WO2009096235A1

WO2009096235A1 - Phosphorus-containing epoxy resin, phosphorus-containing epoxy resin composition, method for producing phosphorus-containing epoxy resin, curable resin composition using the epoxy resin and the epoxy resin composition, and cured product

Info

Publication number: WO2009096235A1
Application number: PCT/JP2009/050494
Authority: WO
Inventors: Tetsuya Nakanishi; Kazuo Ishihara
Original assignee: Tohto Kasei Co., Ltd.
Priority date: 2008-02-01
Filing date: 2009-01-08
Publication date: 2009-08-06
Also published as: JP5587542B2; TWI491637B; TW200946553A; JP2009185087A

Abstract

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

Description

Description Phosphorus-containing epoxy resin and phosphorus-containing epoxy resin composition, production method thereof, curable resin composition and cured product using the resin, and the resin composition TECHNICAL FIELD

The present invention relates to an epoxy resin composition for producing a copper-clad laminate, a film material, a resin-coated copper foil, etc. used for an electronic circuit board, and a sealing material, a molding material, a casting material, an adhesive, 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 production method thereof, a curable resin composition using the resin, and a cured product. Background art

Epoxy resins are widely used in electronic parts, electrical equipment, automotive parts, FR, sports equipment, etc. due to their excellent adhesiveness, heat resistance, and moldability. In particular, copper-clad laminates and encapsulants used in electronic parts and electrical equipment are strongly required to have safety such as fire prevention and delay. Brominated epoxy resins with these characteristics have been used so far. Is used. Although it has a problem of high specific gravity, flame retardancy is imparted by introducing halogen, especially bromine, into epoxy resin, and 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 high specific gravity are undesirable materials from the viewpoint of recent light weight trends, and when used at high temperatures for long periods of time, halide dissociation occurs, This may cause wiring corrosion. In addition, halogens and other harmful substances are generated during the combustion of used electronic parts and electrical equipment, and the use of halogens has become a problem from the viewpoint of environmental safety. It came to be. As a known document regarding the compound represented by the general formula (1) described in the claims, Patent Document 1 includes HCA—HQ (manufactured by Sanko Co., Ltd. 10— (2,5-dihydroxyphenyl) —9, 10— A thermosetting resin obtained by reacting dihydro 9-oxa 1 10-phosphaphenanthrene 1 1 0-oxide) with epoxy resins at a predetermined molar ratio is disclosed. Patent Document 2 discloses a method for producing a phosphorus-containing epoxy resin obtained by reacting an epoxy compound having at least two epoxy groups with diphenylphosphylhydroquinone. 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 polyvalent phenol compound represented by the general formula (2) with an epoxy resin. In Patent Document 5, 9, 10-dihydro-9 monooxa 1 0 -phosphaphenanthrene 1 0-oxide and 1,4-benzobenzoquinone and / or 1,4-naphthoquinone are added to the total water content in the reaction system. The reaction is controlled so that the amount is not more than 0.3% by weight with respect to the total amount of 9,10-dihydro-9 mono-oxa 10-phosphaphenanthrene 10-oxide used in the reaction. It is difficult to contain phosphorus by carrying out step 2 of reacting with bisphenol A type epoxy resin and / or bisphenol F type epoxy resin without purifying the reaction composition obtained in step 1 and step 1 to obtain the composition. A method for producing a flammable bisphenol type epoxy resin is disclosed.

Patent Document 1: Japanese Patent Application Laid-Open No. 04-1- 1 6 6 2

Patent Document 2: Japanese Patent Laid-Open No. 05-5-21400

Patent Document 3: Japanese Patent Laid-Open No. 2 00 0-3 0 9 6 2 4

Patent Document 4: Japanese Patent Laid-Open No. 2 0 2-2 6 5 5 6 2

Patent Document 5: Japanese Patent Laid-Open No. 2 0 06-3 4 2 2 1 7

However, none of the patent documents describes the curing agent and curability.

Patent Document 6 discloses monofunctionality including structural formula 3, which is a compound represented by the general formula (2). There is a description of organophosphorus compounds of “there is a reaction with an epoxy group to form a so-called vent in the resin, so that the crosslinking density of the epoxy resin is reduced, the curing speed is delayed, the heat resistance is lowered, or the machine It is difficult to use an amount that is sufficient to exhibit sufficient flame retardancy, such as a reduction in the mechanical strength, and a monofunctional organic compound as a reactive organic phosphorus compound. Use of phosphorus compounds that are sufficiently flame retardant (generally dozens of weight percent to several tens of weight percent) reduces crosslink density and causes problems such as slowing of the curing rate. Is described.

