JP2009185087A - Phosphorus-containing epoxy resin, phosphorus-containing epoxy resin composition, method for producing phosphorus-containing epoxy resin, curable resin composition using phosphorus-containing epoxy resin, and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly reactive phosphorus-containing epoxy resin suitable for a copper-clad laminate used for an electronic circuit substrate and a sealing material, a molding material, a casting material, an adhesive, an electric insulation coating material, an electric insulation sheet, copper foil with resin, a prepreg, and an electric laminate used in an electronic component, and to provide a phosphorus-containing epoxy resin composition. <P>SOLUTION: The highly-reactive phosphorus-containing epoxy resin is obtained by setting a content of a phosphorus-containing phenol compound, which is represented by general Formula 2 and contains only one phenolic hydroxy group, to ≥2.5% when the phosphorus-containing phenol compound represented by the formula 2 is used. In the formula 2: n is 0 or 1; R1 and R2 may the same or different and each has a straight chain structure, a branched chain structure, or a cyclic structure, or R1 and R2 may connect to each other to form a cyclic structure; and B is any of benzene, biphenyl, naphthalene, anthracene, phenanthrene, and hydrocarbon-substituted derivatives of these compounds. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for producing a copper-clad laminate, a film agent, a resin-coated copper foil, etc. used for an electronic circuit board, and a sealing material, a molding material, a casting material, an adhesive, and an electrical insulation used for an electronic component. The present invention relates to a phosphorus-containing epoxy resin and a phosphorus-containing epoxy resin composition useful as a coating material, a method for producing the same, a curable resin composition using the resin, and a cured product.

  Epoxy resins are widely used in electronic parts, electrical equipment, automobile parts, FRP, sports equipment and the like because of their excellent adhesiveness, heat resistance and moldability. In particular, copper-clad laminates and encapsulants used in electronic components and electrical equipment are strongly required to have safety such as fire prevention and delay. Is used. Although it has the problem of high specific gravity, flame resistance is imparted by introducing halogen, especially bromine, into the epoxy resin, the epoxy group has high reactivity, and excellent curability can be obtained. Therefore, brominated epoxy resins are positioned as useful electronic and electrical materials.

  However, when looking at recent electronic devices, the tendency to place the highest importance on so-called lightness and thinness is becoming increasingly strong. Under such social demands, halides with large specific gravity are undesirable materials from the viewpoint of the recent trend of weight reduction, and when used at high temperatures for a long period of time, the halides dissociate, thereby causing wiring. There is a risk of corrosion. In addition, the use of halogens has become a problem from the viewpoint of environmental safety because it generates harmful substances such as halides when used electronic parts and electrical devices burn, and alternative materials have been studied. It became so.

Reference literature 1 includes HCA-HQ (10- (2,5-dihydroxyphenyl) -9,10-dihydro-9 manufactured by Sanko Co., Ltd.) as a known literature relating to the compound represented by general formula 1 described in the claims. Patent Document 2 discloses a thermosetting resin obtained by reacting (Oxa-10-phosphaphenanthrene-10-oxide) with epoxy resins at a predetermined molar ratio. There is disclosed a method for producing a phosphorus-containing epoxy resin obtained by reacting an epoxy compound having a reaction with diphenylphosphil hydroquinone. Patent Document 3 discloses a method for producing a flame retardant epoxy resin characterized by 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 and a phosphorus-containing flame-retardant epoxy resin composition obtained by reacting a phosphorus-containing polyhydric phenol compound represented by general formula 2 and an epoxy resin. Reference 5 includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1,4-benzoquinone and / or 1,4-naphthoquinone in the total water content in the reaction system. Steps 1 and 1 for obtaining a reaction composition by controlling the reaction to be not more than 0.3% by weight based on the total amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide used A method for producing a phosphorus-containing flame-retardant bisphenol-type epoxy resin by performing step 2 of reacting with a bisphenol A-type epoxy resin and / or a bisphenol F-type epoxy resin without purifying the reaction composition obtained in the above is disclosed. ing.
Japanese Patent Laid-Open No. 04-11626 JP 05-2104070 A JP 2000-309624 A JP 2002-265562 A However, none of the patent documents describes the curing agent and curability.

