TW201122050A - Phosphor-containing epoxy resin, resin composition, and flame retardant hardened article thereof - Google Patents

Abstract

This invention provides a flame retardant, phosphor-containing epoxy resin. It is: a phosphor-containing epoxy resin (D) which obtained by reacting: a phosphor-containing epoxy resin (B) which contains a bisphenol F type epoxy resin (A) as a necessary component, and a phosphor-containing compound (C); wherein the bisphenol F type epoxy resin (A) is represented by general formula (4) wherein n is an intega of 0 or larger, and an oxygen atom bonded with an aromatic ring is bonded at an ort position or a para position when viewed from a methylene group; the phosphor-containing compound (C) is represented by general formula (5) wherein R1, R2 are a hydrocarbon group and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphor atom; R1, R2 may be boned to form a cyclic construction. Y is hydrogen or a functional group having an aromatic ring which has a hydroxyl group; and the bisphenol F type epoxy resin contains such components that are represented by general formula (1), (2), and (3) wherein the compound represented by general formula (1) is contained in the ratio of 0 area% or more to 10 area% or less on a high speed liquid chromatography with respect to the sum of content of the compound represented general formula (1), the content of the compound represented by general formula (2), and the content of the compound represented by general formula (3);

Description

201122050 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an epoxy resin composition and a cured product which are applied to an electronic material. _ Ring and Oxygen Resin, [Prior Art] Epoxy resin is widely used in electronic parts and electric machines because of its adhesion, heat resistance, and molding for use in electronic parts, electric machines, automotive parts, and Fr. Educational supplies, etc. The material is based on the fire (four) prevention, delay, etc., and the safety of the board or the seal is determined to have flame retardancy. In the past, it has been necessary to use these two points. In the epoxy resin, by introducing __ oxy-resin / stinky lye resin is positioned as a useful electronic, electric = however, the recent electronic machine is examined, but the trend of =:::r is found. In view of the recent tendency to reduce the weight of the two substances, it will cause _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ When burning, it will be regarded as a problem. In the case of the whole environment, the use of money, in the vicinity of the substitute materials containing the self-suppressing flame retardant, there are many materials for hydrogen and oxygen, inorganic materials, Research on the synthesis of conjugates, i compounds, etc., in which sputum has been studied in recent years. The use of flame-retardant formulations containing fillers has been disclosed to increase the amount of 6 322427 201122050 plus phosphates in the flame-retardant compound containing % oxygen resin. Red phosphorus and other methods 'but the phosphate ester - 9 ^ from the hydrolysis of the anti-reservoir, and red, mixed high-temperature and high-humidity atmosphere will produce phosphoric acid and affect: secret, so there is a long-term reliability of the body. ^ : Non-exclusive, non-patent read 2 and patent i, 9 〇-dihydro _9_oxa-1 〇 鳞 phenanthrene HC ^; f 10--^ ^ ; 2 10 W heterogeneous 1 )) _ oxide (hereinafter referred to as HCA_HQ) It has a flame retardant epoxy which does not wait for a compound even if it is filled with an acid in a humid atmosphere, and the result is disclosed in Patent Document 2, Patent Document 3, and as an epoxy resin. In the field of application, the electronic inventors may use oxy-resin for the use of electronic materials; == improve the heat resistance and improve the flame-retardant heart while maintaining the bonding force! In addition, the multi-functional epoxy is formulated. Resin door, and again, although high heat resistance can be obtained, the cured product will change the strength of the bond significantly. The (4) π ^ 跪 跪 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于=: 裱 树脂 作为 作为 2002 2002 2002 2002 裱 2002 2002 2002 2002 2002 2002 2002 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 Japanese Patent Laid-Open No. Hei. No. 2003-040969 Patent Document 5: JP-A-2007 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2007-308642, Non-Patent Document 1: IGM Campbell and IDR Stevens,

Chemical Communications, pp. 505-506 (1966) Non-Patent Document 2: Zh. Obshch Khim, 42(11), pp. 2415-2418 (1972) 'Explanation of the Invention Provides a kind of flame retardant BPF epoxy resin hardened

The material is composed of a phosphorus-containing B p F type epoxy resin using a widely used epoxy resin (B P F type epoxy resin), and the heat resistance can be improved while maintaining the adhesion. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have explored a two-shot type epoxy resin (hereinafter referred to as a foot type epoxy resin) as a representative epoxy resin, and I: Bifunctional and n = 特别 特别 特别 特别 特别 特别 特别 特别 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The compound of ° (hereinafter referred to as 〇, 〇, _BFDGE) has a low content of epoxide 322427 8 201122050 resin obtained by reacting with a structural compound, and further provides the above-mentioned filled epoxy resin as an essential component and hardening The resin composition composed of the agent and the flame-retardant resin cured product obtained by curing the resin composition can solve the problem. In other words, the present invention focuses on a phosphorus-containing ring in (10) epoxy resin (8) (which contains The formula (4) =) the double-particulate resin (A) as an essential component) and the compound-containing compound (c) (having the structure of Tongyutong-^), the above-mentioned two-shot type resin (1), the formula (1) .--Double-shot diepoxide called (called =_), 〇 shown in the general formula (2), p' - double F epoxifen propylene side (8), general formula (3) P, P, 'double shot diepoxide bis BFDGE), and The content of the formula (1) is in the form of a high-speed liquid chromatogram, and the content of the bismuth, the bismuth, and the _BFD (8) are compared with the above-mentioned three kinds of double shots. Thin face

(1)

322427 9 201122050

η is an integer above 〇. And the oxygen atom attached to the aromatic ring is attached to the ortho or para position of the fluorene group.

m is any number from 0 or 1.

Ri, R2 represents a sulfhydryl group which may also contain an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. True Rl and 匕 can also be connected in a ring structure. Y represents hydrogen or a functional group having an aromatic ring containing a radical. Further, in the case of the ketone-containing oxy-resin (D), the content of the bis-F-type epoxy resin (A) represented by the formula (4) is relatively high as compared with the bisphenol F-type epoxy resin (A). The sum of the epoxy resin (B) and the phosphorus-containing compound (C) is preferably 20% by weight or more and 85% by weight or less, and the filling ratio is preferably 5% by weight or more and 5% by weight or less. Further, another focus of the present invention resides in a resin composition comprising the above-described scaly epoxy resin (D) as an essential component and a compound comprising a curing agent, and a flame-retardant resin cured product. The resin composition is formed by hardening. 10 322427 201122050 Effects of the Invention • The inventors of the present invention conducted an effort to study the results of the method of cutting rails (IV), and found that: 含, 〇-BFDGE has a low content of epoxy resin and reacts with the compound to form a phosphorus ring. Oxygen resin has no crystallinity and has a lower melt viscosity than a disk-containing oxygen resin prepared by using a BPF type epoxy resin having a high content of 0'0-BFDGE, and can be used as a flame retardant in electronic materials. Epoxy resin has excellent performance; in addition, scaly epoxy resin is an essential component. Langqihua _ 〗 〖Architecture tree has excellent hardening reactivity; and its hardened material has excellent heat resistance. Know the effect of the riser and flame retardancy. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. A BpF plastic epoxy resin, which is one of the representative epoxy resins, is obtained by reacting bisphenol F (abbreviated as BPF) as a raw material and using epidentol with an alkali metal hydroxide or the like, and is characterized by a phase Compared with bisphenol A type epoxy resin, it is a low viscosity liquid resin. The bpf of the raw material of the BPF type epoxy resin is obtained by dehydration condensation reaction of phenol and formaldehyde in the presence of an acid catalyst. Since the reaction has the orientation of the ortho-para position, it is known to have two benzene nuclei. 2, 2,2'-dihydroxydiphenylmethane (hereinafter referred to as 〇, 〇, _BpF), 2 4, _ dihydroxy- phenyl methane (hereinafter referred to as 〇, p'-BPF), 4, Three types of BPF of 4'-dihydroxydiphenylmethane (hereinafter referred to as p,p'-BPF). Further, the produced BPF reacts with unreacted formaldehyde and phenol to form a compound having a number of nucleus or more. With the O 11 322427 201122050 ear ratio or the type of catalyst and other reaction conditions at the time of the reaction, it is possible to obtain a distribution of the T 曰-NI* which is required by the chamber, and the phenol which is not used for the reaction can be distilled. Recycling and use. Among them, the content of the 2 nucleus (ie, dihydroxydiphenylmethane) is about 2% or more, and is sold as BPF. It can be purchased from Mitsui Chemicals Co., Ltd. = Company, Honshu Chemical Industry Co., Ltd., etc. In addition, by the B = sold BPF, it is possible to obtain a component having a size of 3 or more cores as much as possible to be approximated to 〇 by weight. There has been a lot of knowledge about a method for increasing the productivity without increasing the polymer of the three-core or more. For example, Patent Document 6 discloses that the liquid-liquid heterogeneous reaction can be suppressed by using a disc acid aqueous solution as a catalyst under specific conditions. A reaction for producing a polymer having a triple core or more.