Patent Document 6: Japanese Patent Application Laid-Open No. 2100

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. When the gel time, which is an indicator of the reactivity of epoxy resin, is long, the resin flows too much, for example, during curing during lamination, and the resulting laminate has insufficient adhesion, resulting in a decrease in adhesive strength. Problems such as migration and 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 that the storage stability of the pre-preda is deteriorated and long-term storage cannot be performed. As a result of intensive studies to solve the above problems, the present inventor has found that the phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (1) with the epoxy resin, the content of the compound represented by the formula (2) (wt. / _0), the value obtained by dividing the re down content of Li down-containing epoxy resin obtained by reaction with (percent by weight) of 0. It has been found that the curing reactivity of the epoxy resin is remarkably impaired when exceeding 3, and the phosphorus-containing epoxy resin of the present invention has been completed. Means for solving the above-mentioned problems is the scope of the claims. Is as follows.

(1) In a phosphorus-containing epoxy resin obtained by reacting a compound represented by the general formula (1) with an epoxy resin, the compound represented by the general formula (2) in the system before the reaction The phosphorus-containing epoxy is characterized in that the value obtained by dividing the ratio (% by weight) by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction is 0.3 or less. Manufacturing method of resin.

(R 1)

I

(R 2)-(O) n- P = 0 (1) H O— (B ^ -O H

(R 1)

(R 2)-(O) n- I P = 0 (2) O- (B) -0 H

In the formulas (1) and (2), R 1 and R 2 represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear, branched, or cyclic. . In addition, R 1 and R 2 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 bule 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 of (2) as an essential component and a curing agent.

(5) A radically polymerizable resin composition comprising the phosphorus-containing butyl 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 described in (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 described in (4). (9) The epoxy resin composition, the radical polymerizable resin composition, the electronic circuit board material, the sealing material, and the casting material according to any one of (4) to (8) are cured. Cured product. BEST MODE FOR CARRYING OUT THE INVENTION

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). The content of the compound represented by the general formula (2) in the system before the reaction ( (% By weight) divided 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 Is less than 0.05. The compounds represented by the general formula (1) and the general formula (2) react with epoxy resins to change their structure and further contain a phosphorus element. Therefore, they are represented by the general formula (2) in the system before the reaction. the content of the compound (wt. / ₀₎ by dividing the phosphorus content of the phosphorus-containing E port carboxymethyl resin after reaction (wt%), and generally is contained in the phosphorus-containing epoxy resins obtained equation (2 ) Can be used as an index for controlling the curing reactivity of the phosphorus-containing epoxy resin by pre-defining the content ratio of the compound represented by) as the content ratio before the reaction. Further, in addition to the phosphorus-containing compound represented by the general formula (1), even if at least one other phosphorus-containing compound (for example, cyclophenoxyphosphazene) is used in combination, the entire phosphorus-containing compound By predefining the content of the compound represented by the general formula (2) in the interior, it can be usefully used as an index for controlling the curing reactivity of the phosphorus-containing epoxy resin.

The compound represented by the general formula (1) used in the present invention is, for example, Non-Patent Document 1, Non-Patent Document 2, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 9 It is obtained by the method shown in 10. In Patent Document 7, Patent Document 8, and Patent Document 9, HCA (9, 10-dihydro-9 monoxa 1 0-phosphaphenanthrene 1 10-oxide) is always present in an equivalent amount or more with respect to the quinone compound. The reaction is described, and it is described that the reaction solvent is used as a washing solvent after the reaction. this Is intended to remove excess phosphorus compounds.

Non-Patent Document 1: I. G. M. Campbell and I. D. R. Stevens, Chemidal Communications, pp. 505-506 (1 9 6 6)

Non-Patent Document 2: (Zh. Obshch. Khim.), 42 (11), pp. 2415-2418 (1 9 7 2) Patent Document ：: Japanese Patent Application Laid-Open No. Sho 60- 1 2 6 2 93

Patent Document 8: Japanese Patent Laid-Open No. 6 1-2 3 6 7 8 7

Patent Document 9: JP-A-5-3 3 1 1 7 9

Patent Document 10: Japanese Patent Application Laid-Open No. 0-5-3939 45

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

(1)

(R 2)-(O) n-P = 0 + 0 = (B) = 0 →

H

(3) (4)

1) (R 1)

(R 2)-(O) n-P = 0 + (R 2)-(O) n-P = 0 + (R 2)-(O) n-P = 0

H O ~ (B O H H O— (B) -0 H

(1) (3) (2) In the formula, R 1 and R 2 each represent hydrogen or a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic. . In addition, R 1 and R 2 are combined to form a ring structure. You can make it. B represents benzene, biphenyl, naphthalene, phenanthrene, or any of their hydrocarbon substitutes. n is 0 or 1.