Patent Document 6 describes a monofunctional organophosphorus compound containing the structural formula 3 which is a compound represented by the general formula 2, and “reacts with an epoxy group to form a so-called pendant in a resin. In addition, the crosslinking density of epoxy resins is reduced, and there are significant adverse effects such as slowing of the curing rate, lowering of heat resistance or lowering of mechanical strength, and it is difficult to use an amount sufficient to develop a flame retardant wire. The amount of the monofunctional organophosphorus compound as a reactive organophosphorus compound that exhibits sufficient flame retardancy (generally, several dozen to several dozen wt%) ) Is used, the crosslink density is reduced, and there is a problem that the curing rate is delayed.
JP 2000-154234 A

  As a result of examining the reactivity of various phosphorus-containing epoxy resins with a curing agent, the present inventor has found that there is a significant difference in reactivity depending on the obtained phosphorus-containing epoxy resins. If the gel time, which is an indicator of the reactivity of the epoxy resin, is long, for example, the resin flows too much during curing during lamination and crimping, and the resulting laminate has insufficient resin content, resulting in decreased adhesion and migration. Generation, problems such as blistering during solder immersion will occur. In addition, when the gel time is adjusted by increasing the blending amount of the curing catalyst, there are problems such as poor storage stability of the prepreg and long-term storage.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a general formula 2 in the system before the reaction in the phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula 1 with epoxy resins. When the value obtained by dividing the content (% by weight) of the compound represented by the above by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by reaction exceeds 0.3, It has been found that the curing reactivity is remarkably impaired, and the phosphorus-containing epoxy resin of the present invention has been completed. Means for solving the above-mentioned problems are as follows described in the claims. .

  (1) In the phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula 1 and epoxy resins, the content (% by weight) of the compound represented by the general formula 2 in the system before the reaction is reacted. A value obtained by dividing by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained in this way is 0.3 or less.

式（１）及び式（２）において、Ｒ１，Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でも良く、直鎖状、分岐鎖状、環状であっても良い。また、Ｒ１とＲ２が結合し、環状構造となっていても良く、Ｂはベンゼン、ビフェニル、ナフタレン、アントラセン、フェナントレン及びこれらの炭化水素置換体のいずれかを示す。ｎは０または１である。
（２）前記（１）に記された方法により得られたリン含有エポキシ樹脂。
（３）前記（２）に記載のリン含有エポキシ樹脂を用いることを特徴とするリン含有ビニルエステル樹脂。
（４）前記（２）のリン含有エポキシ樹脂を必須成分とし、硬化剤を配合してなるリン含有エポキシ樹脂組成物。
（５）前記（３）のリン含有ビニルエステル樹脂を必須成分とし、ラジカル重合開始剤および／または硬化剤を配合してなるラジカル重合性樹脂組成物。
（６）前記（４）記載のリン含有エポキシ樹脂組成物を用いて得られる電子回路基板用材料。
（７）前記（４）記載のリン含有エポキシ樹脂組成物を用いて得られる封止材。
（８）前記（４）記載のリン含有エポキシ樹脂組成物を用いて得られる注型材。
（９）前記（４）から（８）のいずれかに記載のリン含有エポキシ樹脂組成物、ラジカル重合性樹脂組成物、電子回路基板用材料、封止材、注型材を硬化してなる硬化物。

In 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, branched or cyclic. R1 and R2 may be bonded to form a cyclic structure, and B represents benzene, biphenyl, naphthalene, anthracene, phenanthrene, or a hydrocarbon substituent thereof. n is 0 or 1.
(2) A phosphorus-containing epoxy resin obtained by the method described in (1) above.
(3) A phosphorus-containing vinyl ester resin characterized by using the phosphorus-containing epoxy resin described in (2).
(4) A phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin (2) as an essential component and a curing agent.
(5) A radical polymerizable resin composition comprising the phosphorus-containing vinyl ester resin of (3) as an essential component and a radical polymerization initiator and / or a curing agent.
(6) An electronic circuit board material obtained by using the phosphorus-containing epoxy resin composition according to (4).
(7) A sealing material obtained using the phosphorus-containing epoxy resin composition according to (4).
(8) A casting material obtained using the phosphorus-containing epoxy resin composition according to (4).
(9) A cured product obtained by curing the phosphorus-containing epoxy resin composition, radical polymerizable resin composition, electronic circuit board material, sealing material, and casting material according to any one of (4) to (8). .

  In the phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (1) with epoxy resins, the content (% by weight) of the compound represented by the general formula (2) in the system before the reaction is reacted. The value obtained by dividing by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained in this way is 0.3 or less, so that the gel time is delayed by using the phosphorus-containing epoxy resin. It is possible to provide a phosphorus-containing epoxy resin and an electronic circuit board material excellent in adhesive strength, migration resistance, solder immersion resistance, and storage stability in a prepreg.

  The phosphorus-containing epoxy resin of the present invention is obtained by reacting an epoxy resin with a compound represented by the general formula (1), but the content (% by weight) of the compound represented by the general formula (2) in the system before the reaction. ) By the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction, the value obtained is 0.3 or less, preferably 0.15 or less, more preferably 0.05 or less. is there. The compounds represented by general formula (1) and general formula (2) react with epoxy resins to change the structure and further contain a phosphorus element, and therefore are represented by general formula (2) in the system before the reaction. By dividing the content (% by weight) of the compound by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin after the reaction, the compound represented by the general formula (2) contained in the obtained phosphorus-containing epoxy resin By predefining the content ratio of the derivative as the content ratio before the reaction, it can be used as an index for controlling the curing reactivity of the phosphorus-containing epoxy resin. Furthermore, in addition to the phosphorus-containing compound represented by the general formula (1), even when at least one other phosphorus-containing compound (for example, cyclophenoxyphosphazene) is used in combination, the general formula ( By predefining the content of the compound represented by 2), it can be usefully used as an index for controlling the curing reactivity of the phosphorus-containing epoxy resin.

