HK1040410B - Epoxy resin compositions containing phosphorus and the uses thereof - Google Patents
Epoxy resin compositions containing phosphorus and the uses thereof Download PDFInfo
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Description
The present invention relates to a novel phosphorus-containing epoxy resin composition having flame retardant properties, and a resin sheet, a resin composite metal foil, a prepreg, a laminate, a multilayer board for a circuit board containing the epoxy resin.
For copper-clad laminates used in electronic or electrical equipment and components, measures such as fire-retardant or flame-retardant properties are highly required. Thus, halogenated epoxy resins having flame retardant properties are commonly used in copper clad laminates. In particular, among halogen atoms, by introducing bromine into an epoxy resin, excellent flame retardant properties can be provided to the epoxy resin, and a cured product thereof having a highly active epoxy group and characteristics can be obtained, and thus halogenated epoxy resins, particularly brominated epoxy resins, are known as useful materials for electronic or electrical components. However, when these halogenated epoxy resins are used at high temperatures for a long period of time, they dissociate to form halogen compounds such as hydrogen halide and halogen, followed by the risk of possibly causing a wire corrosion problem, and such a real accident has been reported. In addition, it is pointed out that toxic chemicals such as dioxin and hydrogen halide can be formed, causing serious environmental problems. When used up, the components of the electrical and/or electronic component are calcined. This indicates that the use of halogen-containing flame retardants causes such environmental problems. In view of the current state of epoxy resin compositions, there is a strong need for research to develop a novel epoxy resin composition to replace halogenated epoxy resins. Under the present conditions, the development and commercialization of flame-retardant epoxy resins free of any halogen and copper-clad laminates for printed wiring applications using the same are considered as one subject of satisfying the present demand.
The inventors of the present invention have conducted extensive studies to develop a novel Flame retardant epoxy resin free of any halogen and a copper clad laminate using the same for printed wiring applications, and aimed at the basic theory of Flame retardancy due to phosphorus and phosphorus compounds disclosed in pages 49, 52-59 of "Flame retamination of Polymer" (published by taiseishisa, 1989, tokyo, hitoshi nishizawa). And the inventors of the present invention have found that a novel flame-retardant phosphorus-containing epoxy resin composition suitable for this basic theory can be obtained only by the use of a specific organic phosphorus compound, and moreover, a resin composition obtained by containing a specific epoxy resin as a main component exhibits excellent flame-retardant properties and the physical properties of the cured product thereof are suitable for printed wiring applications. Thus, we have completed the present invention.
As disclosed in EP0806429a2, although flame retardant epoxy resins have been investigated without using any halogen. It is a phosphorus-containing organic compound having an epoxy group, which is prepared from an organic phosphorus compound and an epoxy resin, but it has been pointed out that when a bifunctional epoxy resin is used as a starting material, the concentration of the epoxy group as an active functional group becomes low, and in the case of hardening the epoxy resin, there is a problem that the heat resistance is lowered. In addition, the phosphorus-containing epoxy resin obtained from an organic phosphorus compound and an epoxy resin, for example, disclosed in JP4-11662A, has too high a viscosity to perform a protective action, and it is necessary to lower the actual viscosity by adding another liquid epoxy resin having a lower viscosity. Therefore, an epoxy resin composition using such an epoxy resin generally has a problem that the phosphorus content in the composition is reduced. Further, the phosphorus-containing epoxy resin disclosed in JP11-166035A can be obtained from an organic phosphorus compound and an epoxy resin, and the phosphorus-containing epoxy resin disclosed in JP11-279258a can be obtained from an organic phosphorus compound, a type of quinone compound, and an epoxy resin, however, both types must use a novolac type of epoxy resin as a multifunctional epoxy resin, and have a problem that the adhesive force needs to be lowered.
The object of the present invention is to solve the above problems and to provide a flame retardant epoxy resin composition containing phosphorus and epoxy groups, which has excellent flame retardancy, heat resistance and adhesive force, and can be used for printed wiring applications, including resin sheets, resin composite copper foils (RCC), prepregs, copper clad laminates and build-up wiring boards.