The present inventor found that 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 is not so large as to reduce the crosslinking density. Even with a small amount of the compound represented by the general formula (2), it was found that the reaction rate was significantly delayed, and the present invention was reached, which is not considered in the conventional monofunctional phenol. It was found that the delay effect of the reaction rate of the epoxy resin was specifically large. Therefore, in addition to purifying the compound represented by the general formula (1) at a higher production cost to obtain a high purity, control of the components of the compound represented by the general formula (2) It can solve the problems when used for sealing materials and casting materials.

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 is 0.3 or less, and the obtained epoxy resin containing phosphorus has little influence on the reactivity with the curing agent. That is, the content of the compound represented by the general formula (2)

The value obtained by dividing (% by weight) by the phosphorus content (% by weight) is 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less, and preferably 0.05 or less. To obtain an epoxy resin. The compound represented by the general formula (2) has its content (wt%)

Epoxy resins containing more than 0.3 divided by (% by weight) are inferior in practicality because their reactivity with the curing agent is significantly delayed.

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 and 10, and extraction, washing, and recrystallization after the production. The compound represented by the general formula (2) can be reduced by purification operations such as distillation. Further, the compound represented by the general formula (2) may be reduced depending on the reaction conditions of the compound represented by the general formula (1) regardless of these methods.

Specific examples of the compound represented by the general formula (1) include HC A—H represented by the structural formula 1. Q (manufactured by Sanko Co., Ltd. 1 0- (2,5-dihydroxyphenyl) 1 1 0-dihydro-9-oxa 1 10-phosphaphenanthrene 1 10-oxide), HC A represented by structural formula 2 -NQ (1 0— (2,7—dihydroxy naphthyl) 1 1 0—dihydr 1-9—oxer 1 0—phosphaphenanthrene 1 0—oxide), PPQ (Difuenore, Hokuko Chemical Co., Ltd.) Phosphininohydroquinone), diphenenolephosphininolentotoquinone, C PHO—HQ (Cyclooctylene phosphiel 1,4-benzenediole made by Yomoto Chemical Co., Ltd.), cycloocty Renphosphininole 1,4-naphthalenediol, phosphorus-containing phenol compounds disclosed in Japanese Patent Laid-Open No. 2000-2 6 5 5 62, and the like may be mentioned, but two or more kinds may be used in combination.

