TW200946553A - Epoxy resin containing phosphorus, epoxy resin composition containing phosphorus and method for preparation thereof, and curing resin composition using said resin and said resin composition and cured product - Google Patents

Abstract

Disclosed is a method for producing a phosphorus-containing epoxy resin, wherein a phosphorus-containing epoxy resin is obtained by reacting a compound represented by general formula (1) with an epoxy resin. The method is characterized in that the value obtained by dividing the content (wt%) of a compound represented by general formula (2) in the system before reaction by the phosphorus content (wt%) in the phosphorus-containing epoxy resin obtained by reaction is not more than 0.3.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper laminate, a film, an epoxy resin composition (4), and the like, which are used for manufacturing an electronic circuit board, and useful A sealing epoxy material used as an electronic component, a sealing material for a molding material, an adhesive, an electrical insulating coating material, a cut epoxy resin, and a dish-containing epoxy resin composition, a method for producing the same, and a resin used therefor A curable resin composition and a cured product. [Prior Art] Since epoxy resin is excellent in adhesion, heat resistance, and moldability, it is widely used in electronic parts, electric machines, automobile parts, FRp (10) (10) inf〇rced pi_cs' fiber reinforced plastics, sports products, and the like. Among them, since the copper-clad laminates and sealing materials used in electronic parts and electrical equipment are strongly required to prevent fires and delay fires, it has been used so far that desertified epoxy resins having such characteristics are used. Although it has a significant problem, it can impart flame retardancy by virtue of the ring, and the resin is particularly attractive, and the epoxy group has high reactivity and excellent hardenability. Epoxy tree scorpion - straightly positioned as a useful electronic and electrical material. However, in recent electronic machines, the so-called light and short is considered to be the heaviest: the tendency is getting stronger. In this kind of social demand, from the recent light weight:: The point of view is that the important halogen is the better material. When the shirt is used and used for a long time, the dissociation of the halide occurs, and wiring occurs. The rot of the rot. Furthermore, the use of electronic components and electrical products that have been completed is environmentally safe. Therefore, it has been gradually studied that the use of halogens is considered a problem instead of harmful substances such as photographic elements. Regarding the public literature aspect of the compound represented by the general formula (1) described in the patent application scope, the 4 literatures! The system reveals that hca is called (10-(2,5-di-diphenyl)_9,1〇2 gas _9-oxyl phenanthrene 10 oxide manufactured by Sanguang Co., Ltd.) (l0_(2,5_dlhydr〇xyphenyi) 9,i〇^ydr〇_9 〇xa-

10-ph〇SphaPhenanthrene_10_〇xide) A thermosetting resin obtained by reacting an epoxy resin with a molar ratio of a predetermined ratio. The invention discloses a method for producing a phosphorus-containing epoxy resin obtained by reacting an epoxy compound having at least two epoxy groups with diphenylphosphinyl hydroquinone. Patent Document 3 discloses a method for producing a flame-retardant epoxy resin, which comprises reacting an epoxy resin, a phosphine compound having an aromatic group on a phosphorus atom, and a quinone compound in the presence of an organic solvent. Patent Document 4 discloses a phosphorus-containing epoxy resin obtained by reacting a phosphorus-containing polyvalent phenol compound represented by the formula (2) with an epoxy resin, and a phosphorus-containing flame-retardant epoxy resin composition. Patent Document 5 discloses a method for producing a lining flame-retardant double-presence type epoxy resin, which is carried out in steps 1 and 2, and step 1 is a method for making 9, 〇_dihydro-9-oxy-10-phosphorus杂 〇 〇 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物The reaction product is obtained by reacting a total amount of dihydro-9-oxy-10·phosphaphenanthrene-10-oxide in an amount of 0.3% by weight or less; and Step 2 is not refining the reaction composition obtained in Step 1. It is reacted with a double-presence A type epoxy resin and/or a bisphenol F type epoxy resin. 5 200946553 Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 However, any of the special patents, Japanese Patent Laid-Open No. Hei 04-1, 1662, and the Japanese Patent Laid-Open No. Hei 05-214070 JP-A-2002-265562, JP-A-2006-342217, JP-A-2006-342217, No. JP-A-2006-342217, the disclosure of which is incorporated herein by reference. (2) The description of the compound represented by the organophosphorus compound of one of the structural formula 3, wherein "the epoxy resin is formed by reacting with the epoxy resin group to form a so-called pendant in the resin. The crosslink density of the class is reduced, the hardening rate is slow, the heat resistance is lowered, or the mechanical strength is lowered, and the disadvantages are increased, and it is difficult to use an amount that sufficiently exhibits the degree of flame retardancy." It is also described that the use can sufficiently exhibit flame retardancy. A degree of the amount (generally about 10% by weight to tens of % by weight) of a monofunctional organic compound compound as a reactive organic phosphorus compound, the crosslinking density is reduced and the hardening speed is delayed. Room and other problems. Patent Document 6: JP-A-2000454234 SUMMARY OF THE INVENTION The present inventors have investigated the reactivity with various hardeners of phosphorus-containing epoxy resins, and found that the reactivity of the obtained phosphorus-containing epoxy resin is Significant difference. When the gelation time of the epoxy resin is long, the resin may excessively flow when hardened by lamination, and the resulting laminate may have a decrease in adhesion due to insufficient resin component, and migration may occur. 200946553 (mlgratl 〇n), such as swelling during welding and impregnation. Further, when the amount of turbidity is adjusted by increasing the amount of the catalyst, the storage stability of the prepreg material is deteriorated, and the problem cannot be stored for a long period of time. In order to solve the above problems, this month's people repeatedly tried hard to study the results, and found that the compound represented by the general formula (1) and the epoxy resin reacted to the scaly % oxygen tree in the month before the reaction. The content (% by weight) of the compound represented by the formula (7) is divided by the filling ratio of the gas containing resin obtained by the reaction (the amount of the ruthenium obtained by the reaction is more than 〇.3 _, the hardening reactivity of the epoxy resin) The method for solving the above problems is as follows. The method for manufacturing the phosphorus-containing epoxy resin is characterized in that the method for producing the phosphorus-containing epoxy resin is as follows. In the phosphorus-containing epoxy resin obtained by reacting the compound represented by the formula (1) with an epoxy resin, the content (% by weight) of the compound represented by the formula (2) in the system before the reaction is divided by the reaction. The phosphorus content (% by weight) of the phosphorus-containing epoxy resin is 0.3 or less. Ο (R 1 ) (R2) - (1) (Ο) η - Ρ = 〇I Η 0-( Β - Ο Η