The ratio of 〇B, _BPF to 〇p, _BpF included in BPF will have a large impact on the type of catalyst used. When the reaction of the ortho position is significantly slower than the reaction of the para position, the reaction of the para position is selectively performed, and the phenolic resin of the above 3 nucleus is not easily formed, and the molar ratio of the desired/formic acid can be reduced. In other words, since the amount of added phenol can be reduced, the energy cost required for heating or cooling, distillation after the reaction to recover phenol is reduced, and in terms of the amount of formaldehyde per batch, the yield is increased due to an increase in the amount of formaldehyde. , significantly improve productivity. In addition, when a catalyst having a high selectivity of p,p'-BPF is used, a by-product such as ruthenium, osmium or -BPF may be mixed in an amount of about 1% by weight, but by a method such as distillation or recrystallization, p can be improved. , p, - BPF purity 'reduced 〇, 〇-BPF content rate. There have been many prior art documents on epoxy resins obtained by using BPF. For example, Patent Document 7 discloses that a resin having a low viscosity can be obtained by epoxidizing p,p'-BPF and the cured product is excellent in heat resistance. However, root 12 322427 201122050 • According to the inventor's opinion, the BPF plastic epoxy resin obtained by using p,p'-BPF is only a low-viscosity liquid immediately after manufacture, and it still causes over time. Crystallization 'has the problem of long-term storage stability. The same applies to the BPF type epoxy resin obtained by using BPF having a high P,P'-BPF content. Although the composition has different degrees of crystallinity depending on the composition, it still causes crystallization over time. The rate of crystallization is based on the content of P'P'-BFDGE. However, in the epoxy resin, a curable resin composition such as a curing agent, a catalyst, or a filler may be accelerated to crystallize. Among them, Patent Document 8 discloses that the conditions for the crystallinity can be solved, and high heat resistance and high adhesion to metals can be obtained. Further, in Patent Document 9, crystals are not precipitated by containing a certain amount of a trifunctional component or hydrazine, p, -BPF and storing at 5 ° C for one week. Most of these prior documents are based on the conditions of using a ruthenium, a P-BFDGE component, a ruthenium, a 〇'-BFDGE component, or an epoxide of a polyfunctional component contained in a BPF as a solvent to attenuate the crystallinity of p p ' _ BFDGE. the study. Patent Document 7 and Patent Document 8 do not specifically describe the flame retardancy. Further, Patent Document 10 discloses that a heat resistance and a flame retardancy condition are obtained by using an epoxy resin having a double moon frame in a BPF skeleton, and the double epoxide has high flame retardancy. The skeleton, but its crystallinity is very strong, and its melting point is also very high. Therefore, the % oxygen resin obtained by copolymerization of BPF and epihalohydrin also has crystallinity and exhibits a solid state. Therefore, it is necessary to heat and mix and homogenize it during use. In addition, bisphenol is less versatile and less economical than BPF. 13 322427 201122050