Composition

Epoxy resins that react with the compound represented by the general formula (1) preferably have a glycidyl ether group. Specifically, Epototo YDC— 1 3 1 2, ZX— 1 0 2 7 (Hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), ZX— 1 2 5 1 (Bifnol type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YD— 1 2 7, Epo Tote YD— 1 2 8, Epototo YD— 8 1 2 5, Epototo YD— 8 2 5 GS, Epototo YD— 0 1 1, Epototo YD—900, Epototo YD— 9 0 1 (BPA type epoxy manufactured by Tohto Kasei Co., Ltd. Resin), Epototo YDF— 1 70, Epototo YD F— 8 1 70, Epototo YD F— 8 70 GS, Epototo Y DF— 200 1 (BPF type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epototo YD PN— '6 3 8 (Phenol nopolak type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epoto YDCN—70 1 (Crezo Lunopolak type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Z X- 1 2 0 1 (Made by Tohto Kasei Co., Ltd.) Bisphenol fluorene type epoxy resin), NC-3000 (Nippon Kayaku Co., Ltd., biphenyl alcohol phenol type epoxy resin), EP PN—500 1 H, EP PN-50 2 H (Nippon Kayaku Co., Ltd.) Multifunctional epoxy resin) ZX— 1 3 5 5 (East Naphthalenediol type epoxy resin manufactured by Tosei Kasei Co., Ltd.), E SN— 1 5 5, E SN— 1 85 V, ESN— 1 7 5 (0 Naphthol aralkyl type epoxy resin manufactured by Toto Kasei Co., Ltd.), E SN— 3 5 5; ES N- 3 7 5 (Ginaf Toll Aralkyl Type Epoxy Resin, Toto Kasei Co., Ltd.), E SN— 4 7 5 V, E SN— 4 8 5 (Alpha-Naph Toll Aralkyl Type Epoxy, Toto Kasei Corporation) Epoxy resins produced from phenolic compounds such as polyphenolic resins such as resin) and Epihaguchi hydrin, Epototo® 4 34, Epototo YH— 4 34 GS (Diaminodiphenylmethane manufactured by Tohto Kasei Co., Ltd.) Tetraglycidyl ether) and other carboxylic acids such as YD— 1 7 1 (Dimer acid type epoxy resin manufactured by Tohto Kasei Co., Ltd.) Although an epoxy resin produced from the polyhedrin the like may be used in combination of two or more kinds it is not limited thereto. However, it is obtained by dividing the content (wt%) of the compound represented by the general formula (2) in the system before the reaction by the phosphorus content (wt%) of the phosphorus-containing epoxy resin obtained by the reaction. The resulting value should be 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less, and preferably 0.05 or less. The synthesis method is the same as the reaction of normal polyfunctional funinols and epoxy resins. A compound represented by the general formula (1) and an epoxy resin are charged and reacted by heating and melting. However, it is 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 with stirring at a reaction temperature of 10 00 to 20 0 ^, more preferably 1 2 0 to 1 80 80 ¾. If the rate of this reaction is slow, a catalyst can be used to improve productivity if necessary. Specific catalysts include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, tris (2, 6 Various catalysts such as phosphines such as phosphine, phosphonium salts such as etyltriphenyl phosphonium bromide, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used. Depending on the viscosity during the reaction, a reaction solvent may be used. Specific examples include benzene, toluene, xylene, cyclopentanone, and cyclohexanone, but are not limited to these, and two or more types may be used.

Various epoxy resin modifiers may be used in combination as required. However, by dividing the content (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 obtained value should be 0.3 or less, preferably 0.15 or less, more preferably 0.1 or less, and desirably 0.05 or less. Denaturing agents include bisphenol Α, bisphenol-nore F, bisphenolenore AD, tetrobinorebisphenolenole A, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, biphenol, tetramethyl. Biphenol, Dihydroxyaphthalene, Dihydroxydiphenenoleethenole, Dihydroxyoxy / Lebens, phenol novolac resin, cresolol nopolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, Naf Tollnovo Various phenols such as lac resin, terpene phenol resin, heavy oil-modified phenol resin, brominated phenol novolac resin, various phenols and hydroxy aldehydes, croton aldehydes, and various aldehydes such as dario oxal Polyhydric phenol resin obtained by condensation reaction with, aniline, phenylene diamine, toluidine, xylidine, jetyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenylketone , Diaminodiphenylsulfide, diaminodiphenylsulfone, bis (aminophenol) fluorene, diaminojetyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide , Diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bisaminophenoxypheneoleatere, bisaminophenoxypheneole, bisaminophenoxyrenolephone, Examples include amine compounds such as bisaminophenoxyphenolepropane and diaminonaphthalene.

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, and still more preferably 1.0 to 3.1% by weight. The content of phosphorus 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. / ₀ , more preferably 0.6 to 3% by weight. The phosphorus content in the organic component of the phosphorus-containing epoxy resin composition is 0.2 wt. / If it is less than ₀ , it is difficult to ensure flame retardancy, and if it is more than 5% by weight, the heat resistance is adversely affected, so it is desirable to adjust from 0.2% to 4% by weight.

The epoxy equivalent of the phosphorus-containing epoxy resin used in the present invention is preferably 2 ′ 0 0 to 15 500 g Z eq, more preferably 2 5 0 to 1 000 gZe q, more preferably 30 0 to 8 0 0 g / eq. If the epoxy equivalent is less than 2 000 g Z eq, the adhesiveness is poor, and if it exceeds 1 5,000 g Z eq, the heat resistance is adversely affected and adjusted to 2 0 0 to 1 5 000 g / eq. It is desirable to do. As the curing agent for the phosphorus-containing epoxy resin composition of the present invention, commonly used epoxy resin curing agents such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters are used. These curing agents may be used alone or in combination of two or more.