Examples of the compound represented by the general formula (1) used in the present invention include Non-Patent Document 1, Non-Patent Document 2, which is a general Russian magazine, Patent Document 7, Patent Document 8, Patent Document 9, and Patent Document 10. Obtained by the method shown. In Patent Literature 7, Patent Literature 8, and Patent Literature 9, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is always reacted with a quinone compound in a state where an equivalent amount or more exists. And the use of a reaction solvent as a washing solvent after the reaction is described. This is for the purpose of removing excessive phosphorus compounds.
IGMCampbell and IDR Stevens, Chemidal Communications, pp. 505-506 (1966) (Zh. Obshch. Khim.), 42 (11), 241-25-2418 (1972) JP 60-126293 A JP-A-61-2236787 JP-A-5-331179 JP 05-39345 A

  In addition, the compound represented by the general formula (1) is produced by the methods disclosed in Non-Patent Document 1, Non-Patent Document 2, and Patent Documents 7 to 10, and the production cost is reduced by purification means such as washing and recrystallization. It is known that the purity is increased to 99% or more. At that time, the compound represented by the general formula (2) is by-produced together with other impurities. The reaction formula is shown in Formula 1. Reaction formula 1 is an example in which the compound represented by general formula (1) and the compound represented by general formula (2) are produced, but the compound represented by general formula (3) represented in reaction formula 1 remains. .

Reaction formula 1

式中、Ｒ１，Ｒ２は水素または炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状、環状であってもよい。また、Ｒ１とＲ２が結合し、環状構造となっていてもよい。Ｂはベンゼン、ビフェニル、ナフタレン、フェナントレンおよびこれらの炭化水素置換体のいずれかを示す。ｎは０または１である。

In the formula, R1 and R2 each represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear, branched or cyclic. R1 and R2 may be bonded to form a cyclic structure. B represents benzene, biphenyl, naphthalene, phenanthrene, or any of these hydrocarbon substitutes. n is 0 or 1.

  The inventor of the present invention uses an amount of the epoxy resin obtained by using the compound represented by the general formula (1) containing the compound represented by the general formula (2) as an impurity component so that the crosslinking density decreases. Even with a small amount of the compound represented by the general formula (2), it was found that the reaction rate was remarkably delayed, leading to the present invention, which is unthinkable with conventional monofunctional phenols. It was found that the delay effect of the reaction rate of the epoxy resin was particularly large. Therefore, in addition to refining the compound represented by the general formula (1) at a higher production cost to obtain a high purity, management of the components of the compound represented by the general formula (2) It is possible to solve the problems when used as a stopper or casting material.

  A value obtained by dividing the content (% by weight) of the compound represented by the general formula 2 in the system before the reaction by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction is 0. The resulting phosphorus-containing epoxy resin has a small effect on the reactivity with the curing agent. That is, a value obtained by dividing the content (% by weight) of the compound represented by the general formula (2) by the phosphorus content (% by weight) is 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less. , Desirably 0.05 or less and react to obtain an epoxy resin. Epoxy resins containing a compound represented by the general formula (2) whose content (wt%) divided by phosphorus content (wt%) exceeds 0.3 are reactive with curing agents. Since it delays remarkably, it becomes inferior to practicality.

  The compound represented by the general formula (1) used in the present invention can be produced by the methods disclosed in Non-Patent Documents 1 and 2 and Patent Documents 7 to 10, and extraction, washing, recrystallization, The compound represented by the general formula 2 can be reduced by a purification operation such as distillation. Moreover, you may reduce the compound shown by General formula (2) with the reaction conditions of the compound shown by General formula 1 irrespective of these methods.

Specific examples of the compound represented by the general formula (1) include HCA-HQ represented by Structural Formula 1 (10- (2,5-dihydroxyphenyl) -10-dihydro-9-oxa-10 manufactured by Sanko Co., Ltd.). -Phosphaphenanthrene-10-oxide), HCA-NQ represented by structural formula 2 (10- (2,7-dihydroxynaphthyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) , PPQ (Dioxinphosphinylhydroquinone), Diphenylphosphinylnaphthoquinone, CPHO-HQ (Cyclooctylenephosphinyl-1,4-benzenediol manufactured by Nippon Chemical Industry Co., Ltd.), Cyclooctylenephos Finyl-1,4-naphthalenediol, phosphorus-containing disclosed in JP-A-2002-265562 Phenol compounds, and the like, but may be used in combination of two or more.
Structural formula 1