η — Ρ = Ο (2) Ο - (Β)-〇Η In the formula (1) and formula (2), R1 and R2 represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear or branched. Shape, ring. Further, it may be bonded to R2 to form a cyclic structure, and B may be any of benzene, phenyl, naphthalene, anthracene, ruthenium, and 7 200946553. η is 0 or 1. (2) A phosphorus-containing epoxy resin obtained by the method of the above (1), (3) a phosphorus-containing vinyl ester resin using the epoxy resin of the above (2). (4) A composition comprising an epoxy resin comprising the above-mentioned (2) containing a king epoxy resin as an essential component and blending a curing agent. (5) A radical polymerizable resin composition comprising the above-mentioned (3) disc-containing vinyl ester resin as an essential component, and a radical polymerization initiator and/or a curing agent. (6) A material for an electronic circuit board obtained by using the phosphorus-containing epoxy resin composition of the above (4). (7) A sealing material obtained by using the disc-containing epoxy resin composition of the above (4). (8) A casting material obtained by using the phosphorus-containing epoxy resin composition of the above (4). (9) A cured product of the phosphorus-containing epoxy resin composition, the radical polymerizable resin composition, the electronic circuit board material, and the sealing material of any one of the above (4) to (8) The material is hardened. [Embodiment] The epoxy resin containing the epoxy resin of the present invention is obtained by reacting an epoxy resin with a compound represented by the formula (1) to obtain a chemical composition represented by the general formula (2) in the system before the reaction. The ratio (% by weight) divided by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction is 〇3 or less, preferably 〇15 or less, and more preferably 200946553 is 〇·〇5 or less. The compound represented by the general formula (1) and the general formula (2) reacts with the epoxy resin to change its structure, and further contains the phosphonium in the right side, so the general formula in the system before the reaction is previously performed. (2) The content ratio (% by weight) of the compound expressed is divided by the phosphorus content of the phosphorus-containing epoxy resin after the reaction (the weight is represented by the formula (2) contained in the obtained phosphorus-containing epoxy resin) The content ratio of the compound is defined as the content ratio before the reaction, and can be used as an index for controlling the hardening reactivity of the phosphorus-containing epoxy resin. Further, in addition to the cerium-containing phosphorus compound represented by the general formula (1), other In the case of at least one of a phosphorus-containing compound (for example, cyclophenoxyphosphazene), it is also possible to use a compound represented by the formula (2) in advance as a percentage of the total content of the phosphorus-containing compound. It is used as an index for controlling the hardening reactivity of the phosphorus-containing cyclic oxime resin. The compound represented by the formula (1) used in the present invention can be, for example, non-patent document 1, Russian, general, and non-patent document 2 Patent 7. Patent Document 8, Patent Document 9, and Patent Document 10 are obtained. 专利 Patent Document 7, Patent Document 8, and Patent Document 9 describe the compound 'HCA (9,10-II) in relation to benzene. Hydrogen-9-oxy-10-fluorene phenanthrene oxide) The reaction is carried out in a state in which the equivalent amount or more is often present. The reaction solvent is used as a washing solvent after the reaction is described. The purpose is to remove the excess used. Non-Patent Document 1: IGM· Campbell and IDR Stevens, Chemidal Communications, pp. 505-506 (1966) Non-Patent Document 2: (Zh. Obshch. Khim.), 42(ll), pp. 2415-2418 (1972) 200946553

Patent Document 7: Japanese Patent No. BB 寻 特 特 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb bb 01 01 01 01 01 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is manufactured by the method disclosed in 7 to 1G, and the manufacturing cost of the purification means such as washing and recrystallization is increased, and the purity is 99% or more. At this time, the compound represented by the formula (2) is produced in association with other impurities. The reaction is shown in the reaction formula. In the reaction formula i, for example, a compound represented by the formula (1) and a compound represented by the formula (2) are produced, and the compound of the formula (3) represented by the reaction formula 1 remains. Reaction formula !2) — (〇) n—P*s〇 +

I Η (3) (1) 12) - (Ο) η-Ρ = 0 -f i ηο-<β^-οη

(3) CR2) - <〇)

Ο- (Β>-〇Η (2) wherein IU and R2 represent hydrogen or a hydrocarbyl group, and each of the phases is the same or the same, and may be linear, branched or cyclic. Further, R1 may be bonded to R2. A cyclic structure. B represents any one of benzene, biphenyl, naphthalene, phenanthrene, and the like, and η is hydrazine or 1. The present inventors have found that the use of the formula (2) in the form of an impurity component is used. 200946553 The compound represented by the formula (1) shows that the compound represented by the formula (7) has a very small amount of the oxygen-reducing resin, that is, *, and the reaction rate is invented, and the conventional monofunctional benzene is expected to be in the future. = End:,:::: The compound represented by the general formula (1) is purified to be of high purity.

The management of the compound components of the electronic circuit ιγ) can also solve the problems when used in earth plates, sealing materials, casting materials, and the like. The eighth characteristic is that the yield (% by weight) of the compound represented by the formula (2) in the system before the reaction is divided by the phosphorus content (weight ❶/.) of the phosphorus-containing epoxy resin obtained by the reaction. Below 0.3, the resulting disc-containing epoxy resin has little effect on the reactivity with the hardener. That is, the content (% by weight) of the compound represented by the formula (7) is divided by the phosphorus content (% by weight) to obtain