If necessary, 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 or an imidazole. In the phosphorus-containing epoxy resin composition of the present invention, an organic solvent can also be used for viscosity adjustment. 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 methylethylketone, alcohols such as methanol and ethanol. , Aromatic hydrocarbons such as benzene, toluene, etc., and one or more of these solvents may be used, and the epoxy resin concentration is 30 to 80. It can mix | blend in the range of weight%.

Examples of the filler 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, and crystalline silica. .. Inorganic fillers such as silica balloons may be mentioned, but pigments may be added. The reason for using a general inorganic filler is an improvement in impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame retardant aid and can ensure flame retardancy even if the phosphorus content is low. In particular, if the blending amount is not more than 10%, the impact resistance effect is small. However, if the blending amount exceeds 1550%, the adhesiveness, which is a necessary item for laminate applications, decreases. Further, fibrous fillers such as silica, glass fiber, pulp fiber, synthetic fiber, and ceramic fiber, organic fillers such as fine particle rubber, and thermoplastic elastomer can be contained in the resin composition.

Examples of the electronic circuit board material obtained with the phosphorus-containing epoxy resin composition as described above include a resin sheet, a metal foil with resin, a pre-preda, and a laminate. Resin sheet The production method is not particularly limited. For example, a phosphorus-containing epoxy resin composition as described above is preferably used for a carrier film that does not dissolve in an epoxy resin composition such as a polyester film or a polyimide film. After coating to a thickness of ˜100 μm, it is dried by heating at 100 to 200 ¾ 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 subjected to surface treatment with a release agent in advance, the molded resin sheet can be easily peeled off. Here, it is desirable that the thickness of the resin sheet is 5 to 80 μm.

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

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

Next, a method for producing a laminate using the above resin sheet, resin-coated metal foil, pre-preda and the like will be described. When forming a laminate using a pre-preda, one or more pre-predas are laminated, metal foil is placed on one or both sides to form a laminate, and this laminate is heated and pressurized to laminate and integrate. . Here, as the metal foil, copper, aluminum, brass, nickel or the like alone, alloy, or composite metal foil can be used. Conditions for heating and pressurizing the laminate may be appropriately adjusted by heating and pressurizing under conditions for curing the epoxy resin composition. However, if the pressurization pressure is too low, bubbles remain in the resulting laminate. However, since electrical characteristics may deteriorate, it is preferable to apply pressure under conditions that satisfy the moldability. For example the temperature in 1 6 0-2 2 0, 4 9 pressure. 0~4 9 0. 3 NZ cm 2 (5~ 5 O kgf / cm 2), between the heating pressing time 4 0-2 4 0 minutes Can be set respectively. Furthermore, a multilayer board can be produced using the single-layer laminated board thus obtained as an inner layer material. In this case, first, circuit formation is performed 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 be blackened to obtain an inner layer material. An insulating layer is formed on one or both sides of the circuit forming surface of the inner layer material with a resin sheet, a resin-coated metal foil, or a pre-predator, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. To do. When the insulating layer is formed from a resin sheet, a laminate is formed by arranging resin-attached sheets on the circuit forming surfaces of a plurality of inner layer materials. Alternatively, a resin sheet is placed between the circuit forming surface of the glazing layer material and the metal foil to form a laminate. 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 hardened resin sheet as an insulating layer. Here, as the metal foil, the same metal foil as that used for the laminated plate used as the inner layer material can be used. 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 the 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 applying to a thickness of 5 to 100 / m, it is dried by heating at 100 to 200 ° ¾ 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 m. A printed wiring board can be formed on the surface of the multilayer laminated board formed in this manner by further forming via holes and circuits by an additive method or a subtractive method. Furthermore, by repeating the above construction method using this printed wiring board as an inner layer material, a multilayer board can be formed. When forming an insulating layer with a metal foil with resin, the metal foil with resin is layered on the circuit forming surface of the inner layer material so that the resin layer of the metal foil with resin faces the circuit forming surface of the inner layer material. Arrange to form a laminate. Then, by heating and pressing this laminate, and integrally molding 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 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 a prepreg, a laminate is formed by placing one or more prepregs on the circuit forming surface of the inner layer material, and further placing a metal foil on the outside. To do. Then, the laminate is heated and pressed to be integrally formed, whereby the cured product of the pre-preda is formed as an insulating layer and the outer metal foil is formed as a conductor layer. Here, as the metal foil, the same metal foil as that used for the laminated plate used as the inner layer plate can be used. Further, the heating and pressing can be performed under the same conditions as the formation of the eaves layer material. A printed wiring board can be formed by further forming a via hole or a circuit on the surface of the multilayer laminated board thus formed by an additive method or a subtractive method. Furthermore, by repeating the above-described construction method using this printed wiring board as an inner layer material, a multilayer board can be formed.