Generally, the BPF type epoxy resin which is sold is obtained by polycondensation of BPF and epihalohydrin as described above, and various liquids are present to the solid state depending on the reverse unit, and generally can be purchased from Dongdu Chemical Co., Ltd. , jER Co., Ltd., DIC Corporation, Hexion Specialty Chemicals, etc. As a representative grade liquid BPF type epoxy resin, YDF-170C, manufactured by Tohto Kasei Co., Ltd., jER806 (manufactured by JER Co., Ltd.), EPICLON 830 (manufactured by DIC Corporation), and ΤΕ0ΤΕ 862 (Hexion Specialty Chemicals) Company system) and so on. In the liquid resin, when it is crystallized, it is necessary to dissolve again before use, and since the workability is deteriorated, the resin which can be widely used is generally designed to have a storage stability. For example, when measured by HPLC analysis used in the present invention, the sum of the areas of YDF-170 relative to 〇, 〇'-BFDGE and 〇'P'-BFDGE and p,p'-BFDGE, 〇, 〇'-BFDGE The area accounts for 14% to 16% of area. '〇, p, -BFDGE covers an area of 45. From /G to 48% area, the area of p, p, -BFDGE accounts for 38% to 40% area. As for other commercial products, the 〇' 〇'-BFDGE content rate is more than 10%. Regarding the isomer composition of the widely used and economical epoxy resin raw material, the physical properties of the epoxy resin obtained by the reformer, especially the BPF obtained by using the reduced productivity of B, P, and BFDGE. The problem of storage stability due to the crystallization of Epoxy resin is not fully studied. That is, a method of obtaining an epoxy resin having high heat resistance, copper foil peel strength, interlayer adhesion, and flame retardancy by controlling the isomer composition of the BPF has not been known until now. 322427 14 201122050 . As mentioned above, the PPF type ring gas tree with a high content of p,p,-BFDGE is only a liquid epoxy resin which is low in workability after being manufactured, and is excellent in processability, and is at room temperature. In the normal state, pp is precipitated when it is stored for a long period of time, that is, it is a solid resin. Therefore, it needs to be heated, dissolved, mixed, etc. before use, so it is not a resin excellent in workability. However, even a crystalline BPF type epoxy resin can be reacted with a hindrance compound to obtain a scaly epoxy resin having no crystallinity. Further, the phosphorus-containing oxygen-containing resin cured product of the present invention has high heat resistance as compared with a BPF-type epoxy resin having a high BFDGE content of ruthenium, osmium and BFDGE. However, it has been found that the cured product of the phosphorus-containing epoxy resin of the present invention has not only reduced the adhesion force, but surprisingly, the adhesion between the copper box and the laminate, and the adhesion between the layers of the glass cloth and the glass cloth of the laminate are also At the same time improve. In addition, it has been found that in the flame retardancy of the cured product, the cured product of the oxygen-containing resin of the present invention has a higher hardness than that of the cured epoxy resin obtained by using a clear epoxy resin having a higher content of bismuth-BFDGE. Excellent properties. The BPF type epoxy resin used in the present invention is represented by the formula (4), and the -BFDGE content is 10% by area or less. Here, 〇, 〇 - BFDGE content rate means the area % of the peak value (0) with respect to the sum of the peak (8), the peak (P), and the peak (9) in the j-th graph. In addition, the O'p-BFDGE content rate is defined as the area occupied by the peak value (p) with respect to the sum of the bee value (8), the peak value (P), and the peak value (Q) in Fig. 1 The P BFDGE content rate is defined as the area % of the peak (9) relative to the sum of the peak (〇), the peak (P), and the peak (8) in the graph. BpF-type ring 322427 15 201122050 using yttrium, 〇'-BFDGE content of 1 G area% or less The phosphorus-containing epoxy resin of the present invention obtained by using an oxy-resin and using 〇'〇'-BFDGE content rate exceeding 1 〇 area% Compared with the phosphorus-containing epoxy resin obtained by the epoxy resin of the 兕{!· type epoxy resin, the melt viscosity is low and the workability is excellent: in terms of the physical properties of the cured product, the resin is made higher than the conventional technique. Heat resistance, in addition to not only high adhesion, but also improved flame retardancy. When using the BPF type epoxy resin used in the present invention to obtain a phosphorus-containing moon 〇, the 〇, 〇-BFDGE content is 〇 area% or more and 1 area. Below %, preferably 0 area. /fl above 8 area% or less. More preferably, the area is more than 5%, and the area is ◦/◦ or less, and it is preferably 〇 area% or more and 4.5 area% or less. When the content of the crucible, the crucible, and the body content exceeds 10% by area, the amount of the component remaining unrelated to the reaction at the time of hardening increases, and the heat resistance or the adhesion and the flammability are affected. 9 In addition, the BPF is used. The epoxy resin is used in an amount of 20% by weight or more and 85% by weight or less based on the phosphorus-containing epoxy resin obtained by the reaction. It is preferably 22% by weight or more and 8% by weight or less, more preferably 24% by weight or less. % by weight or more and 75% by weight or less, wherein the calculation is based on the value of the solid component irrespective of the dilution solvent. When the amount of the BPF type epoxy resin is 20% by weight, there is no significant difference from the prior art. When the use amount is more than 85% by weight, the use amount of the phosphorus-containing compound is inevitably decreased, so that the problem of insufficient flame retardancy or crystallization is formed. Further, the oligomer of the 3-nuclear body or more contained in the BPF of the present invention The content rate of the component is not particularly limited. Generally, the content of the oligomer component of the trinuclear or higher is less than 20% by weight, but the content is not limited thereto, and it is hardly contained by distillation. By. The compound of the formula 322427 16 201122050 used in the present invention also contains an oligomer derived from bpf ~ octopus, Γ T 0 nucleus or more, and is particularly important. The focus is on the use of a BPF type epoxy resin having a low content of 〇'-BFDGE. Hereinafter, a method for producing the phosphorus-containing epoxy resin (9) of the present invention will be specifically described. In the present invention, the BPF type epoxy resin and the like are included. The scalloped acid is reacted to obtain a liquid-containing resin containing the epoxy resin as in the general formula (5) (2), and has at least one functional group reactive with an epoxy group in the molecule. In (5), γ represents hydrogen or a functional group having an aromaticity 'm is 0 or 卜. Further, Ri and Rz represent an aromatic hydrocarbon group, and may contain a hetero atom such as oxygen, nitrogen, a can, or sulfur. And & can be independent of each other, or can be connected to form a ring structure. When m=1, the ring structure is connected with & and the ring structure can inhibit the overflow caused by hydrolysis. Specific examples of the compound represented by the formula (5) include 9 a-one gas-9-oxa-10-虱1〇-(2,5-dihydroxyphenyl)-9' 10-dihydro-9-oxa-1〇-phosphaphenanthrene-phosphonium-10-oxide (HCA) or its derivative Μ-oxide (HCA-HQ), 1〇-(2,7-dihydroxynaphthyl)-9, 10_dihydro~9~oxa-10-fill phenanthrene-10-oxide (HCA-NQ However, it is not limited to the above, and may be used singly or in combination of two or more types. The phosphorus-containing epoxy resin (D) of the present invention can be obtained by the reaction without impairing the properties of the resin. An epoxy resin other than the BPF epoxy resin of the present invention is used. The epoxy resin used herein preferably has two or more epoxy propyl groups in the oxime group, but is not particularly limited. With the following: EPOTOHTO YDC-1312, EPOTOHTO ΖΧ-1〇27 (Dongdu 322427 17 201122050 Chemical Co., Ltd., hydroquinone epoxy resin), epotohto ZX-1251C Dongdu Chemical Co., Ltd., bisphenol Epoxy resin), EPOTOHTO YD-127, EPOTOHTO YD-128, EPOTOHTO YD-8125, EPOTOHTO YD-825GS' EPOTOHTO YD-011 'EPOTOHTO YD-900 'EPOTOHTO YD-901 (made by Dongdu Chemical Co., Ltd., BPA type) Epoxy resin), EPOTOHTO YDPN-638C manufactured by Dongdu Chemical Co., Ltd., phenolic epoxy resin), EPOTOHTO YDCN-701 (made by Dongdu Chemical Co., Ltd., phenolic epoxy resin), EPOTOHTO ZX-1201C Dongdu Chemical Co., Ltd. Co., Ltd., bisphenol oxime epoxy resin), NC-3000 (manufactured by Sakamoto Chemical Co., Ltd., exophenylene phenolic epoxy resin), EPPN-501H, EPPN-502H (Japanese chemical Co., Ltd., polyfunctional epoxy resin), EPOTOHTO ZX-1355 (made by Dongdu Chemical Co., Ltd., naphthalene glycol epoxy resin), EPOTOHTO ESN-155, EPOTOHTO ESN-185V, EPOTOHTO ESN-175C Dongdu Chemicals Co., Ltd. Co., Ltd., /5-naphthol aralkyl epoxy resin), EPOTOHTO ESN-355, EPOTOHTO ESN-375C manufactured by Dongdu Chemical Co., Ltd., dihydroxynaphthalene aryl epoxy resin), EPOTOHTO ESN-475V, EPOTOHTO ESN-485C Dongdu Chemical Co., Ltd. made of naphthol aralkyl epoxy resin) and other phenolic compounds such as polyphenols and epoxy resins manufactured by epihalohydrin; EPOTOHTO YH-434, EPOTOHTO YH-434GS (Dongdu Huacheng Co., Ltd. Epoxy resin manufactured by the company, diamine diphenyl decane tetraglycidylamine and other amine compounds and epihalohydrin; EPOTOHTO YD-171 (made by Dongdu Chemical Co., Ltd., dibasic acid type oxygen resin) _Acid and epoxicone epoxy resin; EPOTOHTO FX-289B, EPOTOHTO FX-305C Dongdu Huacheng Co., Ltd. 18 322427 .201122050, company's 'phosphorus-containing epoxy resin', PHE coffee _ erf__Dongdu Huacheng. Phosphorus-containing epoxy resin obtained by reacting an epoxy resin such as a phosphorus-containing phenoxy resin with a modifier such as a phosphorus-containing compound, but is not limited to such 'can be used alone or used alone 2 or more types. Phenols can also be used when the phosphorus-containing epoxy resin (8) of the present invention is obtained by the reaction. The phenols used herein are desirably those which are based on the i molecule, but are not particularly limited. Specifically, it may be exemplified by a double resin such as BPA or BPF, a secret resin such as a secret resin or a secret resin, a soluble resin, a condensed fat having a benzene dimethyl skeleton, a biphenol, and a naphthalene. The alcohol, hydroquinone, resorcin, catechol, and the like are not limited thereto as long as they are conventionally used, and may be used singly or in combination of two or more types. The method for obtaining the phosphorus-containing epoxy resin (D) of the present invention may be a mixture of at least one type of a compound selected from the group consisting of HCA HCA HQ or HCA-MQ and a BPF type epoxy resin. The method of carrying out the reaction. Other methods include a method in which HCA is reacted with an anthraquinone compound represented by benzoquinone or naphthoquinone in an inert solvent, and then a BpF-type epoxy resin or the like is added thereto and stirred to carry out a reaction. At this time, the compound represented by benzene is excessively metered relative to the brewed compound. In any case, the reaction of the phosphorus-containing compound with the oxime resin is usually carried out at a reaction temperature of from 1 hour to 1 hour in the range of the reaction time, and the epoxidized tree of the present invention can be obtained. The purpose of the month (8). In addition, when the reaction is slow, it is possible to use a catalyst to improve productivity. Further, when the viscosity at the time of the reaction is high, an inert solvent may be used as needed. 19 322427 201122050 Specific catalysts can use tertiary amines such as benzoguanidine diamine, quaternary ammonium salts such as vaporized tetramethylammonium; phosphines such as triphenylphosphine and tris(2,dioxyl)phosphine Classes; scalloped ethyltriphenyl scales and other scale salts; 2-mercaptoimidazole, 2-ethyl-4-ylhydrazine and other imidazoles and other catalysts. In addition, as a specific example of the reaction solvent, the present invention is not limited thereto, and two or more types may be used alone or in combination. The filling ratio of the scale-containing oxygen resin (D) of the present invention is preferably from 15 to 5.0% by weight, more preferably from 1.8 to 4.5% by weight. When the content of the phosphorus-containing phenol resin is 1.5% by weight or less, the flame retardancy may not be maintained. Further, when the content of the dish exceeds 5.