Next, it is preferably (5 or less, more preferably μ or less, and it is desirable to carry out a reaction under 〇〇5 or less to obtain an epoxy resin. The content (% by weight) of the compound represented by the general formula (7) is divided by the phosphorus content. (% by weight) The reactivity of the epoxy resin having a enthalpy of more than 〇3 and the curing agent is remarkably delayed, so that the practicability is poor. The compound represented by the formula (1) used in the present invention can be used by Non-Patent Document 1 ～2, and the methods disclosed in Patent Documents 7 to 10 are produced, and the compound represented by the formula (2) can be reduced by a purification operation such as extraction, washing, recrystallization, distillation, etc. after production. In the above-mentioned methods, the compound represented by the formula (2) is reduced by the reaction conditions of the compound represented by the formula (1). Specific examples of the compound represented by the formula (1) include the structural formula 1. Table 11 200946553 shows HCA-HQ (manufactured by Sanko Co., Ltd. (2,5-di-phenyl)-10-dihydro-9-oxy-10-pyrene-10-oxidation HCA-NQ (10-(2,7-di-p-naphthyl)_ι〇_ dihydrofuryloxyl 〇 鳞 scale represented by Structural Formula 2 Phenanthrene-10-oxide), PPQ (Beixing Chemical Industry Co., Ltd. diphenylphosphinyl hydroquinone), diphenylphosphinyl naphthoquinone, CPHO-HQ (Sakamoto Chemical Industry Co., Ltd. Cyclooctylphosphinyl-14-benzenediol), cyclooctylphosphinyl-1,4-naphthalenediol, phosphorus-containing phenol compound disclosed in JP-A-2002-265562, etc. 2 or more. Structure 1