As a result of evaluating the properties of the laminate containing the phosphorus-containing epoxy resin of the present invention and the composition, the content of the compound represented by the general formula (2) is 2.5% by weight or less. The phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (1) with epoxy resins is highly reactive with the curing agent, and the balance between the flowability of the resin and the curability during curing is high. well The pre-preda and the laminate obtained by heat-curing the pre-preda were flame retardant without containing a halide and were a resin composition having excellent solder heat resistance. Example

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 of the compound represented by the general formula (2) contained in the compound represented by the general formula (1) was measured using HPLC. A column of CD 00 6 of C adenza CD—C 1 8 manufactured by Imtakt was used by using an apparatus of A g i l e nt l l O Ose r e e s manufactured by Hew l e t t P a c k e r d. Water and methanol were used as eluents, sample measurement was started at 60% methanol, and a gradient was made to reach 100% methanol in 16 minutes. The flow rate was 0.5 m 1 / min and the measurement was performed at a wavelength of 2 66 nm using a UV detector. In addition, flame retardancy was measured according to the UL (Unde r w r i t e r L a B r o r r a t r ic s) standard. The varnish gel time was measured at 1600. The peel strength of the copper foil was measured according to JIS C 64 8 15.7, and the adhesion between layers was measured by peeling between one pre-preda and the remaining three sheets according to JIS C 64 8 15.7. Solder heat resistance was measured at 2 80 according to JISC 6 4 8 15.5, and the presence or absence of blistering or peeling was visually inspected. In addition, the glass transition temperature and the heat generation amount of the cured product were measured with Seiko Instruments Inc. EX STR 6600. Curing calorific value retention rate is the percentage of the total curing calorific value of the pre-preder after storage at 60 at 72 hours, assuming that the total curing calorific value of the pre-predator immediately after creation is 100%. The smaller the number, the worse the storage stability.

(Confirmation of the structure of the compound represented by the general formula (2))

The HPLC of HCA—HQ represented by structural formula 1 was measured as a compound of general formula (1). In addition, this was fractionated, and the retarding component of the curing reaction was taken out and measured by FD-MAS S, FT IR, and Proton NMR. From the measurement results of MAS S, the molecular weight is 3 24 and FT I When the R results were compared with HC A_HQ, a decrease in phenolic hydroxyl groups, a decrease in benzene 3 substitutions, and an increase in benzene 2 substitutions were observed. From proton NMR results, it was confirmed that HCA was bonded at the p-position to the hydroxyl group derived from hydroquinone. Based on the above, the peak at 13.6 minutes was confirmed as structural formula 3. As a compound of the general formula (1), 1 0- (2, 7-dihydroxynaphthyl) 1 1 0-dihydro 1 9 oxa 1 1 0-phosphaphenanthrene 1 1 0-oxide was analyzed in the same manner. The component of structural formula 4 was confirmed.

Structural formula 3

Synthesis example 1

In a four-necked glass separable flask equipped with a stirrer, thermometer, cooling tube, and nitrogen gas inlet, HCA— HQ 3 1. 7 2 parts by weight and YD F— 1 7 0 6 8. 2 8 parts by weight are charged and heated to 1 20 in a nitrogen atmosphere I did it. As a catalyst, 0.32 part by weight of triphenylphosphine was added, and the reaction was carried out at 16O for 4 hours. The purity of the compound represented by the general formula (1) is 99.5 wt. / ₀ . 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 0.03% 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

A compound represented by the general formula (2), specifically, a compound represented by the general formula (1) containing 0.17% by weight of the compound represented by the structural formula 3 except that the compound HC A—HQ was used. The same operation as 1 was performed. The purity of the compound represented by the general formula (1) is 99.4 weight. / ₀ . The content of the compound represented by the general formula (2) contained in the reaction system is 0.05 weight. / ₀ . The epoxy resin thus obtained had an epoxy equivalent of 484.lg / eq and a phosphorus content of 3.0% by weight.