The focus of the present invention is therefore a phosphorus-containing epoxy resin composition comprising an epoxy resin composition (a), which contains a phosphorus-containing epoxy resin (A) and a hardener, wherein the phosphorus-containing epoxy resin (A) is a phosphorus-containing resin composition, the composition is prepared by reacting a phosphorus-containing organic compound (B) with at least one epoxy resin (C) selected from the group consisting of formula 1, formula 2, or formula 3, wherein the content of the epoxy resin (C) is 20 to 45 wt%, the organic compound (B) is obtained by reacting 1.01 to 2mol of an organic phosphorus compound (B) having one active hydrogen atom bonded to a phosphorus atom with 1mol of a quinone compound, in addition, another important point of the present invention is a flame-retardant epoxy resin composition comprising phosphorus and an epoxy resin, the phosphorus-containing epoxy resin composition is characterized in that the total content of phosphorus in the whole resin composition is 0.5-4 wt%.
Wherein R is1Is a hydrogen atom and/or a phenyl group, m is an integer including 0,
wherein R is2Is a hydrogen atom and/or a phenyl group, n is an integer including 0,
wherein R is3Is a hydrogen atom and/or a phenyl group, 1 is an integer including 0, and X is-CH2-、-O-、-CO-、-SO2-、-S-、-CH(C6H5)-、-C(C6H5)2-, a bond or formula (4).
Other important applications of the present invention are a resin sheet, a resin composite copper foil, a prepreg impregnated and coated on a sheet-type inorganic and organic substrate and a resin sheet thereof, a printed wiring board, and a built-up printed wiring board obtained by heating and curing the prepreg.
The present invention will be described in more detail below.
As illustrative examples of the quinone compound used in the present invention, 1, 4-benzoquinone, 1, 2-benzoquinone or 1, 4-naphthoquinone may be mentioned. These quinone compounds can be used alone or in combination, and in addition, there is no limitation on them.
As illustrative examples of the organophosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom of the present invention, there may be mentioned 3, 4, 5, 6-dibenzo 1, 2-oxyphosphate (hexacyclic) -2-oxide (3, 4, 5, 6-dibenzo-1, 2-oxyphosphane-2-oxide) (abbreviated as HCA, product of Sanko Chemicals Co., Ltd. Osaka, Japan), diphenylphosphineoxide or other compounds. These organophosphorus compounds (b) can be used alone or in combination, and in addition, they are not limited.
The reaction of the quinone compound with the organophosphorus compound (b) having an active hydrogen atom bonded to a phosphorus atom can be carried out, for example, by the methods disclosed in JP5-214068A, Zh. Obshch. Khim.42(11)2415-2418(1972), which is the common journal of chemistry of Russia, JP60-126293A, JP61-236787A or JP 5-331179A. However, in the present invention, 1.01 to 2mol, suitably 1.01 to 1.5mol, more suitably 1.01 to 14mol of the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom should be reacted with 1mol of the quinone compound, and when the molar ratio is more than 2, the reaction between the epoxy group and the organic phosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom occurs, so that a large amount of components having no epoxy group (bridging site as a hardening agent) is formed, and the heat resistance and the adhesive force are lowered. In contrast, when the molar ratio of the organophosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom to the quinone compound is less than 1.01: 1, the two reactants do not react in an appropriate direction, and the organophosphorus compound (b) or the quinone compound is present. In particular, if the pure quinone is still present, physical properties such as heat resistance will be affected because the pure quinone has no reactive groups to react with the epoxy resin.
