect to the theoretical epoxy equivalent. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 6

In the same manner as in Example 1, 148 parts of HCA and 106 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 446 parts of bisphenol F type epoxy resin (trade name YDF-170 manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 170 g/eq.), 0.02 parts of DMPP as a catalyst, and reaction at 165 ° C were added thereto. After the reaction, 37 parts of PGM was added for 2 hours, and then diluted with 58 parts of PGM and 138 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 75%, varnish viscosity 350 mPa. s, the actual measured epoxy equivalent of 342 g / eq., phenolic hydroxyl equivalent of 900 g / eq., phosphorus content of 3.0%, no turbidity was observed in the solvent solubility test. The weight average molecular weight was 825, the number average molecular weight was 434, and the dispersion was 1.90. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.51 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 551 g/eq. The ratio of the epoxy equivalent to the actually determined epoxy equivalent was 62%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 7

In the same experimental apparatus as in Example 1, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name of Sanko Co., Ltd.) was added. HCA-HQ 220 parts and YDF-170481 parts, and added 0.04 parts of DMPP as a catalyst. After reacting at 165 ° C for 1.5 hours, add 78 parts of PGM for 2 hours, then dilute with PGM 43 parts, MEK 179 parts, and cool to room temperature. End the reaction stop. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 500 mPa. s, the actual measured epoxy equivalent is 308 g/eq., the phenolic hydroxyl equivalent is 1200 g/eq., the phosphorus content is 3.0%, and no turbidity is observed in the solvent solubility test. The weight average molecular weight was 1,153, the number average molecular weight was 612, and the dispersion was 1.88. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.48 equivalents based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 474 g/eq. The theoretical epoxy equivalent, the ratio of the actually determined epoxy equivalent is 65%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 8

In the same manner as in Example 1, 123 parts of HCA and 88 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 488 parts of YDPN-638, 0.01 parts of tri-p-tolylphosphine as a catalyst, and 0.01 parts of ginseng (p-tert-butoxyphenyl)phosphine were added thereto, and after reacting at 165 ° C for 3 hours, PGM 78 was added. The reaction was carried out for 3 hours at a reflux temperature or lower. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 3800 mPa. s, the actual measured epoxy equivalent is 376 g/eq., the phenolic hydroxyl equivalent is 2900 g/eq., the phosphorus content is 2.5%, and no turbidity is observed in the solvent solubility test. The weight average molecular weight was 7256, the number average molecular weight was 985, and the dispersion was 7.37. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.40 equivalent, and the theoretical epoxy equivalent is 432 g/eq., relative to 1 equivalent of the epoxy group of the epoxy resin (a). The theoretical epoxy equivalent, the ratio of the actually determined epoxy equivalent is 87%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Example 9

The same procedure as in Example 8 was carried out except that the catalyst was 0.02 parts of tris-2,4-dimethylphenylphosphine. After reacting at 165 ° C for 3.5 hours, 78 parts of PGM was added, and the reaction was carried out for 3 hours under reflux temperature. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 3800 mPa. s, the actual measured epoxy equivalent was 369 g/eq., the phenolic hydroxyl equivalent was 2500 g/eq., the phosphorus content was 2.5%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 7,448, the number average molecular weight was 996, and the dispersion was 7.48. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.40 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 432 g/eq. The ratio of the epoxy equivalent to the actually determined epoxy equivalent was 85%. The properties of the synthesis and the properties of the epoxy resin are shown in Table 1.

Embodiment 10 to Embodiment 14, Example 17, and Example 18

In the phosphorus-containing epoxy resin obtained in the examples, BRG-557 (a group of phenol novolac hardener active hydrogen equivalents of 105 g/eq.) and a hardening accelerator were blended in a solid content shown in Table 2. An epoxy resin composition in which 50% of the nonvolatile matter dissolved in PGM/MEK was obtained was obtained. The obtained epoxy resin composition was impregnated with a glass cloth (WEA 116E 106S136, manufactured by Nippon Textile Co., Ltd., 0.1 mm), and dried in a hot air circulating oven at 150 ° C for 10 minutes to obtain a prepreg. Four pieces of the prepreg obtained were superposed on a copper foil (35 μm thick by 3EC-III Mitsui Mining Co., Ltd.), and vacuum pressure was applied at 2 MPa under the conditions of 130 ° C × 15 minutes + 190 ° C × 80 minutes. A 0.5 mm thick laminate was obtained. The blending ratio and the evaluation results of the laminate are shown in Table 2.