Structural formula 2

The epoxy resin which reacts with the compound represented by the formula (1) is preferably a glycidyl ether group. For example, Ep〇t〇ht〇YDC-13 12, ZX-1027 (dihydroxybenzene type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), ZX-125 1 (manufactured by Dongdu Chemical Co., Ltd.) Bisphenol ring 200946553 Oxygen resin), Epotohto YD-127, Epotohto YD-128, Epotohto YD-8125, Epotohto YD-825GS, Epotohto YD-011, Epotohto YD-900, Epotohto YD-901 (Dongdu Chemical Co., Ltd.) BPA type epoxy resin), Epotohto YDF-170, Epotohto YDF-8170, Epotohto YDF-870GS, Epotohto YDF-2001 (BPF type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), Epotohto YDP N-638 (East Phenol novolak type bismuth resin manufactured by Huacheng Co., Ltd.), Epotohto YDCN-701 (cresol phenolic phenol lacquer epoxy resin manufactured by Dongdu Chemical Co., Ltd.), ZX-1201 (double made by Dongdu Chemical Co., Ltd.) Phenolphthalein type epoxy resin), NC-3000 (biphenyl aralkyl phenol type epoxy resin manufactured by Sakamoto Chemical Co., Ltd.), EPPN-501H, EPPN-5〇2H (Sakamoto Chemical Co., Ltd.) Multifunctional epoxy resin) ZX-1355 (Dongdu Huacheng Naphthalenediol type epoxy resin manufactured by Co., Ltd.), ESN-155, ESN-1 85 V, ESN-175 (泠-naphthol aralkyl type epoxy resin manufactured by Dongdu Chemical Co., Ltd.), ESN- 355, ESN-375 (Ninadu Chemical Co., Ltd. bisphthol aralkyl epoxy resin), ESN-475V, 9 ESN-485 (Anaphthol aralkyl ring made by Dongdu Chemical Co., Ltd.) Epoxy resin such as phenolic compound such as polyvalent phenol resin and epoxy resin manufactured by epoxidized propane (epiohto ΥΗ-434, Epotohto YH-434GS (diaminobiphenyl manufactured by Dongdu Chemical Co., Ltd.) Ethylene compound such as methyl methane tetraglycidyl ether) and epoxy resin produced by epoxy-propane, YD-171 (dimer acid type epoxy resin manufactured by Tohto Kasei Co., Ltd.) and other carboxylic acids and epoxy teeth An epoxy resin or the like produced by propane is not limited thereto, and two or more kinds thereof may be used in combination. However, it is necessary to divide the content (% by weight) of the compound represented by the formula (2) in the system before the reaction in 2009, and to obtain the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction. The enthalpy is 0.3 or less, preferably 〇·ΐ5 or less, more preferably 〇1 or less, and it is desirable to fill in the form of 0.05 or less. The synthesis method is the same as the reaction of the usual polyfunctional phenols and epoxy resins, and the compound represented by the formula (1) and the epoxy resin are filled and heated and melted to carry out a reaction. In addition, it is necessary to divide the content (% by weight) of the compound represented by the formula (2) in the system before the reaction by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction, and to obtain 〇3. Hereinafter, it is preferably 〇b or less, more preferably 0.1 or less, and is desirably filled in such a manner as 〇.05 or less. The reaction temperature is 1〇〇. (:~200. (:, more preferably i2〇°c~180°C, the reaction is carried out under stirring. When the reaction rate is slow, the catalyst can be used as needed to improve the productivity. Use: a third-grade amine such as benzyldimethylamine, a tetra-ammonium salt such as tetramethyl gasification, a phosphine such as triphenylphosphine or a tris(2,6-dimethoxy-extension) phosphine, Various catalysts such as ethyltriphenyl evolution scale scale salts, imidazoles such as 2-methyl miso 2-ethyl-4-mercaptoimidazole, etc. Further, depending on the viscosity during the reaction, a reaction solvent can also be used. In addition, it is not limited to these, but it is also possible to use two or more types together, and various epoxy resin denaturation agents can also be used together, if necessary. The content of the compound represented by the formula (2) in the system of p-reaction (the weight divided by the phosphorus content of the phosphorus-containing epoxy resin obtained by the reaction (% by weight) β /〇) must be scared. It is preferably 0.3 or less, preferably 0.15 or less, more preferably 0.05 or less, and the denaturing agent is bisphenol a, double-prepared F, and double 200946553. Tetrabutyl double a, hydroquinone, methyl benzene, dimethyl benzene, dibutyl benzene, resorcin, methyl resorcinol, double Phenol, tetramethylbisphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxystilbene, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol Resin, phenol aralkyl resin, naphthol novolac resin, terpene phenol resin, heavy oil modified phenol resin, brominated phenol novolac resin and other phenols, various benzenes and benzophenones, butadiene Polyvalent phenolic resin, aniline, phenylenediamine, toluidine, xylidine, diethyl hydrazine obtained by condensation reaction of various aldehydes such as diphenylglyoxal Phenylenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone, diaminodiphenyl sulfide, diaminodiphenyl sulfide Diaminodiphenyl sulfone, bis(aminophenyl)anthracene Diaminodiethyldimethylmethane, diaminodiphenyl ether, diaminophenylhydrazine, diamine biphenyl, dimethyldiamine biphenyl, biphenyltetramine , bisaminophenyl onion, bisaminophenoxybenzene, bisaminophenoxyphenyl mystery, bisaminophenoxyphenyl, bisaminophenoxybenzene, bisaminobenzene An amine compound such as oxyphenylpropene or diaminonaphthalene. The phosphorus content of the phosphorus-containing epoxy resin used in the present invention is preferably from 0.3 to 4% by weight, more preferably from 0.5 to 3.6% by weight, still more preferably. The content of phosphorus in the organic component of the phosphorus-containing epoxy resin composition containing the phosphorus-containing epoxy resin is preferably from 1.0 to 4% by weight, more preferably from 0.4 to 3.5% by weight, based on 1.0 to 3.1% by weight. More preferably, it is 0.6 to 3% by weight. Organic component in phosphorus-containing epoxy resin composition 15 200946553 ,. When the amount of the right amount is 0.2% by weight or less, it is difficult to ensure flame retardancy, and if it is 5% by weight or more, the heat resistance is adversely affected. Therefore, it is preferably adjusted to 0.2% by weight to 4% by weight. Further, the epoxy equivalent of the phosphorus-containing epoxy resin used in the present invention is preferably 1,500 g/eq', more preferably 25 Å to 1 〇〇〇 g/eq, still more preferably 3 Å. At 200 g/eq, if the adhesion deteriorates by more than 15 〇〇g/eq, the heat resistance may be adversely affected. Therefore, it is preferably adjusted to 200 to 1500 g/eq. The phosphorus-containing epoxy resin composition of the present invention As the hardener, various hardeners for epoxy resins which are generally used, such as phenolic laurels, acid livers, amines, hydrazines, and acid vinegars, can be used, and the hardeners can be used only for the sclerosing agent. Two or more types can be used. The phosphorus-containing epoxy resin composition of the present invention may be blended with a hardening accelerator such as a tertiary amine, a tertiary ammonium salt, a phosphine or an imidazole, as needed. The scaly epoxy resin composition of the present invention can also be used as an adjustment for viscosity by using an organic solvent. Examples of the usable organic solvent include ethers such as guanamines such as N,N-dimethylformamide and ethers such as ethyl ketone monodecyl ether, oximes such as nets and methyl hydrazine, alcohols such as methanol and ethanol, and benzene and hydrazine. An aromatic hydrocarbon such as benzene may be used alone or in combination of two or more kinds, and the epoxy resin concentration may be 30 to 80 parts by weight. / Range of 〇. The filler used in the phosphorus-containing epoxy resin composition of the present invention may, for example, be aluminum arsenide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, finely divided cerium oxide, or fused silica. An inorganic filler such as oxidized, crystalline cerium oxide or silica balloon may be blended with a pigment or the like. Reasons for using a general inorganic filler are, for example, improved impact resistance. 