% by weight, the molecular weight thereof becomes large, so that the solubility of the solvent is remarkably deteriorated and it becomes difficult to use. The curing agent used in the preparation of the phosphorus-containing epoxy resin (D) of the present invention to obtain a curable resin composition may be various phenol resins or acid anhydrides, amines, hydrazines, acid polyesters, and amine groups. Triazines and other known hardeners for epoxy resins which are conventionally used, and these hardeners may be used alone or in combination of two or more types. When the epoxy-containing epoxy resin (D) of the present invention is used as an essential component, and an epoxy resin hardener or the like is blended to obtain an epoxy resin composition, it is possible to avoid damage to the characteristics of the epoxy resin (D). Also use other epoxy resins. The epoxy resin used herein is preferably one having two or more epoxy propyl groups per molecule. Specifically, ΕΡ0Τ0ΗΤ0 YDC-1312, EPOTOHTOZX-1〇27 (made by Dongdu Chemical Co., Ltd., hydroquinone type epoxy resin), ΕΡ0Τ0ΗΤ0 ZX-125K manufactured by Dongdu Chemical Co., Ltd., double-twisted epoxy resin) ΕΡ0Τ0ΗΤ0 YD-127, ΕΡ0Τ0ΗΤ0 YD-128, 20 322427 201122050 ΕΡ0Τ0ΗΤ0 YD-8125 ' ΕΡΟΤΟΗΤΟ YD-825GS > ΕΡΟΤΟΗΤΟ YD-011, EPOTOHTOYD-900, EPOTOHTOYD-901 (made by Dongdu Chemical Co., Ltd., ΒΡΑ-type epoxy resin ), YDF-170, ΕΡΟΤΟΗΤΟ YDF-8170 ^ ΕΡΟΤΟΗΤΟ YDF-870GS > ΕΡΟΤΟΗΤΟ YDF-2001 (made by Dongdu Chemical Co., Ltd., BPF type epoxy resin), ΕΡΟΤΟΗΤΟ YDPN-638 C manufactured by Dongdu Chemical Co., Ltd., phenolic Type epoxy resin), ΕΡΟΤΟΗΤΟ YDCN-701 (made by Dongdu Chemical Co., Ltd., phenolic epoxy resin), ΕΡΟΤΟΗΤΟ ΖΧ-120Κ Dongdu Chemical Co., Ltd., bisphenol oxime epoxy resin), NC-3000 ( Sakamoto Chemical Co., Ltd., bis-phenylene phenolic epoxy resin) EPPN-501H, EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., polyfunctional epoxy resin), ΕΡΟΤΟΗΤΟ ZX-1355C manufactured by Dongdu Chemical Co., Ltd., naphthalene glycol epoxy resin), ΕΡΟΤΟΗΤΟ ESN-155, ΕΡΟΤΟΗΤΟ ESN -18 5V, ΕΡΟΤΟΗΤΟ ESN-175 (made by Dongdu Chemical Co., Ltd., 10,000-naphthol aralkyl type epoxy resin), ΕΡΟΤΟΗΤΟ ESN-355, ΕΡΟΤΟΗΤΟ ESN-375C Dongdu Chemical Co., Ltd. 'Dihydroxynaphthalene aralkyl type Epoxy resin), ΕΡΟΤΟΗΤΟ ESN-475V, ΕΡΟΤΟΗΤΟ ESN-485 (made by Dongdu Chemical Co., Ltd., α-prepared ^• hospital type epoxy resin) and other epoxy compounds such as oxime compounds and epihalohydrin Resin; ΥΗ 434-434, ΕΡΟΤΟΗΤΟ YH-434GS (made by Dongdu Chemical Co., Ltd., diamine diphenyl decane tetraglycidylamine) and other amine compounds and epihalohydrin epoxy resin; ΕΡΟΤΟΗΤΟ YD-17K Dongdu Chemical Epoxy resin manufactured by carboxylic acid and epihalohydrin, manufactured by Co., Ltd., dimer acid type epoxy resin; ΕΡΟΤΟΗΤΟ FX-28 9B, ΕΡΟΤΟΗΤΟ FX-305C Dongdu Chemical Co., Ltd., phosphorus-containing gas tree 21 322427 201122050 grease), ΡΗΕΝ0Τ0ΗΤ0 ERF-001 (made by Dongdu Chemical Co., Ltd., containing phenoxy resin) and other epoxy resins and phenols The phosphorus-containing epoxy resin obtained by the modification of the compound or the like is not limited thereto, and two or more types may be used in combination. For the curable resin composition comprising the phosphorus-containing epoxy resin (D) of the present invention as an essential component and a curing agent or the like, a tertiary amine, a quaternary ammonium salt, a phosphine, or an imidazole may be formulated as needed. For the curable resin composition comprising the phosphorus-containing epoxy resin (D) of the present invention as an essential component and a curing agent or the like, an organic solvent may be used to adjust the viscosity. An ether such as an organic solvent alcohol monoterpene ether; an aromatic hydrocarbon such as acetone or methyl ethyl group; an alcohol such as an ethyl alcohol or the like; and one type of the solvent may be used. The resin concentration in the resin composition solution may be 20% by weight or more and less than 100 lbs., and the phosphorus-containing epoxy resin (8) of the present invention is used as an essential component, and the curing (4) is used. For the sclerosing tree remainder, the filler can also be blended as needed. Specific examples thereof include: hydrazine hydroxide, oxidized town t, calcined talc, clay, kaolin, titanium oxide, broken glass powder, fine powder of cerium oxide, molten cerium oxide, crystalline dioxin: diarrhea, porosity Dioxo cut, dioxane gas material inorganic filler, can also adjust the lungs. The material may be (4) known to be used (4), and t may be used in combination of two or more types. The reason for using an inorganic filler is to improve the impact resistance. 322427 22 201122050 In addition, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it can act as a flame retardant aid and ensure flame retardancy even if the phosphorus content is small. In particular, when the blending amount is 10% or more, the impact resistance is high. However, if the blending amount exceeds 150%, the durability of the necessary items for the use of the laminate will be lowered. Further, a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber, or a fine particle rubber or a thermoplastic elastomer 荨 organic filler may be contained in the above resin composition. The same can be used in the same manner as the above-mentioned ones, and it is also possible to use one or more of them. The material for the electronic circuit board obtained by the above-mentioned curable resin composition may be a resin sheet, a metal foil with a resin, a prepreg or a laminate. The method of producing the resin sheet is not particularly limited. For example, the phosphorus-containing epoxy resin composition (preferably having a thickness of 5) may be applied to a carrier film which is insoluble in a curable resin composition such as a polyester film or a polyimide. To 1 〇〇 #m), and then dried at 1 (10) to 2 rc for 1 to 40 minutes to form a sheet. In general, a method called a method is used to form a resin sheet. At this time, in the case of applying a sheet containing the fluorinated % oxyresin composition, if the surface treatment is carried out by using a release agent, the formed resin sheet can be easily peeled off. Here, the resin is preferably formed to 5 to 8 Å. The order is then described with respect to the gold shot 1 obtained by using the above-mentioned curable resin composition. Gold shot I can use copper,! 2 ° gold, composite metal box of s, yellow steel, nickel, etc. The method of using a metal bisλ having a thickness of 9 to 7 G/zm and having a fluorophore-containing flame retardant resin composition and a metal-white resin-containing metal foil is preferably not limited, for example, 322427 23 201122050 One surface of the metal foil is coated with a resin varnish (the curable resin composition is subjected to a solvent-adjusted viscosity) by a roll coater or the like, and then dried by heating to dry the resin component (step B) to form a resin layer. When the resin component is semi-hardened, for example, it can be heated and dried at 100 to 2003⁄4 to i. The thickness of the resin portion having the metal network of the resin here is preferably 5 to 11 〇 em. Next, the prepreg obtained by using the above curable resin composition will be described. The sheet-like substrate may be an inorganic fiber such as glass or a woven or non-woven fabric of an organic fiber such as polyester, polyacryl, polyacryl, polyimine or kewei, but is not limited thereto. The method for producing the prepreg from the curable resin composition and the substrate is not particularly limited. For example, the substrate may be impregnated with a resin varnish (the epoxy resin composition is subjected to solvent-adjusted viscosity), and then impregnated. Heating and drying to semi-harden the resin component (B-step), for example, drying at 100 to 20 (TC heating to 〇4 minutes. Here, the amount of resin in the prepreg is 3 〇 to 8 〇 wt% relative to the whole. 。 々 针对 々 々 々 々 々 々 々 々 々 々 々 々 々 々 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 And arranging the metal crucible on one side or both sides to form a laminate, and then heating and pressurizing the laminate to form a layer. The metal town can use a single alloy of copper, inscription, brass, and the like. , composite metal _. The conditions for heating and pressurizing the laminate, the conditions for hardening the curable resin composition can be appropriately adjusted to heat (4) when the pressure is too low, the inside of the laminate obtained sometimes remains. The bubbles are reduced in electrical properties, so it is preferably pressurized to satisfy the formability of strips 322427 24 201122050. The heating and pressurizing conditions can be set, for example, to a temperature of 160 to 220 ° C, a pressure of 0.5 to 5 MPa, and a heat and pressure. The time is 40 to 240 minutes. In addition, the single-layer laminate obtained by the above method can be used as the inner layer to form the multilayer board. At this time, the circuit is first formed on the laminate by an additive method or a subtraction method, and then The surface of the formed circuit is treated with an acid solution to carry out a blackening treatment to obtain an inner layer material, and a circuit is formed on one side or both sides of the inner layer material and formed by using a resin sheet, a metal foil with a resin, or a prepreg. The insulating layer forms a conductor layer on the surface of the insulating layer to form a multilayer board. When the insulating layer is formed by using the resin sheet, a resin sheet is disposed on the circuit forming surface of the plurality of inner layers to form a laminate, or in the inner layer. A resin sheet is disposed between the circuit forming surface and the metal foil to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, thereby forming the cured resin sheet into an insulating layer. At the same time, multilayering of the inner layer material is formed, or the inner layer material and the metal foil as the conductor layer are formed into a resin sheet cured product as an insulating layer. Here, the metal case may be the same as that used for the laminated board used as the inner layer material. The heat and pressure forming 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 circuit-forming surface resin on the outermost layer of the inner layer is coated with a composition containing a hydrogen-containing resin. Or a scaly epoxy resin to form a jellyfish (preferably a thickness of 5 to 100 / ζ πθ, then 1 〇〇 to 2 〇 (rc heat drying 丨 to 卯 minutes to form a sheet. - generally speaking It is formed by a method called a material method, and the thickness after drying is preferably 5 to 8 Q/m. The surface of the multi-layered laminate formed by the above method may be further formed by an addition method or a subtraction method 322427 25 201122050 Through hole or circuit to form a printed wiring board. Further, a multilayer board of a plurality of layers can be formed by using the printed wiring board as an inner layer and repeating the above method. Further, when the insulating layer is formed by using a metal foil with a resin, a metal foil with a resin is placed on the circuit forming surface of the inner layer material so that the resin layer of the metal case with the resin faces the circuit forming surface of the inner layer. To form a laminate. Then, the laminate is heated and pressurized to be integrally molded, whereby the resin of the resin layer of the resin-containing metal foil is made into an insulating layer, and the metal case on the outer side becomes a conductor layer. Here, the heat and pressure forming can be carried out under the same conditions as the formation of the inner layer. Further, when the insulating layer is formed by the prepreg, a prepreg (one or a plurality of laminated sheets) is disposed on the circuit forming surface of the inner layer, and a metal foil is disposed on the outer side to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, whereby the cured product of the prepreg is made into an insulating layer, and the metal foil on the outer side becomes a conductor layer. Here, the metal foil can also be used in the same manner as the user of the laminate used 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. The surface of the multilayered laminate formed in the above manner may be further subjected to formation of a via hole or a circuit by an additive method or a subtractive method to form a printed wiring board. Further, a multilayer board of a plurality of layers can be formed by using the printed wiring board as an inner layer and repeating the above method. EXAMPLES Examples are described in detail below, but the present invention is not limited thereto. BPF type epoxy resin is used in different 〇, 〇, -BFDGE content rates. Specifically, 'BPF type epoxy resin V system 〇, 〇'-BFDGE content rate is %%' BPF type epoxy resin W system 〇, 〇, -BFDGE content rate is 4. 9 26 322427 201122050 area%, BPF type epoxy resin X system 〇, 〇'-BFDGE content is 5.8 area%, BPF type epoxy resin Y system 〇, 〇'-BFDGE content rate is 9.5 area% of 'BPF type epoxy The resin Z is 〇, and the o'-BFDGE content is 14.2 area%. Among them, BPF type epoxy resin Z is ETOPOHTOYDF-170 manufactured by Dongdu Chemical Co., Ltd. Other general traits of epoxy equivalents are set forth in Table 1 of the Examples. Further, in the examples of Table 2, it is simply referred to as BPF type epoxy resin. The BPF type epoxy resin used in each of the synthesis examples is as specified in Table 2 of the examples. The phenolic epoxy resin is manufactured by Dongdu Chemical Co., Ltd. ΕΡ0Τ0ΗΤ0 YDPN-638. For the phosphorus compound, HCA-HQ manufactured by Sanko Co., Ltd. and Sanko Co., Ltd. were used. In addition, HCA-HQ' is used to carry out the reaction of HCA manufactured by Sanko Co., Ltd. and Kawasaki Kasei Kogyo Co., Ltd. in 1,4-naphthalene brewing in a solvent of benzene, and after filtration and purification, it is purified by recrystallization. 1〇_(2,7-di-naphthyl)-9,10-dihydro-9-oxa-i〇_phosphaphenanthrene- 1 〇_oxide. The clumsy compound is produced using Kanto Chemical Co., Ltd. to test the special grade 1,4 benzene. The naphthylquinone compound was prepared by Kawasaki Kasei Kogyo Co., Ltd., 4-naphthoquinone. Others that are not specifically described are synthesized using a commonly sold reagent. In Table 2, the 〇, 〇 -bfdge content ratios were obtained by analysis in the following manner. For the separation column, AgUent 11() seHes 27 322427 201122050 (manufactured by HewLett Packerd Co., Ltd.) equipped with Cadenza CD-C18 CD006 (manufactured by Imtakt Co., Ltd.) was used. The temperature of the tube chamber was set to 4 ° C, and the eluent was analyzed using (a) water and (b) acetonitrile at a flow rate of 1 mL/min using the gradient conditions shown in Table 1. Table 1 Time min 0. 00 5. 00 13. 00 30. 〇〇 30. 01 (b) Phase % 60 ~ 60 80 100~~ 60 In addition, the detection is performed by an absorbance detector, based on a 28 〇 nm wave.