Example 15, Example 16, Example 19

Phosphorus-containing epoxy resin obtained in the examples and YDCN-704 (Nippon Steel In the cresol novolac type epoxy resin of Chemical Co., Ltd., the dicyandiamide (DICY active hydroxyl equivalent 21 g/eq.) as a curing agent and a hardening accelerator are formulated with the solid content shown in Table 2. An epoxy resin composition in which 50% of the nonvolatile matter dissolved in PGM/MEK was obtained was obtained. The obtained epoxy resin composition was impregnated with a glass cloth (a thickness of 0.1 mm manufactured by Tosoh Corporation, WEA 116E 106 S 136), and dried in a hot air circulating oven at 150 ° C for 10 minutes to obtain a prepreg. Four pieces of the obtained prepreg were overlapped with copper foil (35C of thickness of 3EC-III Mitsui Mining Co., Ltd.), and vacuum pressure was applied at a temperature of 130 ° C × 15 minutes + 170 ° C × 70 minutes. , a 0.5 mm thick laminate is obtained. The blending ratio and the evaluation results of the laminate are shown in Table 2.

Comparative example 1

In addition to adding 99 parts of HCA, 71 parts of 1,4-naphthoquinone, 531 parts of YDPN-638, and 0.02 parts of triphenylphosphine (hereinafter referred to as TPP) instead of DMPP as a catalyst, the rest is the same as in Example 1. The operation was carried out in the same manner, and after reacting at a reaction temperature of 160 ° C for 5 hours, it was diluted with 78 parts of PGM, and then reacted at reflux temperature for 11 hours. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 41900 mPa. s, the actual measured epoxy equivalent is 325 g/eq., the phenolic hydroxyl equivalent is 10000 g/eq. or more, the phosphorus content is 2.0%, and no turbidity is observed in the solvent solubility test. The weight average molecular weight was 14,495, the number average molecular weight was 1316, and the dispersion was 11.01. Further, the functional group equivalent of the compound (b) having a reactive functional group is 0.29 equivalents based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 328 g/eq. The ratio of the epoxy equivalent to the actually determined epoxy equivalent was 99%. The synthesis conditions and the properties of the epoxy resin are shown in Table 3.

Comparative example 2

In the same manner as in Example 1, 123 parts of HCA and 88 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 488 parts of YDPN-638 and 0.02 parts of TPP as a catalyst were added thereto, and after reacting at a reaction temperature of 160 ° C for 4 hours, the mixture was diluted with 78 parts of PGM, and then reacted at a reflux temperature for 4 hours. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 6720 mPa. s, the actual measured epoxy equivalent is 395 g/eq., the phenolic hydroxyl equivalent is 6000 g/eq., the phosphorus content is 2.5%, and no turbidity is observed in the solvent solubility test. The weight average molecular weight was 8036, the number average molecular weight was 1056, and the dispersion was 7.61. Further, the functional group of the compound (b) having a reactive functional group is 0.40 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 423 g/eq., relative to the theoretical ring. The ratio of oxygen equivalent, actually measured epoxy equivalent, was 93%. Table 3 shows the loading amount and the insertion ratio, and the properties of the resin.

The storage stability test was carried out in the same manner as in Example 2, and the molecular weight change was observed to obtain a weight average molecular weight of 9166, a number average molecular weight of 1,172, and a dispersion of 7.82.

Comparative example 3

In the same manner as in Example 1, 123 parts of HCA and 88 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 488 parts of YDPN-638 and 0.02 parts of TPP as a catalyst were added thereto, and after reacting at a reaction temperature of 160 ° C for 4 hours, it was diluted with 78 parts of PGM, and then reacted at reflux temperature for 3 hours. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 5600 mPa. s, the actual measured epoxy equivalent 381 g / eq., phenolic hydroxyl equivalent 3800 g / eq., phosphorus content 2.5%, the turbidity was observed in the obtained phosphorus-containing epoxy resin. The weight average molecular weight was 7731, the number average molecular weight was 962, and the dispersion was 8.04. Further, the functional group of the compound (b) having a reactive functional group is 0.40 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 423 g/eq., relative to the theoretical ring. The ratio of oxygen equivalents to the actually determined epoxy equivalents was 90%. Table 3 shows the loading amount and the insertion ratio, and the properties of the resin.

Comparative example 4

In the same manner as in Example 1, 99 parts of HCA and 71 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. 531 parts of EPPN-501H, 37 parts of PGM, and 0.02 parts of TPP as a catalyst were added thereto, and after reacting at a reaction temperature of 160 ° C for 5 hours, 41 parts of PGM was added, and the mixture was reacted at reflux temperature for 9 hours. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 28000 mPa. s, the actual measured epoxy equivalent is 305 g/eq., the phenolic hydroxyl equivalent is 10000 g/eq. or more, the phosphorus content is 2.0%, and no turbidity is observed in the solvent solubility test. The weight average molecular weight was 6656, the number average molecular weight was 1335, and the dispersion was 4.92. Further, the functional group of the compound (b) having a reactive functional group is 0.28 equivalents based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 305 g/eq., relative to the theoretical ring. The ratio of oxygen equivalent, actually measured epoxy equivalent, is 100%. Table 3 shows the loading amount and the insertion ratio, and the properties of the resin.