200946553 When using a metal hydroxide such as Hydrazine or Hydrogen, it acts as a flame retardant, and gp #人a can ensure flame retardancy even when the amount of phosphorus is small. Especially if it is equipped. When the amount is not more than 1 〇 /〇, the effect of impact resistance is small. However, if the compounding amount exceeds 150 /. Then, as a necessary item for the use of the laminate, the adhesion will be lowered. Further, the resin composition may contain an organic filler such as cerium oxide, glass fiber, pulp fleur, synthetic fiber, or fibrous H-dimensional filler, microparticle rubber or thermoplastic elastomer. The material for the electronic circuit board obtained by the above-mentioned phosphorus-containing epoxy resin composition may be a resin sheet, a resin-attached metal case, a prepreg or a laminate. The method for producing the resin sheet is not particularly limited. For example, a carrier film which is not dissolved in the epoxy resin composition such as a polyester film or a polyamide film, and the above-mentioned phosphorus-containing epoxy resin composition is preferably 5~ After the thickness of 1 〇〇〆m, it is heated and dried at 100 to 200 ° C for 1 to 40 minutes to form a sheet. The resin sheet is generally formed by a method called casting. At this time, if the sheet coated with the phosphorus-containing epoxy resin composition is subjected to surface treatment with a release agent in advance, the resin sheet formed into the φ type can be easily peeled off. Here, the thickness of the resin sheet is preferably set to 5 to 80 / X m °. Next, the resin-attached metal foil obtained by using the above phosphorus-containing epoxy resin composition will be described. As the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used. It is preferable to use a metal foil having a thickness of 9 to 7 μm. The method of producing a resin-attached metal foil from a flame-retardant resin composition containing a phosphorus-containing epoxy resin and a metal foil is not particularly limited, and for example, coating the surface of the metal foil with a roll coater After the resin varnish having the viscosity-adjusted viscosity of the phosphorus epoxy resin composition, the resin is subjected to heat drying to semi-harden (B-stage) the fat component of the tree 17 200946553 to form a resin layer. When the resin component is semi-hardened, for example, it may be heated at 100 to 20 (rc heating 丨~仂 minutes. Here, the thickness of the resin portion of the metal pig to which the resin is attached is preferably 5 to 110. Next, (4) using the above A prepreg obtained by a scaly epoxy resin composition. The sheet-like substrate may be an inorganic material such as glass, a polyester, or the like, a polyamine, a polyacrylamide, a polyimine, or a Kevlar fiber. The woven fabric or the non-woven fabric of the fiber is not limited thereto. The method for producing the prepreg from the epoxy resin composition and the substrate is not particularly limited, and for example, the substrate is impregnated and impregnated into the ring. After the oxygen resin composition is subjected to a resin varnish whose viscosity has been adjusted by a solvent, it is heated (4). The resin component is semi-cured (B-staged), for example, it can be dried for 1 to 4 minutes. Here, the amount of the resin in the prepreg is preferably from 3 to 8 % by weight based on the resin component. Next, a resin sheet, a metal case with a resin, a prepreg or the like may be used to produce a laminate. Method In the case of prepreg to form a laminate, one or several sheets of prepreg are laminated, and metal pigs are arranged on one side or both sides to form a laminate, and the laminate is heated and pressurized to be laminated. Here, the metal box can be made of copper, aluminum, brass, nickel, etc. alone, alloy, composite metal. The condition of heating and pressurizing the laminate can be 'under the condition that the epoxy resin composition will harden. If the pressure is relatively low, the pressure is likely to remain in the interior of the obtained laminate. The electrical characteristics may be lowered. Therefore, it is preferable to pressurize under the condition that the formability is satisfied. The set temperature is 16〇~2赃, the pressure 18 200946553 is 49.0~490.3N/cm2 (5~50kgf/cm2), and the heating and pressing time is 4〇~24〇 minutes. The single-layer laminated board thus obtained can be further used as The inner layer is made of a multi-layered board. In this case, first, the laminated board is subjected to circuit formation by an addiction method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution to impart blackening. Processing 'acquired a layer. The circuit forming surface on one side or both sides of the inner layer is formed of a resin sheet, a resin-attached metal V#, or a prepreg to form an insulating layer ' while forming a β conductor layer on the surface of the insulating layer to form a layer. In the case of forming an insulating layer from a resin sheet, a resin sheet is disposed on a circuit forming surface of a plurality of inner sheets to form a laminate. Alternatively, a resin sheet is disposed between the circuit forming surface of the inner layer and the metal foil to form a laminate. The laminate is then heated and pressurized to form a body of the resin sheet, thereby forming a cured product of the resin sheet as an insulating layer, and at the same time forming a multilayer of the inner layer material, or an inner layer material and a layer as a guide layer. The cured product of the resin sheet is formed as an insulating layer between the metal foils. Here, the metal case can be the same as that used for the laminated board used as the inner layer. And heating and shaping can be carried out under the same conditions as the formation of the inner layer. When the resin is coated on the laminate to form an insulating layer, the epoxy resin composition containing the composition or the flame retardant epoxy resin composition containing the epoxy resin containing phosphorus is applied to preferably 5 The thickness of the ~100 em is used as the outermost layer of the inner layer material to form the surface resin'. Then, it is dried by heating for 1 to 90 minutes to form a sheet. It is generally formed by a method called casting. The thickness after drying is preferably formed to be 5 to 80/zm. Through-hole formation and circuit formation may be applied to the surface of the multilayered laminate thus formed by addition and subtraction to form a printed wiring board. 19 200946553 Further, by repeating the above-described method by using this printed wiring board as an inner layer material, a multilayered multilayer board can be further formed. In the case where the insulating layer is formed of a metal foil with a resin, the metal foil with the resin is placed on the inner layer so that the resin layer of the metal foil with the resin and the circuit forming surface of the inner layer are opposed to each other. The circuit forms a face' to form a laminate. Then, the laminate is formed by heat and pressure, and a cured product of a resin layer of a resin-attached metal foil is formed as an insulating layer' while forming a metal foil on the outer side thereof as a conductor layer. Here, the heat press molding can be carried out under the same conditions as the formation of the inner layer. In the case where the insulating layer is formed of a prepreg, the prepreg ® sheet or a plurality of layers are placed on the circuit forming surface of the inner layer, and the metal foil is placed on the outer side to form a laminate. Then, the laminate is heated and pressed into a single body to form a cured product of the prepreg as an insulating layer, and a metal foil on the outer side thereof is formed as a conductor layer. Here, the metal foil can be used in the same manner as the user who uses the laminate as the inner layer. Further, the heat and pressure forming can be carried out under the same conditions as the formation of the inner layer. A through-hole formation and circuit formation may be applied to the surface of the multilayered laminate thus formed by an additive method, a subtractive method, and a printed wiring board. Further, by repeating the above-described method by using the printed wiring board as an inner layer material, a plurality of layers of the multilayer board can be formed. As a result of evaluating the properties of the laminate obtained by using the phosphorus-containing epoxy resin of the present invention and the composition, the content of the compound represented by the formula (2) was 5.5% by weight. The dish-containing epoxy resin obtained by reacting the compound represented by the following formula (1) with an epoxy resin is highly reactive with a curing agent; and the prepreg having a good balance between fluidity and hardenability of the resin during curing. 20 200946553 The laminate obtained by heat-hardening the prepreg is a resin composition which does not contain a sinter compound and has flame retardancy and is excellent in solder heat resistance. EXAMPLES The present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. The content of the compound represented by the formula (2) contained in the compound represented by the formula (1) is measured by HPLC. A device of Agilentl 10 〇series made by Hewlett • Packerd was used, and a column of CD006 of Cadenza CD-C1 8 made by Imtakt was used. The eluate was measured using water and methanol' starting with 60% sterol and gradient to sterol 100% at 16 minutes. The flow rate was set to 0 5 ml/min, and the measurement was carried out at a wavelength of 266 nm using a uv detector. Also 'flame retardance is based on uL (Underwriter