構造式２

Structural formula 2

  Epoxy resins that react with the compound represented by the general formula (1) preferably have a glycidyl ether group. Specifically, Epototo YDC-1312, ZX-1027 (Hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), ZX-1251 (Biphenol type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YD-127, Epototo YD-128, Epototo YD-8125, Epototo YD-825GS, Epototo YD-011, Epototo YD-900, Epototo YD-901 (BPA type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epototo YDF-170, Epototo YDF-8170, Epototo YDF-70G Epototo YDF-2001 (BPF type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDCN 701 (Cresol novolac type epoxy resin manufactured by Toto Kasei Co., Ltd.), ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Toto Kasei Co., Ltd.), NC-3000 (Biphenylaralkylphenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), EPPN- 501H, EPPN-502H (Nippon Kayaku Co., Ltd. polyfunctional epoxy resin) ZX-1355 (Toto Kasei Co., Ltd. naphthalenediol type epoxy resin), ESN-155, ESN-185V, ESN-175 (Toto Kasei Co., Ltd.) β-naphthol aralkyl epoxy resin), ESN-355, ESN-375 (manufactured by Tohto Kasei Co., Ltd., dinaphthol aralkyl epoxy resin), ESN-475V, ESN-485 (manufactured by Toto Kasei Co., Ltd., α-naphthol aralkyl epoxy resin) An epoxy resin produced from a phenolic compound such as a polyhydric phenol resin and the like, and an epihalohydrin, an amine compound such as Epototo YH-434, Epototo YH-434GS (diaminodiphenylmethane tetraglycidyl ether manufactured by Toto Kasei Co., Ltd.), and an epihalohydrin An epoxy resin produced from carboxylic acids such as YD-171 (a dimer acid type epoxy resin manufactured by Toto Kasei Co., Ltd.) and an epihalohydrin, and the like are not limited to these. You may use together more than a kind. However, the value obtained by dividing the content (% by weight) of the compound represented by the general formula 2 in the system before the reaction by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction. It must be charged so that it is 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less, and desirably 0.05 or less.

  As a synthesis method, similarly to the reaction of ordinary polyfunctional phenols and epoxy resins, the compound represented by the general formula (1) and the epoxy resins are charged and reacted by heating and melting. However, it was obtained by dividing the content (% by weight) of the compound represented by the general formula (2) in the system before the reaction by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction. The value should be 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less, and desirably 0.05 or less. The reaction is carried out at 100 to 200 ° C., more preferably 120 to 180 ° C. with stirring as the reaction temperature. If the rate of this reaction is slow, a catalyst can be used as needed to improve productivity. Specific catalysts include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, Various catalysts such as phosphonium salts such as phenylphosphonium bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used. A reaction solvent may be used depending on the viscosity during the reaction. Specific examples include benzene, toluene, xylene, cyclopentanone, cyclohexanone, and the like, but are not limited thereto, and two or more kinds may be used.

  Various epoxy resin modifiers may be used in combination as required. However, the value obtained by dividing the content (% by weight) of the compound represented by the general formula 2 in the system before the reaction by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction. It must be charged so that it is 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less, and desirably 0.05 or less. Examples of the modifier include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, methyl hydroquinone, dimethyl hydroquinone, dibutyl hydroquinone, resorcin, methyl resorcin, biphenol, tetramethyl biphenol, dihydroxynaphthalene, dihydroxy diphenyl ether, dihydroxy stilbene, Various phenols such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, terpene phenol resin, heavy oil modified phenol resin, brominated phenol novolak resin, Various phenols and hydroxybenzaldehyde, Polyhydric phenol resin obtained by condensation reaction with various aldehydes such as crotonaldehyde, glyoxal, aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone , Diaminodiphenyl sulfide, diaminodiphenyl sulfone, bis (aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bis Aminophenoxyphenyl ether, bisaminophenoxy Phenyl, bis aminophenoxy phenyl sulfone, bis aminophenoxy phenyl propane, amine compounds such as diamino naphthalene.

  The phosphorus content of the phosphorus-containing epoxy resin used in the present invention is preferably 0.3 to 4% by weight, more preferably 0.5 to 3.6% by weight, still more preferably 1.0 to 3.1% by weight. The phosphorus content in the organic component in the phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin is preferably 0.2 to 4% by weight, more preferably 0.4 to 3.5% by weight, Preferably it is 0.6 to 3 weight%. If the content of phosphorus in the organic component in the phosphorus-containing epoxy resin composition 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. It is desirable to adjust from 2% by weight to 4% by weight.

  The epoxy equivalent of the phosphorus-containing epoxy resin used in the present invention is preferably 200 to 1500 g / eq, more preferably 250 to 1000 g / eq, and still more preferably 300 to 800 g / eq. When the epoxy equivalent is less than 200 g / eq, the adhesiveness is inferior, and when it exceeds 1500 g / eq, the heat resistance is adversely affected, so it is desirable to adjust to 200-1500 g / eq.