Comparative Example 5

In the same manner as in Example 1, 99 parts of HCA and 71 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. Yu Qi 531 parts of EPPN-501H, 37 parts of PGM, and 0.02 parts of TPP as a catalyst were added, and after reacting at a reaction temperature of 160 ° C for 5 hours, 41 parts of PGM was added, and the reaction was carried out at reflux temperature for 7 hours. Thereafter, it was diluted with 43 parts of PGM and 179 parts of MEK, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 2500 mPa. s, the actual measured epoxy equivalent is 289 g/eq., the phenolic hydroxyl equivalent is 5500 g/eq., the phosphorus content is 2.0%, and no turbidity is observed in the solvent solubility test. The weight average molecular weight was 3062, the number average molecular weight was 953, and the dispersion was 3.21. Further, the functional group of the compound (b) having a reactive functional group is 0.28 equivalents based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 305 g/eq., relative to the theoretical ring. The ratio of oxygen equivalent, actually measured epoxy equivalent, was 95%. Table 3 shows the loading amount, the insertion ratio, and the properties of the resin.

Comparative Example 6

In the same manner as in Example 1, 108 parts of HCA and 80 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. ESN-375833 parts and TP part of TPP as a catalyst were added thereto, and after reacting at a reaction temperature of 150 ° C for 3 hours, 113 parts of PGM was added, and the mixture was reacted at reflux temperature for 3 hours. Thereafter, 63 parts of PGM and 262 parts of MEK were diluted, and the mixture was cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 700mPa. s, the actual measured epoxy equivalent was 239 g/eq., the phenolic hydroxyl equivalent was 4000 g/eq., the phosphorus content was 1.5%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 2073, the number average molecular weight was 716, and the dispersion was 2.90. Further, the functional group of the compound (b) having a reactive functional group is 0.20 equivalent, and the theoretical epoxy equivalent is 254 g/eq., relative to the theoretical ring, with respect to 1 equivalent of the epoxy group of the epoxy resin (a). The ratio of oxygen equivalent, actually measured epoxy equivalent, was 94%. In Table 3 The amount, the ratio, and the properties of the resin are indicated in the middle.

Comparative Example 7

In the same manner as in Example 1, 209 parts of HCA and 150 parts of 1,4-naphthoquinone were placed in the same manner as in Example 1, and the reaction was carried out in the same manner as in Example 1 to obtain HCA-NQ. YDF-170641 parts and 0.092 parts of TPP as a catalyst were added thereto, and after reacting at 165 ° C for 4 hours, it was diluted with MEK 429 parts, and cooled to room temperature to terminate the reaction. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile component 70%, varnish viscosity 440 mPa. s, the actual measured epoxy equivalent was 409 g/eq., the phenolic hydroxyl equivalent was 1700 g/eq., the phosphorus content was 3.0%, and no turbidity was observed in the solvent solubility test. The weight average molecular weight was 1,160, the number average molecular weight was 603, and the dispersion was 1.92. Further, the functional group of the compound (b) having a reactive functional group is 0.50 equivalent based on 1 equivalent of the epoxy group of the epoxy resin (a), and the theoretical epoxy equivalent is 539 g/eq., relative to the theoretical ring. The ratio of oxygen equivalent, actually measured epoxy equivalent, was 76%. Table 3 shows the loading amount, the insertion ratio, and the properties of the resin.

Comparative Example 8

In the same manner as in Example 7, 314 parts of HCA-NQ, 687 parts of YDF-170, and 0.06 parts of TPP as a catalyst were added, and after reacting at 165 ° C for 4 hours, it was diluted with MEK 429 parts, and cooled to room temperature to cause a reaction. termination. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile content 70%, varnish viscosity 510 mPa. s, the actual measured epoxy equivalent 301 g / eq., phenolic hydroxyl equivalent 800 g / eq., phosphorus content 3.0%, in the solvent solubility test, after the resin solution was placed at 25 ° C for 7 days to see To crystallization, turbidity. The weight average molecular weight was 1,126, the number average molecular weight was 587, and the dispersion was 1.92. Further, the functional group of the compound (b) having a reactive functional group is 0.48 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin (a), and the theory The epoxy equivalent was 474 g/eq., and the ratio of the actually determined epoxy equivalent was 64% with respect to the theoretical epoxy equivalent. Table 3 shows the loading amount, the insertion ratio, and the properties of the resin.