The area % obtained by absorption is quantified. Figure i shows the HPLC chart of the BpF type epoxy resin V used. 〇, 〇' - BFDGE is the peak value (〇), 〇, P' - BFDGE is the peak value (P), p, p' _BFDGE is the peak value (Q). Further, the individual content rate is expressed by area % by dividing the peak area of each individual by the sum of the peak (〇), peak (p), and peak (Q) areas. The content ratio of each component was determined by the following formula. 〇'〇' - BFDGE content rate [area%] = (0) area / {(〇) area KP) Area + (Q) area} xl 〇〇 % O'p' - BFDGE content rate [area % MP) area /u〇) Area κρ) Area + (Q) Area}xl〇〇% P, P' - BFDGE content rate [area%>(Q) area/u〇) area + (ρ) Area + (Q) area }xl〇〇% BPF type epoxy resin has a polynuclear body with three kinds of isomers or by-products, which is very complicated in analysis. Therefore, the foot (3) is used as a representative component and analyzed by the following method. For the g-column, three HLC-8220 (manufactured by TOSOH Co., Ltd.) having a series connection of 322427 28 201122050 TSK-GEL 2000HXL and TSK-GEL 1000HXL (all manufactured by TOSOH Co., Ltd.) was used. The temperature in the column chamber was set to 40 ° C, the tetrahydrofuran was used as the eluent, and the flow rate was set to 1 mL/min. Further, the detection was carried out using a refractive index (ri) detector and quantified in area %. Fig. 2 shows a GPC chart of the BPF type epoxy resin V used. The peak (R) is a mixture of p,p' -BFDGE and o,p' -BFDGE and 〇,〇' -BFDGE. The high molecular weight component other than the peak (R) is a mixture of an epoxide of a trinuclear or higher component contained in the BPF or a compound represented by the formula (4), wherein η is a component of 1 or more or various by-products. In Table 1, the nucleus η = 0 component content rate is the area of the peak (r) divided by the total area and expressed by area %. Example 1 A 2 L separable flask equipped with a mixer, a thermometer, a cooling tube, and a nitrogen inlet was charged with 209. Og, toluene 400. 〇g, and dissolved at 75 ° C with stirring. After completely dissolving, while paying attention to the temperature _, a small amount of 1,4-naphthoquinone 148.3 g was added successively, and the temperature was maintained in the range of 8{rc to 9 °C for 30 minutes. Then, the temperature was raised to the reflux temperature of toluene for 2 hours to carry out dehydration and aging in the system to obtain a phosphorus compound. The 〇'〇'-BFDGE content was 4. 4 area kBpf? type epoxy resin V 642.7 g, and then the temperature was raised to 150 ° C to distill off benzene. Then, triphenylphosphine as a reaction catalyst is dissolved in toluene and added to the reaction system. The triphenylphosphine phase is added to the phosphorus-containing compound by 1% by weight. It was then heated to 165 and it was reacted for 4 hours. After the completion of the reaction, a small amount of methyl ethyl ketone was successively added dropwise to the oxime while cooling and dissolved. The solid content of the resin solution was adjusted to 70% by weight in 322427 29 201122050. Example 2 A BPF type epoxy resin W having a 〇'-BFDGE content of 4.9 % by area was used in the same manner as in Example 1 except that the BPF type epoxy resin was used, and the solid content was 70% by weight. A phosphorus-containing epoxy resin solution. Example 3 A BPF type epoxy resin X having a 含有, o'-BFDGE content of 5.8 area% was used except for the BPF type epoxy resin, and the same operation as in Example 1 was carried out to obtain a solid content of 70% by weight. A phosphorus-containing epoxy resin solution. Example 4 In the same manner as in Example 1, except that the BPF type epoxy resin was used, the 〇'-BFDGE content was 9.5 area% 2 BPF type epoxy resin Y, and the solid content was 70% by weight. Phosphorus-containing epoxy resin solution. Comparative Example 1 A BPF type epoxy resin Z having a 〇'-BFDGE content of 14.2 area% was used except for a BPF type epoxy resin, and the same operation as in Example 1 was carried out to obtain a solid content of 70% by weight. A phosphorus-containing epoxy resin solution. Example 5 In the same apparatus as in Example 1, 139.4 g of HCA and 290. Og of toluene were charged and dissolved by stirring at 75 °C. After completely dissolving, 71.4 g of naphthoquinone was added in small portions while paying attention to the temperature, and the temperature was maintained in the range of 80 ° C to 90 ° C for 30 minutes. Then, the temperature was raised to the reflux temperature of toluene and maintained for 2 hours to carry out dehydration and aging in the system to obtain a mixture of phosphorus compounds. Here, the PF, o'-BFDGE content was 4. 4 area% of the BPF type ring 30 322427 201122050 Oxygen resin V 300.0g and the phenolic type epoxy resin 489 3g, and then the temperature was raised to 150C to distill off toluene. The same operation as in Example 进行 was carried out to obtain a phosphorus-containing epoxy resin solution having a solid content of 75% by weight. Comparative Example 2 A BPF-type epoxy resin z having a 含有, 〇BFDGE content of 14 2 area% was used as the BPF type epoxy resin, and the same operation as in Example 5 was carried out to obtain a solid content of 75% by weight. Phosphorus epoxy resin solution. Example 6 In the same apparatus as in Example 1, HCA-HQ 31*3. 5g and 〇, o'-BFDGE content was 5.8 area% of BPF type epoxy resin χ 686.5g 'then heat up to 150 乞 dehydration in the system. Then, triphenylphosphine as a reaction catalyst is dissolved in methyl ethyl ketone and added to the reaction system. The diphosphine is added in an amount of 0.1% by weight relative to the phosphorus-containing compound. Then, the temperature was raised to 165 ° C to carry out a reaction for 4 hours. After the completion of the reaction, a small amount of mercaptoethyl ketone was successively added dropwise to the system while cooling and dissolving. The solid content of the resin solution was adjusted to 70% by weight. Comparative Example 3 A BPF type epoxy resin Z having a 〇'-BFDGE content of 14.2 area% was used except for a BPF type epoxy resin, and the same operation as in Example 6 was carried out to obtain a solid content of 75% by weight. A phosphorus-containing epoxy resin solution. Example 7 In addition to the same apparatus as in Example 1, HCA-NQ 289. 5g and 〇, 〇'-BFDGE content was 5.8 area% of bpf type epoxy resin X 710. 5g 'The rest was carried out The same operation as in Example 6 was carried out to obtain a solid-containing 322427 31 201122050 into a 70% by weight phosphorus-containing epoxy resin solution. Comparative Example 4 A BPF type epoxy resin Z having a 含有, 〇, _BFDGE content of 14.2 area% was used except for the BPF type epoxy resin, and the same operation as in Example 6 was carried out to obtain a solid content of 75% by weight. Phosphorus-containing epoxy resin solution. Comparative Example 5 4 g of HCA 139 and 290.0 g of toluene were charged in the same apparatus as in Example 1, and stirred and dissolved at 75 °C. After completely dissolving, a small amount of naphthoquinone 81. 5 g was added successively while paying attention to the temperature, and the temperature was maintained in the range of 8 Torr to 9 〇 ° C for 30 minutes. Then, the temperature was raised to the reflux temperature of toluene and maintained for 2 hours to carry out dehydration and aging in the system to obtain a mixture of phosphorus compounds. Here, 〇'-BFDGE was contained in an amount of 4.4 area% of BPF type epoxy resin V 150.0 g and phenol type epoxy resin 629. lg, and then the temperature was raised to 150 C to distill off benzene. The same operation as in Example i was carried out, and a phosphorus-containing epoxy resin solution having a solid content of 75% by weight was obtained. Comparative Example 6 A BPF type epoxy resin z having a 含有'_BFDGE content of 14.2 area% was used except for a BPF type epoxy resin, and the same operation as in Example 5 was carried out to obtain a phosphorus content of 75% by weight of a solid content. Epoxy resin solution. Comparative Example 7 In the same apparatus as in Example 1, Βρρ type epoxy resin V916.4g was charged, and then the temperature was raised to 15 (rc was subjected to systemic dehydration. Then, triphenylphosphine as a reaction catalyst was dissolved in mercaptoethyl group. The ketone is further added to the reaction system. Triphenylphosphine is added to the phosphorus-containing compound by adding 〇.丨% by weight. 32 322427 201122050 Then, the temperature is raised to 165 ° C to carry out a reaction for 4 hours. After the completion of the reaction, the mixture is directly cooled and cooled. A semi-solid phosphorus-containing epoxy resin is obtained. The phosphorus content ratios shown in Tables 3 and 4 are not analytical values, but are theoretical values obtained from the added amounts. The epoxy equivalents described are by K-7236. The obtained value was obtained by observing the presence or absence of crystallization of the resin solution obtained in the presence of 〇. The comparative example 5 was a liquid resin containing no solvent. The melt viscosity was MST Engineering Co., Ltd. The dV-lS was measured, and the standard sample was JS52000 manufactured by NIPPON GREASE Co., Ltd. in accordance with JB Z8809. The measurement temperature was 150 ° C. The softening point was evaluated according to the ring and ball method described in JIS K 5601-2-2, and All reviews The price is carried out in a glycerin bath. The dicyandiamide is prepared by using DYHARD-ΙΠ manufactured by NIPPON CARBIDE INDUSTRIES Co., Ltd. to prepare dicyandiamide/n,n-dimercaptoamine/2-methoxyethanol=4 /15/15 (weight ratio). The phenol resin was prepared by using the BRG-555 manufactured by Showa Polymer Co., Ltd. to prepare a phenol resin/methyl ethyl ketone = 90/10 (weight ratio). In addition, 2_ethyl- 4_Methylimidazole was prepared using 2E4MZ manufactured by Shikoku Chemicals Co., Ltd. to prepare a catalyst solution of 2-ethyl-4-methylimidazole/methylethyl ketone = 1/1 (by weight). The diluted solution was prepared by the composition of methyl ethyl _/2-methoxyethanol = ι / (weight ratio). The preparation was carried out according to the values shown in Tables 5 and 6. The values stated in the table are the values of the solid components. The actual blending is carried out in the form of a solution, wherein the monocyanodiamine is formulated in such a manner that the ratio of active hydroquinone to the epoxy group is 5. The epoxy resin solution and the dicyanocide are formulated. After the diamine solution, the phenolic resin solution, and the catalyst solution, the diluted solution is added to perform 322427 33 201122050 adjustment. The body composition was 50% by weight, and a curable resin composition solution (varnish) was obtained. The glass cloth was WEAn6E1G6S136 manufactured by Toyobo Co., Ltd., and the copper enamel system was manufactured by Mitsui Metals Mining Co., Ltd. Immersed in the prepared resin composition solution, dried in a hot air circulating oven of 150 Torr for 7 minutes, and then cut into a predetermined size to obtain a prepreg. Four simple prepregs prepared by the above method were prepared. Two types of laminates were obtained by vacuum heating and pressurizing the four prepregs with the above-mentioned prepreg and sandwiching them. Under the conditions of vacuum heating and pressurization, after 13 minutes of preheating under vacuum for 15 minutes, and then in the 17th generation with a pressure of 2MPa '70 minutes, the secret piece is used for hardening. The copper pig used in this time has bright and rough surface, and the double-sided The rough surface is used as the surface of the prepreg as the surface of the laminate. The time required for gelation is achieved by heating to 16 (the hot plate of TC is taken to measure the curable resin composition solution 0.2 mL, and it is transferred to a hot plate, and then the composition is given by a ferrite rod). It is regarded as the gelatinization time of varnish. The so-called gelatinization here means that the reaction converges over time, and the reaction converges, and the Teflon rod and the resin become an oxygen-free silky moment. 17 (1) lg of the semi-hardened (prepreg powder) of the pre-impregnated resin obtained by the release of the prepreg, and transferred to a hot plate, and then mixed with iron iron rod The time required for gelation is regarded as the pre-dip gelation time. The so-called gelation system here is the same as the above, meaning that the reaction converges over time as the resin viscosity increases, and the iron gas dragon stick and The time between the resins was 322427 34 201122050. The thermomechanical analysis was carried out using Seiko Instruments Co., Ltd. • TMA/SS120U. The test piece was measured using a copper-free laminate to measure the linear expansion ratio in the z-axis direction. The test is from room temperature to 2 〇 (Tc up to 5 ° C / m The temperature rise rate of in was measured and 2 cycles were performed. At this time, the load s was 19 _ 6 N ' The temperature of the recursive extrapolation point of the linear expansion rate in the second cycle was Tg (TMA). The viscoelasticity measurement system used Seiko The DMS 12 0 manufactured by Instruments Co., Ltd. was used. The test piece was a laminate without copper foil. The test was performed at room temperature to 280 ° C, and the shear measurement was performed at a temperature increase rate of 2 ° C/min. The temperature at which the tan accounted for the maximum value was set to Tg (DMS). The differential thermal analysis was performed using DSC 6 2 〇 manufactured by Seiko Instruments Co., Ltd. The sample was prepreg powder, and the test was performed at room temperature. Two cycles were performed at a heating rate of liTc/min up to 200 ° C. The temperature Tig of the recursive extrapolation point at which the heat capacity of the sample in the second cycle began to increase was Tg (DSC). The flammability test was performed according to Underwriter. The Laboratory-94 (hereinafter referred to as UL-94) was tested in the laboratory. The test piece was a laminate without copper foil. The judgment was based on the above specifications, and the total burning time of the item was the total burning time of the five test pieces. The peel strength of the knot is recorded in accordance with JIS C-6481. The test method was carried out to measure the peeling test between the copper foil and the laminate. In addition, the peeling test was also carried out by the same method between the glass cloth and the glass cloth to measure the interlayer adhesion. Among them, the measurement was performed by Shimadzu Corporation. Co., Ltd. 35 322427 201122050 EZ-S was carried out. The gel fraction was obtained by the following procedure: First, a copper-free foil laminate was cut out, and the content of the resin in the laminate was determined by thermogravimetric analysis. Using EXSTAR 6〇〇〇 manufactured by Seiko Instruments Co., Ltd., the temperature is raised from room temperature to 7 〇 in an air atmosphere at a temperature increase rate of 1 〇〇c/min, and is maintained at 7 〇〇t: This state was analyzed every hour. The test tank was used by the maker. After the analysis, only the glass cloth remained in the test cell, and it was confirmed by visual observation that there was no organic matter, and the weight reduction rate obtained by the analysis was made into resin. Then, the same laminate was cut into strips of 10 mm x 2 mm squares, gently washed with water to remove the powder produced during cutting, and then dried at 100 ° C for 24 hours to obtain about 3 g of the sample. The weight was then added to 3 mL of tetrahydrofuran, which was subjected to ultrasonic diffusion treatment for 30 minutes, and then allowed to stand at room temperature for 23.5 hours. Then it was carried out; the weight was measured, dried, and accurately taken before and after observation. In the test, the change in weight I is shown in Table 3. The weight of the resin component after the transition drying is expressed in % by weight when the weight of the resin component in the initial stage is _ weight/in. The formula used is as follows. Η Η ( (sample weight before extraction _ sample weight after extraction) 试 sample weight before Κ extraction χ resin content rate)} χ 1 〇〇 [%] Example 8 to Example 11 and Comparative Example 8 Example 8 to In Example u and Comparative Example 8, a curable resin composition obtained by containing a fat and a cured product were used. Among these, the second, the rate of 'hardener type is the same condition, and only the composition of BPF type epoxy oxime is different. First, by reducing the BPF type epoxy resin 曰 322427 36 201122050 〇, the 〇-BFDGE content rate significantly improves the heat resistance. In addition, it is surprisingly possible to see an increase in the adhesion force between the adhesion forces, in particular between the glass cloths. Further, in the flame retardancy test, a phosphorus-containing epoxy resin obtained by using a BPF type epoxy resin having a low content of 〇, 〇, and _BFDGE has a short total burning time and exhibits high flame retardancy. It is considered to be based on the fact that the cured product of the resin having a high content of yttrium-BFDGE has a low gel fraction, and many low molecular components are detected by GPC in the tetrahydrofuran of the extraction solvent, so that the hardening reaction is irrelevant. The residual monomer or oligomer component may have an easily decomposable component and a flammable component, and may have a poor hardening reactivity, and the 〇'-BFDGE is resistant to hardening reactivity, heat resistance, and resistance. Flammability, adhesion, etc. will be greatly affected. Example 12 and Comparative Example 9 In Example 12 and Comparative Example 9, the amount of the BPF-type epoxy resin used was less than that of Example 8 and the like. The difference between the actual -12 and the comparative example 9 was compared with that of the example 8 and the comparative example 8. Although the difference is small, the use of BPF-type epoxy resin with a low content of ◦, ◦, and ge ge has high fuel economy and a slight increase in interlayer adhesion. Further, the hardened ytterbium-containing epoxy resin obtained by the BPF type epoxy resin having a low _bfdge content in the blocking test has a short total burning time and exhibits high flame retardancy. Example 13 and Comparative Example 1 Although Example 13 and Comparative Example 10 have different types of Wei-containing compounds as in Example 8, but the use of ◦, ◦' _BFDGE has a low content of the type of ring-shaped latex resin (4) heat High, (4) and the strength has also improved. In addition, in the flame retardancy test, a type of epoxy tree 322427 37 201122050 which is known to have a low content of ruthenium, osmium, and ugly is known to have a 3 pulan% oxygen resin cured product, which has a short total burning time and exhibits high flame retardancy. Sex. Example 14 and Comparative Example 11 Example 14 and Comparative Example 11 have phosphorus-containing compounds different from those of Example 8 and the like in the same manner as in Example 13 and Comparative Example 1, but the content ratio of 〇'o'-BFDGE was used. The low BPF type epoxy resin has high heat resistance and interlayer adhesion. Further, in the flame retardancy test, a phosphorus-containing epoxy resin obtained by using a BPF type epoxy resin having a low content of bismuth-BFDGE has a short total burning time and exhibits high flame retardancy. Comparative Example 12 and Comparative Example 13 The amount of use of the BPF-type epoxy resin used in Comparative Example 12 and Comparative Example 13 was reduced, and the difference from the conventional technique was small, to the extent that there was no significant difference. Comparative Example 14 When too much BPF type epoxy resin was used, the amount of the phosphorus-containing compound used was necessarily small. Therefore, the obtained phosphorus-containing epoxy resin precipitates crystals upon standing at room temperature for 14 days. Further, the obtained cured product does not have flame retardancy. The measurement results of the above examples and comparative examples are shown in Tables 1 to 6. Table 2 VWXYZ 'white solid white solid white solid light yellow liquid light yellow liquid epoxy equivalent g/eq 168.4 167.9 167.3 167.5 167.2 〇,〇' -BFDCiE content rate (〇) wood 1 area% 4.4 4.9 5.8 9.5 14.2 o , p' - BFDGE content rate (P) wood 1 area% 25.5 35.1 41.8 45.5 47.6 p,p' -BFDGE 牟 area % j 70.1 60.0 52.4 45.0 38.2 BFDGE (2 nucleus η = 〇 composition vm wood 2 area% 77.7 77.5 77.7 78.3 79.9 Wood 1 using HPLC analysis *2 using GPC analysis 38 322427 201122050 Table 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 HCA Wood 1 209.0 209.0 209.0 209.0 139.4 HQ-HQ Wood 2 313.5 HCA-NQ 289.5 1,4-NQ Wood 3 148.3 148.3 148.3 148.3 71.4 BPF type epoxy resin V (o, o' - BFDGE content 4.4%) 642.7 300.0 BPF type epoxy resin W (o , o' - BFDGE content rate 4.9%) 642.7 BPF type epoxy resin X (o, o' - BFDGE content 5.8%) 642.7 686.5 710.5 BPF type epoxy resin Y (o, o' - BFDGE content rate 9.5 %) 642.7 BPF type epoxy resin Z (o, o' - BFDGE contains 14.2%) Phenolic Epoxy Resin*4 489.3 Phosphorus Content 3.0 3.0 3.0 3.0 2.0 3.0 2.4 Epoxy Equivalent 536 530 529 530 290 488 346 Crystallization Precipitation No No No No No ICI Melt Viscosity (150 ° C) 2533 2290 2372 2731 678 1444 529 Softening point 92.2 93.1 92.4 93.8 71.3 83.0 75.2