Synthesis example 3

A compound represented by the general formula (2), specifically, a compound represented by the general formula (1) containing 0.33 wt% of the compound represented by the structural formula 3 except that HC A—HQ was used. The same operation as 1 was performed. 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 0.1% by weight. The epoxy equivalent of the obtained epoxy resin was 4 88.4 gZe q, and the phosphorus content was 3.0% by weight.

Synthesis example 4

A compound represented by the general formula (2), specifically, a compound represented by the general formula (1) containing 0.65% by weight of the compound represented by the structural formula 3 except that the compound HC A—HQ was used. The same operation as 1 was performed. 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 0.2 1% by weight. The epoxy equivalent of the obtained epoxy resin was 4 88.3 gZe q, and the phosphorus content was 3.0% by weight. Synthesis example 5

A compound represented by the general formula (2), specifically, a compound represented by the general formula (1) containing 0.95% by weight of the compound represented by the structural formula 3 except that the compound HC A—HQ was used. The same operation as 1 was performed. 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 4 8 7.7 g / e q, and the phosphorus content was 3.0% by weight.

Synthesis example 6

A compound represented by the general formula (2), specifically, a compound represented by the general formula (1) containing 1.20% by weight of the compound represented by the structural formula 3 except that the compound HC A—HQ was used. The same operation as 1 was performed. 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 4 8 6.3 g / e q, and the phosphorus content was 3.0% by weight.

Synthesis example 7

In the same apparatus as in Synthesis Example 1, 21.15 parts by weight of HCA and 50 parts by weight of toluene were charged, heated to 75 in a nitrogen atmosphere, and dissolved. Parabenzoquinone was added thereto in small portions over 30 minutes, and the temperature was raised after holding at 85 for 30 minutes, and the reaction was carried out 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. To this was charged 68.39 parts by weight of YD F-1700 and heated to 150 to remove toluene by refluxing. The content of the compound represented by the general formula (2) contained in the reaction system is 0.76 weight ⁰ /. Met. Triphenylphosphine 0.32 part by weight was added and the reaction was carried out at 1600 for 4 hours. The epoxy equivalent of the obtained epoxy resin was 470.2 gZe q, and the phosphorus content was 3.0% by weight. Synthesis example 8

In the same apparatus as in Synthesis Example 1, the content of the compound represented by the general formula (2), specifically the compound represented by the structural formula 3, is 0.01 wt%. Compound HC A—HQ 31.09 parts by weight, HCA 0.63 parts by weight, YDF—1 7 0 68.2 8 parts by weight were charged, and the same operation as in Synthesis Example 1 was performed. The purity of the compound represented by the general formula (1) is 97.3 weight with respect to the total of HC A and HC A—H Q charged. /. Met. The content of the compound represented by the general formula (2) contained in the reaction system was 0.03% by weight. The epoxy equivalent of the obtained epoxy resin was 4 8 0.3 g / e q, and the phosphorus content was 3.0% by weight.

Synthesis example 9

The content of the compound represented by the general formula (2), specifically the compound represented by the structural formula 4, is 0.15 weight. The compound represented by the general formula (1) which is / ₀ , specifically, the compound represented by the structural formula 2 is used as 2 6. 8 6 parts by weight, and YDF— 8 1 70 is used as 7 3.1 4 parts by weight. The same operation as in Synthesis Example 1 was performed except that. The purity of the compound represented by the compound represented by the general formula (1) is 90.1 weight. /. Met. 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 3 2 1.8 gZe q, and the phosphorus content was 2.2% by weight.

Synthesis example 1 0

A compound represented by the general formula (2), specifically, a compound represented by the general formula (1) containing 3.10% by weight of the compound represented by the structural formula 3 except that the compound HC A—HQ was used. The same operation as 1 was performed. 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 resulting resin had an epoxy equivalent of 4 7 1. l g / e q and a phosphorus content of 3.0 weight. /. Met.

Synthesis example 1 1

In the same apparatus as in Synthesis Example 1, HCA 2 1.15 parts by weight and toluene 40 parts by weight were charged. In a nitrogen atmosphere, the solution was heated to 75 to dissolve. 69.13 parts by weight of YDF-1700 was added and dissolved, and 3 parts by weight of parabenzoquinone 9.73 was added in small portions over 2 hours. After completion of the addition, the mixture was maintained 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 formula (2) contained in the reaction system was 1.08% by weight. The obtained epoxy resin had an epoxy equivalent of 444.4 g / eq and a phosphorus content of 3.0% by weight.