Laboratories) specifications were measured. The varnish gel time was measured at 16 °c. The copper foil peeling strength was measured in accordance with JIS C 648 1 5·7, and the interlayer adhesion force was measured by Q peeling between the prepreg i sheet and the remaining three sheets in accordance with JIS C 6481 5.7. The solder heat resistance was carried out at 280 ° C according to JIS C 6481 5.5, and the presence or absence of swelling or peeling was visually observed, and those without swelling or peeling were referred to as 〇, and others were designated as X. Further, the glass transition temperature and the hardening calorific value of the cured product were measured by Exster 6000 manufactured by Seiko Instruments Co., Ltd. The hardening heat retention rate is stored at 60 when the total hardening heat of the prepreg immediately after the finishing is set to 100 ° / ❶. (: The total hardening heat of the prepreg after 72 hours is obtained as a percentage, so the smaller the number, the worse the storage stability. (Structure confirmation of the compound represented by the general formula (2)) For the compound, the HPLC of 21 200946553 HCA-HQ represented by Structural Formula 1 is determined, and the delayed component of the hardening reaction is taken.

The measurement was carried out by FD-MASS, FTIR, and proton NMR. By MASS

As a result of the measurement, it was found that the molecular weight was 324, and the result of FTIR was compared with hCA-HQ. It was confirmed that the phenolic hydroxyl group was decreased, the benzene trisubstituted product was decreased, and the benzene disubstituted product was increased. From the results of proton NMR, it was confirmed that HC A was bonded to the hydroxyl group derived from benzophenone at the p site. From the above, it was confirmed that the peak value of 13.6 minutes was the structural formula 3. In the case of the compound of the formula (1), 1〇_(2,7·di-based zeoyl)dihydro-9-oxy-10-linofan-1〇-oxide is also subjected to the same eight It is fine to the composition of Structure 4. $ % structured structure 4 〇

〇Η Synthesis Example 1 In a detachable flask equipped with a stirring device, a thermometer, a cooling slab, or a mouth glass, the compound shown in 4 mi) as an introduction device was filled in. 200946553 HCA HQ 31.72 parts by weight, YDF l7〇 68 28 parts by weight, heated to 12 Gt in an atmosphere. Triphenylphosphine (3) as a catalyst was added to react for 4 hours. The purity of the compound represented by the formula (1) was 99.5% by weight. The compound represented by the formula (7) contained in the reaction system is specifically that the content of the compound represented by the structural formula 3 is 0 〇〇 3 by weight 2, and the epoxy equivalent of the epoxy resin is 3.0% by weight. ❹ ❹ Synthesis Example 2 Except for the compound HC1A HQ represented by the formula (1), which is a compound represented by the formula (2), specifically, 17% by weight of the compound represented by the formula 3, Example i the same operation. The purity of the compound represented by the formula is ...% by weight. The amount of the compound represented by the reaction system is 4845 by weight, and the amount of the epoxy compound is 484.lg/eq, and the filling ratio is 3% by weight. Synthesis Example 3 In addition to the use of the compound represented by the formula (2), specifically, the compound represented by the formula 3, 33% by weight of the compound represented by the formula (1), HCA-HQ i the same operation. The compound represented by the formula has a purity of 991% by weight. The compound represented by the general formula (2) contained in the reaction system contains the main ingredient. / is 〇·10% by weight. The epoxy of the obtained epoxy tree was 958.4 g/eq, and the phosphorus content was 3 〇% by weight. Synthesis Example 4 Except that the compound represented by the formula (7) is used, specifically, the compound represented by the formula (3) represented by the formula 3, G.65% by weight, represented by the formula (1), the compound 23, 200946553, HCA-HQ, is carried out. The same operation as in Synthesis Example i. The compound represented by the formula has a purity of 98% by weight. The content of the compound represented by the formula (2) contained in the reaction system was 〇21% by weight. The epoxy equivalent of the obtained epoxy resin was 488.3 g/eq, and the lining rate was 3.0% by weight. Synthesis Example 5 In addition to the compound HCA-HQ represented by the formula (1), which is a compound represented by the formula (2), specifically, 95% by weight of the compound represented by the structural formula 3, The same operation as in Synthesis Example i. The purity of the compound represented by the formula was 98.2% by weight. The content of the compound represented by the formula (2) contained in the reaction system is 〇 3 〇 by weight. The epoxy equivalent of the epoxy resin obtained by the method was 487.7 g/eq', and the disc content was 3.0% by weight. Synthesis Example 6 In addition to the compound represented by the formula (2), specifically, the formula 3 was used. The same procedure as in the synthesis example i was carried out except for the compound HCA-HQ represented by the formula of 12% by weight of the compound. The purity of the compound represented by the formula was 97.9% by weight. The reaction system contained the wanted The epoxy resin equivalent weight of the epoxy resin obtained by the compound represented by the formula (2) was 486.3 g/eq, and the phosphorus content was 3.0% by weight. Synthesis Example 7 The same apparatus as in Synthesis Example 1 was used. 15 parts by weight of HCA 杳 21 and 50 parts by weight of toluene were heated to 75 lt. t under nitrogen atmosphere, and dissolved therein. In this case, a small amount of parabenz〇qUin〇ne was filled in minutes. 10.47 parts by weight, the temperature was raised at 85 t for 3 minutes, and the reaction was carried out for 3 hours at a reflux temperature. The compound represented by the formula (2) contained in the compound HCA-HQ of 24 200946553, represented by the formula, was specifically That is, the content of the compound represented by Structural Formula 3 is 2.40% by weight / ^ Further, the purity of the compound represented by the formula (1) is 95% by weight, and 68.39 parts by weight of YDF_17〇 is filled therein, and the mixture is heated to remove the toluene. The reaction system contains the formula (2). The content of the compound expressed is 〇.76 weight

%° added triphenylsulfone (0.32 parts by weight) at 160 ° C

Reaction for 4 hours. The epoxy resin obtained had an epoxy equivalent of 470.2 g/eq and a lining rate of 3.0% by weight. Synthesis Example 8 In the same apparatus as in Synthesis Example 1, 3.09 parts by weight of the compound represented by the formula (2) HCA-HQ was filled in (the compound represented by the formula (2) is specifically represented by the structural formula 3 The content of the compound was 〇〇1% by weight, 〇63 parts by weight of HCA, and 68.28 parts by weight of YDF_17〇, and the same operation as in Synthesis Example 1 was carried out. The purity of the compound represented by the formula (1) is 97 to 3% by weight based on the total of the HCA and HC AHQ to be filled. The content of the compound represented by the formula (2) contained in the reaction system is 〇〇〇3 wt% " The epoxy equivalent of the oxime tree is 480.3 g/eq, and the disc content is 3 〇 weight 〇/ Hey. Synthesis Example 9 A compound represented by the formula (1) in which the content of the compound represented by the formula (2) (specifically, the compound represented by the structural formula 4) was 〇15% by weight, using 26.86 parts by weight. The same operation as in Synthesis Example 1 was carried out except that 73.14 parts by weight of YDF_817G was used as the compound represented by Structural Formula 2. The compound represented by the formula (1) has a purity of 9 〇·1% by weight. The content of the compound represented by the formula (2) contained in the reaction system of 25 200946553 was 0.04% by weight. The epoxy resin obtained had an epoxy equivalent of 321.8 g/eq and a phosphorus content of 2.2% by weight. Synthesis Example 10 Except for the compound HCA-HQ represented by the formula (1), which is a compound represented by the formula (2), specifically, 3.10% by weight of the compound represented by the formula 3, Example 1 is the same operation. The purity of the compound represented by the formula (1) was 93.0% by weight. The content of the compound represented by the general formula (2) contained in the reaction system was 0.98% by weight. The obtained resin had an epoxy equivalent of 471.1 g/eq and a phosphorus content of 3.0% by weight. ® Synthesis Example 11 Into the same apparatus as in Synthesis Example 1, 21.15 parts by weight of HCA and 4 parts by weight of toluene were charged, and the mixture was heated to 75 ° C under a nitrogen atmosphere, and dissolved. 69.13 parts by weight of YDF-170 was filled in and dissolved, and 9.73 parts by weight of p-benzoquinone was added in small portions every 2 hours. After the end of the addition, the benzene was further removed after the reflux temperature was maintained for 3 hours, and 32 parts by weight of hydrazine was added and reacted at 160 for 4 hours. The content of the compound represented by the formula (2) contained in the compound represented by the formula (1) HCA-HQ is 35 wt%. The purity of the compound represented by the formula (1) was 69.4% by weight. The content of the compound represented by the formula (2) contained in the reaction system is 1 8% by weight. The epoxy resin obtained had an epoxy equivalent of 444.4 g/eq and a phosphorus content of 3 〇 by weight. Synthesis Example 1 2 In addition to the compound represented by the formula (2), specifically, the compound represented by the formula 4, 26% by weight of the compound represented by the formula (1), the compound 26 200946553, specifically, the structural formula The procedure other than the compound represented by 2 was carried out in the same manner as in Synthesis Example 9. The purity of the compound represented by the formula (1) was 77.0% by weight. The content of the compound represented by the formula (2) contained in the reaction system was 〇·7 〇% by weight. The obtained epoxy resin had an epoxy equivalent of 321.4 g/eq and a disk content of 2.2% by weight. According to the formulation shown in Tables 1 and 2, an epoxy resin, a dicyandiamide hardener, an imidazole hardening accelerator obtained in each synthesis example, and dissolved in a solvent were used for evaluation of a laminate. The results of Examples 1 to 9 and Comparative Examples 1 to 3 were summarized in Tables 1 and 2. According to the compounding position shown in Table 3, the phenol novolac resin hardener, the imidazole hardening accelerator, and the 'gluten solution in the solvent' were evaluated for reactivity according to the gel time. The results of Examples 10 to 12 and Comparative Example 4 are summarized in the table; in Table 4, the storage ampoules evaluation system in the case where the catalyst amount is adjusted to the same degree in Example 13 and Comparative Example 5 is used. Finished into a hardening heat retention rate.