*1 HCA-HQ manufactured by Sanko Co., Ltd. *2 HCA-HQ manufactured by Sanko Co., Ltd. *3 manufactured by Kawasaki Chemicals Co., Ltd. 1,4-naphthoquinone*4 manufactured by Dongdu Chemical Co., Ltd. YDPN-638 39 322427 201122050 Table 4 Comparison Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 HCA Wood 1 209.0 139.4 139.4 139.4 83.6 HCA-HQ*2 313.5 HCA-NQ 289.5 1, 4 Na 3 148.3 71.4 81.5 81.5 BPF Type Ring Oxygen resin 丫 (〇, 〇 '-8?00 £ 4.4%) 150.0 916.4 BPF type epoxy resin W (o, o'-BFDGE content 4.9%) BPF type epoxy resin 乂 (〇, 〇 '- 8?00 £ 5.8%) BPF type epoxy resin 〇 (〇, 〇 '-8? 00 £ 9.5%) BPF type epoxy resin 2 (〇, 〇 '-8? 卩 6 £ content rate 14.2 %) 642.7 300.0 686.5 710.5 150.0 Phenolic epoxy resin*4 489.3 629.1 629.1 Filling rate 3.0 2.0 3.0 2.4 2.0 2.0 1.2 Epoxy equivalent 527 288 495 346 310 312 210 Crystal precipitation without or without ICI melt viscosity ( 150°C) 3070 722 1680 545 1800 1930 <50 Softening point 95.7 73.9 86.7 76.0 85 .3 85.6 —