Comparative Examples 9 to 13

In the phosphorus-containing epoxy resin obtained in the comparative example, BRG-557 and a hardening accelerator were blended in the solid content shown in Table 4 to obtain an epoxy resin composition dissolved in PGM/MEK. The obtained epoxy resin composition was impregnated with a glass cloth (WEA 116E106S136, manufactured by Nitto Bose Co., Ltd., thickness: 0.1 mm), and dried in a hot air circulating oven at 150 ° C for 10 minutes to obtain a prepreg. 4 pieces of the obtained prepreg were overlapped with copper foil (35C of thickness of 3EC-III Mitsui Mining Co., Ltd.), and vacuum addition of 2 MPa was performed under the conditions of 130 ° C × 15 minutes + 190 ° C × 80 minutes. Press to obtain a 0.5 mm thick laminate. In the phosphorus-containing epoxy resin obtained in Comparative Example 9 to Comparative Example 11, since the viscosity was high, the nonvolatile content of Comparative Example 9 and Comparative Example 11 was adjusted to 45%, and the nonvolatile content of Comparative Example 10 was adjusted to 48%. The blending ratio and the evaluation results of the laminate are shown in Table 4.

Comparative Example 14 to Comparative Example 16

In the phosphorus-containing epoxy resin obtained in the comparative example and YDCN-704, DICY as a curing agent was blended with the solid content shown in Table 4 to obtain a non-volatile component dissolved in PGM/MEK. Epoxy resin composition. The obtained epoxy resin composition was impregnated with a glass cloth (WEA 116 E 106S136, manufactured by Nippon Textile Co., Ltd., thickness: 0.1 mm), and dried in a hot air circulating oven at 150 ° C for 10 minutes to obtain a prepreg. Four pieces of the prepreg obtained were superposed on a copper foil (35 μm thick by 3EC-III Mitsui Mining Co., Ltd.), and subjected to vacuum pressure of 2 MPa at a temperature of 130 ° C × 15 minutes + 170 ° C × 70 minutes. A 0.5 mm thick laminate was obtained. The blending ratio and the evaluation results of the laminate are shown in Table 4.

As shown in Examples 1 to 9, the method for producing a phosphorus-containing epoxy resin of the present invention has a lower weight average molecular weight and a lower average molecular weight than Comparative Example 1 to Comparative Example 8 of the prior art. low. Therefore, the impregnation property to the glass cloth is good, and workability is excellent. Further, since the ratio of the epoxy equivalent actually measured with respect to the theoretical epoxy equivalent is also low, the present invention is used as compared with Comparative Example 9 to Comparative Example 14 of the prior art as shown in Examples 10 to 19. The obtained phosphorus-containing epoxy resin is also excellent in physical properties after curing as an epoxy resin composition. In the storage stability test at a constant temperature of 50 ° C, the phosphorus-containing epoxy resin of the present invention has a small change in molecular weight distribution and excellent storage stability as compared with the phosphorus-containing epoxy resin of the conventional production method. In the solvent solubility test, the phosphorus-containing epoxy resin of the conventional method has a low epoxy equivalent and is crystallized and turbid when stored. However, the phosphorus-containing epoxy resin obtained by the present invention does not show crystals, turbidity, and solvent dissolution. Sex is also good.

[Industry use possibility]

Since the phosphorus-containing epoxy resin produced by the production method of the present invention has a lower viscosity as an epoxy resin varnish than the conventional phosphorus-containing epoxy resin, it has good impregnation properties to a substrate such as glass cloth. Excellent sex. Moreover, since the phosphorus-containing epoxy resin produced by the production method of the present invention has a lower ratio of the actual measured epoxy equivalent to the theoretical epoxy equivalent than the conventional phosphorus-containing epoxy resin, the physical properties after curing are excellent. .

Claims (1)

A method for producing a phosphorus-containing epoxy resin, which comprises the phosphine-based catalyst represented by the general formula (1) as an essential component, and the epoxy resin (a) and a reactive functional group having a reaction with an epoxy group The compound (b) is reacted; the compound (b) is obtained by using the phosphorus-containing phenol compound represented by the formula (2) as an essential component, and the epoxy equivalent of the obtained phosphorus-containing epoxy resin is represented by Formula 1 The range of 60% to 90% of the theoretical epoxy equivalent is obtained, wherein the reactive functional group of the compound (b) is 0.10 equivalent to 0.94 with respect to 1 equivalent of the epoxy group of the epoxy resin (a). In the range of the equivalent amount, the reactive functional group is at least one of a hydroxyl group, an acid anhydride group, and an active hydrogen group, and the hydroxyl group derived from the phosphorus-containing phenol compound represented by the general formula (2) is regarded as a necessary one. (In the formula, R is hydrogen or a hydrocarbon group having 6 or less carbon atoms, and may contain oxygen; and at least one of R in the formula may be a hydrocarbon group or may contain oxygen, and R may be all the same or different) (wherein, A represents a triyl group having 6 to 20 carbon atoms, and n represents 0 or 1, and R ₁ and R ₂ in the formula are a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and Can be ringed together with the phosphorus atom,)