27 200946553 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Resin Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Type of Compound of Formula 1 HCA-HQ HCA- HQ HCA-HQ HCA-HQ HCA-HQ Compound of formula 1 parts by weight 31.72 31.72 31.72 31.72 31.72 Purity of compound of formula 1 wt% 99.5 99.4 99.1 98.7 98.2 YDF-170 parts by weight 68.28 68.28 68.28 68.28 68.28 In the reaction system Proportion by weight of the compound of the formula 2: 0.003 0.05 0.10 0.21 0.30 Ratio of the compound of the formula 2 contained in the reaction system (% by weight) divided by the phosphorus content (% by weight) - 0.001 0.02 0.03 0.07 0.10 Epoxy equivalent g /eq 480.0 484.1 488.4 488.3 487.7 Phosphorus content Weight % 3 3 3 3 3 Epoxy resin parts obtained by synthesis Example 100.0 100.0 100.0 100.0 100.0 DICY Parts by weight 2.19 2.17 2.15 2.15 2.15 2E4MZ Parts by weight 0.05 0.05 0.05 0.05 0.05 Varnish gel time Second 458 453 556 625 716 Glass Transfer Temperature (TMA) "C 117.8 115.7 116.0 114.7 113.8 Copper foil peel strength kgf^cm 1.98 1.94 1.85 1.81 1.75 Interlayer Then force kg^cm 2.43 2.31 2.61 2.69 2.25 Soldering heat resistance Appearance 〇〇〇〇〇 Flame retardancy UL-94 V-0 V-0 V-0 V-0 V-0 Example 6 Example 7 Example 8 Comparison Example 1 Comparative Example 2 Resin Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 10 Synthesis Example 11 Kind of Compound of Formula 1 HCA-HQ HCA-HQ HCA-HQ HCA-HQ HCA-HQ Formula 1 Compound parts by weight 31.72 31.62* 31.09 31.72 30.88* Purity of compound of formula 1 wt% 97.9 95.0 97.3 93.0 69.4 YDF-170 parts by weight 68.28 68.39 68.28 68.28 69.13 proportion by weight of compound of formula 2 contained in the reaction system 0.38 0.76 0.003 0.98 1.08 Ratio of the compound of the formula 2 contained in the reaction system (% by weight) divided by the phosphorus content (% by weight) - 0.13 0.25 0.001 0.33 0.36 Epoxy equivalent g/eq 486.3 470.2 480.3 471.1 444.4 Phosphorus content Weight % 3 3 3 3 3 Epoxy resin parts obtained by the synthesis example 100.00 100.00 100.00 100.00 100.00 DICY parts by weight 2.16 2.23 2.19 2.23 2.37 2E4MZ parts by weight 0.50 0.50 0.50 0.50 0.50 varnish gel time seconds 802 891 540 1160 1520 glass Transfer temperature (TMA) °C 105.5 103.8 111.2 101.3 99.2 Copper foil peel strength kgf7cm 1.86 1.82 1.72 1.61 1.54 Interlayer adhesion force kgf/cm 2.14 2.59 2.03 2.02 1.77 Soldering heat resistance appearance 〇〇〇 XX Flame retardant UL-94 V-0 V-0 V-0 ν·ο V-0