*1 HCA-HQ manufactured by Sanko Co., Ltd. *2 HCA-HQ manufactured by Sanko Co., Ltd. *3 1,4-naphthoquinone*4 manufactured by Kawasaki Kasei Kogyo Co., Ltd. YDPN-638 manufactured by Tohto Kasei Co., Ltd. 40 322427 201122050 Table 5 Implementation Example 8 Example 9 β Example 10 Example 11 Example 12 Example 13 Example 14 Phosphorus-containing epoxy resin used in the synthesis Example parts by weight of novolac type epoxy resin *1 parts by weight Example 1 90.00 10.00 Example 2 90. 00 10.00 Γ Example 3 90.00 10.00 Example 4 90. 00 10.00 Example S 100.00 0. 00 Example 6 100.00 0.00 Example 7 100.00 0. 00 2 11 diamine * 2 parts by weight 2.36 2.38 2, 39 2.38 3.64 0.00 3.05 Phenolic resin *3 parts by weight 0.00 0.00 0.00 0.00 0.00 21.50 0.00 2-ethyl-4-methylimidazole*4 parts by weight 1.00 1.00 1.00 1.00 0.08 0.07 1.00 Phosphorus content (after compounding relative to solid content) Weight 56 2.6 2.6 2.6 2.6 1.9 2.5 2.3 Varnish gel time 285 236 357 328 394 291 234 Prepreg gel time seconds 164 169 170 201 151 180 144 Tg(TMA) °C 136.7 134.1 133.2 130.5 145.7 121.5 129.6 Tg (DMS) °C 156.1 155.5 154.9 152.1 170.3 145.2 151.4 Tg(DSC) °C 138.2 139.0 138.1 136.6 146.6 122.4 130.5 UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-1 Burning time total seconds 39 34 45 42 21 28 40 Copper foil peel strength KN/rn 1.9 2.0 1.8 1.8 1.6 1 1.6 1.9 Interlayer adhesion KN/id 2.1 2.1 2.0 1.9 1.1 2.0 2.2 Resin content % by weight 51.1 49.5 50.2 50.1 50.6 49.9 50.4 Gel fraction %% 98.4 98.4 98.2 97.6 98.6 97.8 97.6 *1 YDPN-638 manufactured by Dongdu Chemical Co., Ltd. *2 DYHARD-m manufactured by NIPPON CARBIDE INDUSTRIES Co., Ltd.