  As the curing agent of the phosphorus-containing epoxy resin composition of the present invention, it is possible to use usually used curing agents for epoxy resins such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters. These curing agents may be used alone or in combination of two or more.

  The phosphorus-containing epoxy resin composition of the present invention may contain a curing accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine, and an imidazole as necessary.

  In the phosphorus-containing epoxy resin composition of the present invention, an organic solvent can also be used for viscosity adjustment. Examples of organic solvents that can be used include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, benzene and toluene. Aromatic hydrocarbons etc. are mentioned, Only one type of these solvents may be used or two or more types may be used, and it can mix | blend in the range of 30 to 80 weight% as an epoxy resin density | concentration.

  Fillers used in the phosphorus-containing epoxy resin composition of the present invention include aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, fine powder silica, fused silica, crystalline silica, silica Examples include inorganic fillers such as balloons, but pigments and the like may be blended. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, when metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant aid and can ensure flame retardancy even if the phosphorus content is small. In particular, if the blending amount is not 10% or more, the impact resistance effect is small. However, if the blending amount exceeds 150%, the adhesiveness, which is a necessary item for use in a laminated board, is lowered. Moreover, organic fillers, such as fibrous fillers, such as a silica, glass fiber, a pulp fiber, a synthetic fiber, a ceramic fiber, fine particle rubber, and a thermoplastic elastomer, can also be contained in the said resin composition.

  Examples of the electronic circuit board material obtained from the phosphorus-containing epoxy resin composition as described above include resin sheets, metal foils with resin, prepregs, and laminates. The method for producing the resin sheet is not particularly limited. For example, a phosphorus-containing epoxy resin composition as described above is preferably 5 on a carrier film that does not dissolve in an epoxy resin composition such as a polyester film or a polyimide film. After applying to a thickness of ˜100 μm, it is dried by heating at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. A resin sheet is generally formed by a method called a casting method. At this time, if the sheet to which the phosphorus-containing epoxy resin composition is applied is previously subjected to a surface treatment with a release agent, the molded resin sheet can be easily peeled off. Here, the thickness of the resin sheet is preferably 5 to 80 μm.

  Next, the resin-coated metal foil obtained with the phosphorus-containing epoxy resin composition as described above will be described. As the metal foil, copper, aluminum, brass, nickel or the like alone, alloy, or composite metal foil can be used. It is preferable to use a metal foil having a thickness of 9 to 70 μm. The method for producing a flame retardant resin composition containing a phosphorus-containing epoxy resin and a metal foil with a resin from the metal foil is not particularly limited. For example, the phosphorus-containing epoxy resin composition is formed on one surface of the metal foil. A resin varnish whose viscosity is adjusted with a solvent is applied using a roll coater or the like, and then dried by heating to semi-cure the resin component (B-stage) to form a resin layer. In semi-curing the resin component, for example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes. Here, as for the thickness of the resin part of metal foil with resin, it is desirable to form in 5-110 micrometers.

  Next, the prepreg obtained using the above phosphorus-containing epoxy resin composition will be described. As the sheet-like substrate, inorganic fibers such as glass, or woven or non-woven fabrics of organic fibers such as polyester, polyamine, polyacryl, polyimide, Kevlar, etc. can be used, but it is not limited thereto. The method for producing the prepreg from the phosphorus-containing epoxy resin composition and the base material is not particularly limited. For example, the base material is impregnated by immersing the epoxy resin composition in a resin varnish whose viscosity is adjusted with a solvent. Thereafter, the resin component is obtained by heat-drying and semi-curing (B-stage), and can be heat-dried at 100 to 200 ° C. for 1 to 40 minutes, for example. Here, the amount of resin in the prepreg is preferably 30 to 80% by weight.