Synthesis example 1 2

A compound represented by the general formula (2), specifically a compound represented by the general formula (1) containing 2.60% by weight of a compound represented by the structural formula 4, specifically represented by the structural formula 2. The same operation as in Synthesis Example 9 was performed except that the compound was used. 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 0.7% by weight. The epoxy equivalent of the obtained epoxy resin was 3 2 1.4 gZe q, and the phosphorus content was 2.2% by weight.

The epoxy resin, dicyan diamine 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 to 9 and Comparative Examples 1 to 3. A phenol novolak resin curing agent and an imidazole curing accelerator were mixed according to the 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 and the gel time is adjusted to the same level as the retention rate (%) of curing heat generation. 1

*: Total weight of HCA superposition part and parabenzoquinone part by weight

DICY Nippon Carbide Co., Ltd. Dicyandiamide 2E4MZ Shikoku Kasei Co., Ltd. Imidazole Catalyst Table 2

DICY Nippon Carbide Co., Ltd. Dicyandiamide 2E4MZ Shikoku Kasei Co., Ltd. Imidazole Catalysts Table 3

Dicyandiamide 2E4M2 from Shikoku Kasei Co., Ltd. Table 4

DICY Nippon Carbide Co., Ltd. Dicyandiamide

2E4MZ Imidazole catalyst manufactured by Shikoku Kasei Co., Ltd. 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) increases, the gel time becomes remarkably slow, and the curing reaction Affects sex. Tables 1 and 2 evaluated with dicyandiamide curing agent, and Table 3 evaluated with phenol novolac resin curing agent, but the content of the compound represented by general formula (2) is high in any curing agent. Thus, it can be seen that the gel time is remarkably slow, which affects regardless of the type of curing agent. This is because, for example, when a laminated board is made, the resin content is insufficient, resulting in problems such as reduced adhesive strength, migration, blistering and cracking during solder immersion. In addition, as the gel time is adjusted as shown in Comparative Example 5 in Table 4, when the blending amount of the curing catalyst is increased, the curing exothermic retention ratio decreases, and the storage stability in the pre-preda deteriorates, resulting in long-term storage. There are problems such as being unable to. Industrial applicability

In the phosphorus-containing epoxy resin obtained by reacting the compound represented by the general formula (1) with the epoxy resin, the content (weight%) of the compound represented by the general formula (2) in the system before the reaction is expressed as follows. By using a phosphorus-containing epoxy resin characterized in that the value obtained by dividing by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by reaction is 0.3 or less, the gel time is reduced. Without delay, it is possible to provide a phosphorus-containing epoxy resin and an electronic circuit board material excellent in adhesive strength, migration resistance, solder dipping resistance, and storage stability in a pre-preda.

Claims

The scope of the claims

1. In the process for producing a phosphorus-containing epoxy resin obtained by reacting a compound represented by the general formula (1) with an epoxy resin, the content of the compound represented by the general formula (2) in the system before the reaction ( (% By weight) is divided by the phosphorus content (% by weight) of the phosphorus-containing epoxy resin obtained by the reaction to produce a phosphorus-containing epoxy resin characterized by a value of 0.3 or less. Method.

(R 1)

(R 2)-(O) n- P = 0 (1)

H 0- <B ^ -0 H

(1)

(R2)-(O) n- P = 0 (2)

O- (B) -OH In formula (1) and formula (2), R 1 and R 2 represent hydrogen or a hydrocarbon group, each of which may be different or the same, linear, branched It may be annular. Further, R 1 and R 2 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 claim 1.

3. A phosphorus-containing vinyl ester resin, wherein the phosphorus-containing epoxy resin according to claim 2 is used.

4. A phosphorus-containing epoxy resin composition comprising the phosphorus-containing epoxy resin according to claim 2 as an essential component and a curing agent.

5. A radical polymerizable resin composition comprising, as an essential component, the phosphorus-containing bull ester resin according to claim 3 and a radical polymerization initiator and Z or a curing agent.

6. A material for an electronic circuit board obtained by using the phosphorus-containing epoxy resin composition according to claim 4. Fee.

7. A sealing material obtained using the phosphorus-containing epoxy resin composition according to claim 4.

8. A casting material obtained using the phosphorus-containing epoxy resin composition according to claim 4.

9. A cured product obtained by curing the phosphorus-containing epoxy resin composition, the radio resin composition, the electronic circuit board material, the sealing material, and the casting material according to any one of claims 4 to 8.