Wood 3 Showa Polymer Co., Ltd. BRG-555 *4 4E4MZ manufactured by Shikoku Chemical Industry Co., Ltd.

*1 YDPN-638 manufactured by Dongdu Chemical Co., Ltd. *2 1^1^-111 manufactured by NIPPON CARBIDE INDUSTRIES Co., Ltd.

2, 3, 4, 4, 4, 4, 4, 4 The phosphorus-containing epoxy resin obtained by using it in the range of 2% by weight or more and 85% by weight or less with respect to the phosphorus-containing epoxy resin has high heat resistance and high adhesion. In addition, the use of bismuth, bismuth, _BFDGE low BPF epoxy resin obtained by the epoxy resin obtained from the BPF epoxy resin, the total burning time in the flame retardant 5 test has a shorter tendency, so it can be said It shows high flame retardancy. The reason for the flame retardancy is considered to be as follows: a cured product obtained by using a BPF type epoxy resin having a low content of 〇'o'-BFDGE, which is subjected to solvent extraction in the evaluation of gel fraction. The reduction is less, and conversely, the hardened material obtained by the BPF type epoxy resin having a high content of 〇'-BFDGE has many components extracted into the solvent. Analysis of the components extracted into the solvent revealed that many ruthenium, osmium, _BFDGE or oligomeric components having a small molecular weight were detected, so that they were hardened when a BPF type epoxy resin having a high content of yttrium, lanthanum, yttrium was used. The cross-linking of the substance will be insufficient, and the volatile components such as sputum, sputum, etc. will act as an easily combustible component and are not advantageous for flame retardancy. On the contrary, the phosphorus-containing epoxy resin cured product obtained by using Βρρι type epoxy resin having a low content of 〇, 〇, _BFDGE is considered to have sufficient crosslinkability and is excellent in flame retardancy. However, when the BPF type epoxy resin used as the raw material exceeds 85 wt% of the phosphorus-containing epoxy resin obtained by the reaction, the B pf type epoxy resin remaining in the system crystallizes, and not only cannot be uniform. Resin and flame retardancy are also insufficient. Industrial Applicability 322427 42 201122050 The present invention is useful as a flame retardant epoxy resin for electronic materials. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a chromatogram of a compound represented by the formula (4) in the analysis method of high-speed liquid chromatography according to the present invention, specifically, a BPF type epoxy described in the examples. Resin V. The peak (0), the peak (P), and the peak (Q) represent the compound represented by the formula (1) (〇, o' - BFDGE) and the compound represented by the formula (2) (o, p' - BFDGE, respectively). ), a compound represented by the formula (3) (p, p' - BFDGE). Fig. 2 is a chromatogram of the compound represented by the formula (4) in the analysis method of the gel permeation chromatography of the present invention, specifically, the BPF type epoxy resin V described in the examples. The peak (R) represents BFDGE, that is, a mixture of 〇, o' - BFDGE and 〇, p' - BFDGE and p, p' - BFDGE. [Main component symbol description] None 43 322427

Claims (1)

201122050 VII. Patent application scope: 1. A phosphorus-containing epoxy resin, which is a phosphorus-containing epoxy resin (D) obtained by reacting an epoxy resin (B) with a phosphorus-containing compound (C), characterized in that: The epoxy resin (B) contains the bisphenol F type epoxy resin (A) represented by the general formula (4) as an essential component; Wherein η is an integer of 0 or more; and the oxygen atom to which the aromatic ring is bonded is ortho or para to the methylene group; the phosphorus-containing compound (C) is represented by the formula (5); (wherein R!, 匕 represents a hydrocarbon group, which may also contain an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom; and R! and R2 may be bonded to form a cyclic structure; Υ represents hydrogen or has an aromatic ring containing a hydroxyl group; a functional group; m is any one of 0 or 1) Among the components contained in the bisphenol F-type epoxy resin represented by the above formula (4), the ratio of the compound represented by the formula (1) is relative to the formula (1) The sum of the compound shown and the compound represented by the formula (2) and the compound represented by the formula (3) accounts for 0% by area or more and 10% by area or less on the high-speed liquid chromatogram; 1 322427 201122050 2. The phosphorus-containing epoxy resin according to claim 1, wherein the content of the double-type F-type epoxy resin represented by the general formula (4) is relatively higher than that of the double-containing & (4) The sum of the epoxy resin (B) having a phenol F-type epoxy resin (A) as an essential component and the phosphorus-containing compound having a structure represented by the general formula (5) is 20% by weight or more and 85% by weight or less. 5重量以上以下以下以下。 The phosphorus-containing epoxy resin as described in claim 1 wherein the dish content is 1. 5 wt% or more and 5 wt% or less. 4. A resin composition comprising the phosphorus-containing epoxy resin according to any one of claims 1 to 3 as an essential component and formulated with a curing agent. A flame-retardant resin cured product comprising a resin composition as described in claim 4 of the patent application. 322427 2