  Next, a method for producing a laminate using the above resin sheet, metal foil with resin, prepreg and the like will be described. When a prepreg is used to form a laminate, one or more prepregs are laminated, a metal foil is arranged on one or both sides to form a laminate, and this laminate is heated and pressurized to be laminated and integrated. . Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel or the like can be used. Conditions for heating and pressurizing the laminate may be adjusted as appropriate under the conditions for curing the epoxy resin composition, but heating and pressurizing may be performed. However, if the pressure of the pressurization is too low, bubbles remain in the resulting laminate. In addition, since electrical characteristics may deteriorate, it is preferable to apply pressure under conditions that satisfy the moldability. For example, the temperature can be set to 160 to 220 ° C., the pressure can be set to 49.0 to 490.3 N / cm 2 (5 to 50 kgf / cm 2), and the heating and pressing time can be set to 40 to 240 minutes. Furthermore, a multilayer board can be produced by using the single-layer laminated board thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution to perform a blackening process to obtain an inner layer material. An insulating layer is formed with a resin sheet, a metal foil with resin, or a prepreg on one or both sides of the inner layer material, and a multilayer plate is formed by forming a conductor layer on the surface of the insulating layer. Is. When the insulating layer is formed with a resin sheet, a laminate is formed by arranging resin-attached sheets on the circuit forming surfaces of a plurality of inner layer materials. Or a resin sheet is arrange | positioned between the circuit formation surface of an inner-layer material, and metal foil, and a laminated body is formed. Then, the laminate is heated and pressed to be integrally formed, whereby a cured product of the resin sheet is formed as an insulating layer, and a multilayered inner layer material is formed. Alternatively, the inner layer material and the metal foil as the conductor layer are formed by using a cured resin sheet as an insulating layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer material can also be used. Further, the heating and pressing can be performed under the same conditions as the formation of the inner layer material. When an insulating layer is formed by applying a resin to a laminate, the outermost circuit forming surface resin of the inner layer material is a phosphorus-containing epoxy resin composition or a flame-retardant epoxy resin composition containing a phosphorus-containing epoxy resin. Preferably, after coating to a thickness of 5 to 100 μm, it is dried by heating at 100 to 200 ° C. for 1 to 90 minutes to form a sheet. It is generally formed by a method called a casting method. The thickness after drying is preferably 5 to 80 μm. A printed wiring board can be formed by further forming via holes and circuits on the surface of the multilayer laminate formed as described above by an additive method or a subtractive method. Further, by repeating the above method using this printed wiring board as an inner layer material, a multilayer board can be formed. When the insulating layer is formed of a metal foil with resin, the metal foil with resin is overlapped on the circuit formation surface of the inner layer material so that the resin layer of the metal foil with resin faces the circuit formation surface of the inner layer material. Arrange to form a laminate. Then, by heating and pressing this laminate to integrally form it, a cured product of the resin layer of the resin-coated metal foil is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, the heat and pressure molding can be performed under the same conditions as the formation of the inner layer material. When an insulating layer is formed with a prepreg, a laminate is formed by placing one or a plurality of prepregs laminated on the circuit forming surface of the inner layer material, and further placing a metal foil on the outside thereof. . Then, the laminate is heated and pressed to be integrally formed, whereby a cured product of the prepreg is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer board can also be used. Further, the heating and pressing can be performed under the same conditions as the formation of the inner layer material. A printed wiring board can be formed by further forming via holes and circuits on the surface of the multilayer laminate formed as described above by an additive method or a subtractive method. Further, by repeating the above method using this printed wiring board as an inner layer material, a multilayer board can be formed.

  As a result of evaluating the characteristics of the laminate obtained using the phosphorus-containing epoxy resin of the present invention and the composition, the content of the compound represented by the general formula (1) is 2.5% by weight or less. The phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (2) with epoxy resins has high reactivity with a curing agent, and the prepreg has a good balance between the flowability and curability of the resin during curing. And the laminated board obtained by heat-curing the prepreg had a flame retardance without containing a halide, and was a resin composition excellent in soldering heat resistance.

  EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these. The content rate of the compound shown by General formula 2 contained in the compound shown by General formula 1 was measured using HPLC. An Agilent 1100 series device manufactured by Hewlett Packard was used, and a column of CD006 of Cadenza CD-C18 manufactured by Imtakt was used. Water and methanol were used as eluents, sample measurement was started with 60% methanol, and a gradient was made so as to be 100% methanol in 16 minutes. The flow rate was 0.5 ml / min, and measurement was performed with a UV detector at a wavelength of 266 nm. In addition, flame retardancy was measured according to UL (Underwriter Laboratories) standards. The varnish gel time was measured at 160 ° C. The copper foil peel strength was measured in accordance with JIS C 6481 5.7, and the interlayer adhesion was measured by peeling between one prepreg and the remaining three sheets in accordance with JIS C 6481 5.7. 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 examined by visual inspection, and the case where there was no swelling or peeling was rated as “X”. Moreover, the glass transition temperature of the hardened | cured material and the hardening calorific value were measured by Seiko Instruments Inc. Exster6000. Curing calorific value retention rate is the percentage of the total curing calorific value of prepreg after storage for 72 hours at 60 ° C, where the total curing calorific value of prepreg immediately after preparation is 100%. It shows that stability is bad.