Amine two-volume FCA heavy diazole meter Mimi system company limited company weight limit 醗 shares benzene shares on de shares and bi components carization volume national weight this four A day Z c YM HC4 IE *D2I 28 200946553 Table 2 Example 9 Comparative Example 3 Resin Synthetic Example 9 Synthetic Example 12 Species of the compound of Formula 1 HCA-NQ HCA-NQ Compound of Formula 1 Part by weight 26.86 26.86 Compound of Formula 1 Purity wt% 90.1 77 YDF-8170 parts by weight 73.14 73.14 Proportion by weight of the compound of the formula 2 contained in the reaction system % by weight 0.04 0.70 The proportion (% by weight) of the compound of the formula 2 contained in the reaction system divided by the scale content ( % by weight 0.02 0.32 Epoxy equivalent g/eq 321.8 321.4 Phosphorus content Weight % 2.2 2.2 Epoxy resin parts obtained by synthesis Example 100.00 ιαο.οο DICY Parts by weight 3.26 3.27 2E4MZ Parts by weight 0.5 0.5 Varnish gel time seconds 345 907 Glass Transfer temperature (TMA) °C 120.2 107.9 Copper foil peel strength kgf/cm 1.66 1.44 Interlayer adhesion kgj^cm 1.85 1.61 Soldering heat resistance appearance 〇X Flame retardant UL-94 V-0 V-0 O DICY Japan carbi Made from dextran diamine 2E4MZ manufactured by Teko Co., Ltd. _ mouth catalyst 29 200946553 Table 3 Example 10 Example 11 Example 12 Comparative Example 4 Resin Synthesis Example 1 Synthesis Example 4 Synthesis Example 8 Synthesis Example 10 Kind of Compound of Formula 1 HCA-HQ HCA-HQ HCA-HQ HCA-HQ Compound of Formula 1 Parts by Weight 31.72 31.72 31.72 31.72 Purity of Compound of Formula 1 Weight % 99.5 98.7 97.3 93.0 YDF -170 parts by weight 68.28 68.28 68.28 68.28 Proportion by weight of the compound of the formula 2 contained in the reaction system % by weight 0.003 0.21 0.003 0.98 Ratio (% by weight) of the compound of the formula 2 contained in the reaction system divided by the phosphorus content (% by weight ) - 0.001 0.07 0.001 0.33 Epoxy equivalent g/eq 480.0 488.3 480.3 471.1 Broken content% by weight 3 3 3 3 Epoxy resin parts obtained by the synthesis example 100.00 100.00 100.00 100.00 BRG-557 parts by weight 21.67 21.30 21.65 22.08 2E4MZ parts by weight 0.10 0.10 0.10 0.10 varnish gel time seconds 311 528 368 945 DICY Japan Carbide Co., Ltd. dinoniamine 2E4MZ Shikoku 彳b into a company limited by Imidazole Catalyst 30 200946553 Table 4 Example 13 Comparative Example 5 Resin Synthetic Example 1 Synthetic Example 10 Type of Compound of Formula 1 HCA-HQ HCA-HQ Compound of Formula 1 Part by Weight 31.72 31.72 Formula 1 Purity of the compound Weight % 99.5 93.0 YDF-170 Parts by weight 68.28 68.28 Proportion by weight of the compound of the formula 2 contained in the reaction system % by weight 0.003 0.98 Ratio (% by weight) of the compound of the formula 2 contained in the reaction system divided by phosphorus Rate (% by weight) - 0.001 0.33 Epoxy equivalent g/eq 480.0 471.1 Filling content % by weight 3 3 Epoxy resin parts obtained by the synthesis Example 100.00 100.00 DICY Parts by weight 2.19 2.23 BRG-557 Parts by weight 0.00 0.00 2E4MZ Parts by weight 0.50 1.20 Varnish gel time 458 471 Hardening heat retention rate 70.8 51.1 DICY Japan Carbide Co., Ltd. dicyandiamide 2E4MZ Siguo Chemical Co., Ltd. The imidazole catalyst is described in Tables 1, 2, and 3. It is understood that when the content of the compound represented by the formula (2) is increased, the gel time is remarkably slowed, which affects the curing reactivity. Tables 1 and 2 are evaluated by dicyandiamide hardener, and in Table 3, although it is evaluated by a phenol novolak resin hardener, it is carried out by any hardener, and the compound represented by the formula (2) When the content rate is high, the gel time is remarkably slowed, so that it affects regardless of the type of the hardener. For example, in the case of a laminate, the adhesion of the adhesive is reduced due to insufficient resin component, and the occurrence of migration and the occurrence of defects such as expansion and cracking during the weld impregnation. In addition, since the gel time is adjusted to Table 4, when the amount of the curing catalyst is added, the compensatory ratio of the hardened hair strand becomes small, and the female M sighs, and the prepreg is preserved during the warranty period. The storage stability is deteriorated and cannot be long (industrial use). The present invention is used in a system before the reaction by using an epoxy resin obtained by reacting a compound represented by the general formula (1) with an epoxy or a lipid. (2) The content of the compound (% by weight) of the compound represented by the oxime reaction is obtained by the reaction rate (% by weight) of the epoxy resin obtained by the reaction. It is possible to provide a filled epoxy resin and an electronic circuit board material which are excellent in storage stability of the prepreg, which does not delay the gel time, and which has the same force, migration resistance, and solder dipping resistance. ο [Main component symbol description] No 32

Claims (1)

200946553 VII. Patent Application Range·· 1. A method for producing a phosphorus-containing epoxy resin, which is used for producing a phosphorus-containing epoxy resin obtained by reacting a compound represented by the general formula (1) with an epoxy resin, and characterized by The content (% by weight) of the compound represented by the formula (2) in the system before the reaction is divided by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction, and the enthalpy is 0.3 or less: (R) 1) (R2) - (ο) n_p = 〇(1) I Η Ο—(B-hO Η (R 1 ) iR2) - (〇) n_p = 〇(2) I O- (BJ-OH formula (1) and formula ( 2), R1, R2 represents hydrogen or a hydrocarbon group, and each may be different or the same, may be linear, branched, or cyclic; or R1^ bond to form a cyclic structure; B represents benzene, Benzene naphthalene, fluorene, and any of the hydrocarbon substitutes; η is 〇 or i. 2. A phosphorus-containing epoxy resin obtained by the method of claim i. A phosphorus-containing ethyl ester resin using a phosphorus-containing epoxy resin having a patent application scope of 2. 2. A phosphorus-containing epoxy resin composition, which is based on the patent application scope 2 The phosphorus-containing epoxy resin is an essential component and is compounded with a hardener. 5. A radical polymerizable resin composition which is required to apply the phosphorus-containing vinyl ester resin of the third application of the patent. The composition is blended with a radical polymerization initiator and/or a hardener. 33 200946553 6. A material for an electronic circuit board, which is obtained by using a phosphorus-containing epoxy resin composition of the fourth aspect of the patent. 7. - A kind of sealing material, which is obtained from the material containing the epoxy resin composition in the scope of the patent. 8. - A kind of wound casting material, which uses the phosphorus-containing epoxy of the fourth application patent scope The resin composition is obtained by the use of the phosphorus-containing epoxy resin composition, the radically polymerizable resin composition, the electronic circuit board material, and the material of the electronic circuit board according to any one of claims 4 to 8. The sealing material and the casting material are hardened. VIII. Schema: None 34