(Confirmation of the structure of the compound represented by the general formula 2)
HPLC of HCA-HQ represented by Structural Formula 1 as a compound of General Formula 1 was measured. Moreover, this was fractionated, the delay component of hardening reaction was taken out, and it measured by FD-MASS, FTIR, and proton NMR. From the MASS measurement result, the molecular weight was 324, and when the FTIR result was compared with HCA-HQ, a decrease in phenolic hydroxyl group, a decrease in benzene 3-substitution, and an increase in benzene 2-substitution were observed. From the proton NMR results, it was confirmed that HCA was bonded at the p-position to the hydroxyl group derived from hydroquinone. From the above, the peak at 13.6 minutes was confirmed as structural formula 3. As a compound of the general formula 1, 10- (2,7-dihydroxynaphthyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was analyzed in the same manner, and the component of the structural formula 4 was confirmed.
Structural formula 3

構造式４

Structural formula 4

Synthesis example 1
In a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction device, 31.72 parts by weight of HCA-HQ and YDF-170 68.28 as a compound represented by the general formula 1 A part by weight was charged and heated to 120 ° C. in a nitrogen atmosphere. As a catalyst, 0.32 parts by weight of triphenylphosphine was added and reacted at 160 ° C. for 4 hours. The purity of the compound represented by the general formula 1 was 99.5% by weight. The content of the compound represented by the general formula 2 contained in the reaction system, specifically the compound represented by the structural formula 3, was 0.003% by weight. The epoxy equivalent of the obtained epoxy resin was 480.0 g / eq, and the phosphorus content was 3.0% by weight.
Synthesis example 2
The same procedure as in Synthesis Example 1 was performed except that the compound represented by the general formula 2 and specifically the compound HCA-HQ represented by the general formula 1 containing 0.17% by weight of the compound represented by the structural formula 3 was used. I did it. The purity of the compound represented by the general formula 1 was 99.4% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.05% by weight. The epoxy equivalent of the obtained epoxy resin was 484.1 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis example 3
The same operation as in Synthesis Example 1 was performed except that the compound represented by the general formula 2 and specifically the compound HCA-HQ represented by the general formula 1 containing 0.33% by weight of the compound represented by the structural formula 3 was used. I did it. The purity of the compound represented by the general formula 1 was 99.1% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.10% by weight. The epoxy equivalent of the obtained epoxy resin was 488.4 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis example 4
The same operation as in Synthesis Example 1 was performed except that the compound represented by the general formula 2 and specifically the compound HCA-HQ represented by the general formula 1 containing 0.65% by weight of the compound represented by the structural formula 3 was used. I did it. The purity of the compound represented by the general formula 1 was 98.7% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.21% by weight. The epoxy equivalent of the obtained epoxy resin was 488.3 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis example 5
The same operation as in Synthesis Example 1 was performed except that the compound represented by the general formula 2 and specifically the compound HCA-HQ represented by the general formula 1 containing 0.95% by weight of the compound represented by the structural formula 3 was used. I did it. The purity of the compound represented by the general formula 1 was 98.2% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.30% by weight. The epoxy equivalent of the obtained epoxy resin was 487.7 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis Example 6
The same procedure as in Synthesis Example 1 was performed except that the compound represented by the general formula 2 and specifically the compound HCA-HQ represented by the general formula 1 containing 1.20% by weight of the compound represented by the structural formula 3 was used. I did it. The purity of the compound represented by the general formula 1 was 97.9% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.38% by weight. The epoxy equivalent of the obtained epoxy resin was 486.3 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis example 7
An apparatus similar to that of Synthesis Example 1 was charged with 21.15 parts by weight of HCA and 50 parts by weight of toluene, heated to 75 ° C. in a nitrogen atmosphere, and dissolved. To this, 10.47 parts by weight of parabenzoquinone was charged little by little over 30 minutes, maintained at 85 ° C. for 30 minutes, then heated, and reacted at reflux temperature for 3 hours. The content of the compound represented by the general formula 2 contained in the generated compound HCA-HQ represented by the general formula 1, specifically the compound represented by the structural formula 3, was 2.40% by weight. Further, the purity of the compound represented by the general formula 1 was 95.0% by weight. This was charged with 68.39 parts by weight of YDF-170, heated to 150 ° C., and toluene was removed under reflux. The content of the compound represented by the general formula 2 contained in the reaction system was 0.76% by weight. 0.32 part by weight of triphenylphosphine was added and reacted at 160 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin was 470.2 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis example 8
In a device similar to Synthesis Example 1, the compound HCA-HQ represented by the general formula 2 in which the content of the compound represented by the general formula 2 and specifically the compound represented by the structural formula 3 is 0.01% by weight is added. 31.09 parts by weight, 0.63 part by weight of HCA and 68.28 parts by weight of YDF-170 were charged, and the same operation as in Synthesis Example 1 was performed. The purity of the compound represented by the general formula 1 was 97.3% by weight with respect to the total of charged HCA and HCA-HQ. The content of the compound represented by the general formula 2 contained in the reaction system was 0.003% by weight. The epoxy equivalent of the obtained epoxy resin was 480.3 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis Example 9
A compound represented by the general formula 1, specifically a compound represented by the general formula 1 in which the content of the compound represented by the structural formula 4 is 0.15% by weight, specifically a compound represented by the structural formula 2 The same operation as in Synthesis Example 1 was carried out except that 26.86 parts by weight and 73.14 parts by weight of YDF-8170 were used. The purity of the compound represented by the compound represented by the general formula 1 was 90.1% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.04% by weight. The epoxy equivalent of the obtained epoxy resin was 321.8 g / eq, and the phosphorus content was 2.2% by weight.

Synthesis Example 10
The same procedure as in Synthesis Example 1 was performed except that the compound represented by the general formula 2 and specifically the compound HCA-HQ represented by the general formula 1 containing 3.10% by weight of the compound represented by the structural formula 3 was used. I did it. The purity of the compound represented by the general 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
In the same apparatus as in Synthesis Example 1, 21.15 parts by weight of HCA and 40 parts by weight of toluene were charged, heated to 75 ° C. under a nitrogen atmosphere, and dissolved. 69.13 parts by weight of YDF-170 was charged and dissolved, and 9.73 parts by weight of parabenzoquinone was added little by little over 2 hours. After completion of the addition, the mixture was kept at the reflux temperature for 3 hours, and then toluene was removed by reflux. Then, 0.32 parts by weight of triphenylphosphine was added, and the reaction was carried out at 160 ° C. for 4 hours. The content of the compound represented by the general formula 2 contained in the compound HCA-HQ represented by the general formula 1 was 3.50% by weight. The purity of the compound represented by the general formula 1 was 69.4% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 1.08% by weight. The epoxy equivalent of the obtained epoxy resin was 444.4 g / eq, and the phosphorus content was 3.0% by weight.

Synthesis Example 12
A compound represented by general formula 2, specifically, a compound represented by general formula 1 containing 2.60% by weight of a compound represented by structural formula 4, specifically, a compound represented by structural formula 2 was used. The same operation as in Synthesis Example 9 was performed. The purity of the compound represented by the general formula 1 was 77.0% by weight. The content of the compound represented by the general formula 2 contained in the reaction system was 0.70% by weight. The epoxy equivalent of the obtained epoxy resin was 321.4 g / eq, and the phosphorus content was 2.2% by weight.

The epoxy resin, dicyandiamide curing agent, and imidazole curing accelerator obtained in each synthesis example were blended according to the formulation shown in Table 1 and Table 2, and dissolved in a solvent to evaluate the laminate. Tables 1 and 2 summarize the results of Examples 1-9 and Comparative Examples 1-3. A phenol novolak resin curing agent and an imidazole curing accelerator were blended according to the blending formulation shown in Table 3, and dissolved in a solvent to evaluate the reactivity by gel time. Table 3 summarizes the results of Examples 10 to 12 and Comparative Example 4. Table 4 summarizes the storage stability evaluation when the amount of catalyst is adjusted in Example 13 and Comparative Example 5 to adjust the gel time to the same degree as the retention rate (%) of curing heat generation.

  As is clear from the physical properties described in Tables 1, 2, and 3, when the content of the compound represented by the general formula 2 is increased, the gel time is remarkably slowed and the curing reactivity is affected. In Tables 1 and 2, the dicyandiamide curing agent was evaluated, and in Table 3, the phenol novolac resin curing agent was evaluated. When any of the curing agents has a high content of the compound represented by Formula 2, the gel time is increased. Is significantly slowed down, indicating that it has an effect regardless of the type of curing agent. For example, when a laminate is prepared, the resin component is insufficient, resulting in problems such as a decrease in adhesive strength, occurrence of migration, blistering and cracking during solder immersion. Moreover, in order to adjust the gel time as shown in Comparative Example 5 in Table 4, when the blending amount of the curing catalyst is increased, the heat generation retention rate of the curing is reduced, and the storage stability in the prepreg is deteriorated so that long-term storage is possible. There are problems such as being unable to do so.

Claims (9)

In the method for producing a phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (1) with epoxy resins, the content (% by weight) of the compound represented by the general formula (2) in the system before the reaction A value obtained by dividing the above by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction is 0.3 or less.

In 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, branched or cyclic. R1 and R2 may be bonded to form a cyclic structure, and B represents benzene, biphenyl, naphthalene, anthracene, phenanthrene, or a hydrocarbon substituent thereof. n is 0 or 1.   A phosphorus-containing epoxy resin obtained by the method described in claim 1. A phosphorus-containing vinyl ester resin using the phosphorus-containing epoxy resin according to claim 2. A phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin according to claim 2 as an essential component and a curing agent.   A radical polymerizable resin composition comprising the phosphorus-containing vinyl ester resin according to claim 3 as an essential component and a radical polymerization initiator and / or a curing agent.   An electronic circuit board material obtained using the phosphorus-containing epoxy resin composition according to claim 4.   The sealing material obtained using the phosphorus containing epoxy resin composition of Claim 4.   A casting material obtained using the phosphorus-containing epoxy resin composition according to claim 4.   Hardened | cured material formed by hardening | curing the phosphorus containing epoxy resin composition in any one of Claims 4-8, a radically polymerizable resin composition, the material for electronic circuit boards, a sealing material, and a casting material.