The reaction of the quinone compound with the organophosphorus compound (b) having one active hydrogen atom bonded to a phosphorus atom is carried out as follows:
first, the organic phosphorus compound (b) is dissolved in an inert solvent, and then the quinone compound is added to the solution and heated with continuous stirring to complete the reaction. As illustrative examples of the inert solvent, mention may be made of methanol, ethanol, isopropanol, chloroform, N' -dimethylformamide, dioxane, ethylene glycol, methoxypropanol, ethyl glycol diethyl ether, benzene, toluene or xylene, and any type of solvent capable of dissolving the organophosphorus compound (b) may be used without being limited to the solvents mentioned. However, in the quinone compounds, some types of them contain a small amount of an organic acid such as maleic anhydride or phthalic anhydride as an impurity, and when a solvent having an alcoholic hydroxyl group is used, these impurity acids react with the alcoholic hydroxyl group of the solvent, resulting in the formation of a substance that does not participate in epoxy curing, and possibly lowering the heat resistance of the cured epoxy product. Therefore, the use of dioxane, benzene, toluene or xylene is more suitable. The quinone compound is used in the form of a powder or a solution thereof. The reaction of the quinone with the organophosphorus compound as described above is exothermic and the desired amount of quinone is divided into small portions and added, or added dropwise through a solution thereof, to avoid a rapid increase in temperature. After the addition is completed, the reaction mixture of the above quinone and organic phosphorus is maintained at a temperature of 50 to 150 ℃ for 1 to 4 hours.
As an illustrative example of the epoxy resin (C) represented by the general formula 1 of the present invention, there may be mentioned EpotohtoZX-1027 (a hydroquinone type epoxy resin, a product of Tohto Kasei Co., Ltd. Tokyo, Japan), but not limited to such a resin. As an illustrative example of the epoxy resin (C) represented by the general formula 2 of the present invention, there may be mentioned Epotohto ZX-1355(1, 4-dihydroxynaphthalene type epoxy resin, products of Tohto Kasei Co., Ltd. Tokyo, Japan), but there is no limitation to such a resin. As illustrative examples of the epoxy resin (C) represented by the general formula 3 of the present invention, mention may be made of Epotohto YDF-170 and YDF-8170 (bisphenol F type epoxy resin, Tohto Kasei Co., Ltd. Tokyo, product of Japan), Epotohto ZX-1251 (bisphenol epoxy resin, product of Tohto Kasei Co., Ltd. Tokyo, product of Japan), Epotohto ZX-1201 (bisphenol fluorene type epoxy resin, product of Tohto Kasei Co., Ltd. Tokyo, product of Shin Nittetu Chemicals Co., Ltd. Tokyo, product of Japan), or ESLV-50TE (diphenyl thioether type epoxy resin, product of Shin Nittus Co., Ltd. Shi. The epoxy resins (C) of the general formula 1, the general formula 2 and the general formula 3 can be used alone or in combination with each other, and the mixing ratio is 20 to 45 wt%, suitably 20 to 43 wt%, more suitably 20 to 41 wt% for 100 wt% of the phosphorus-containing epoxy resin (A). If the blending ratio is less than 20 wt%, the bond strength, particularly between copper-clad laminates, is lowered, and if the blending ratio exceeds 45 wt%, the heat resistance of the cured product of the above composition is lowered.
If the total content of the epoxy resins (C) of the general formulae 1, 2 and 3 is within the range of 20 to 45 wt% in the above composition, other types of epoxy resins may be additionally used. As other types of epoxy resins, there may be mentioned epoxy resins having more than 2 epoxy groups in 1 molecule resin, specifically bisphenol type epoxy resins other than general formula 3, resorcinol (resolcinol) type epoxy resins, polyethylene glycol type epoxy resins, trifunctional type epoxy resins, tetrafunctional type epoxy resins, and novolak type epoxy resins, but not limited thereto.
The reaction between the phosphorus-containing organic compound (B) obtained by reacting a quinone compound with an organic phosphorus compound (B) having one active hydrogen atom bonded to a phosphorus atom and the epoxy resin (C) containing at least one selected from the group consisting of formula 1, formula 2 and formula 3 can be carried out by a known conventional method. That is, the epoxy resin (C) is added to the phosphorus-containing organic compound (B) and heated to a reaction temperature of 100-200 ℃ and, suitably, 120-180 ℃ with continuous stirring to complete the reaction. If the reaction rate is too low, a suitable catalyst may be used to increase the yield or to promote the reaction, if necessary, in order to increase the yield. As specific examples of the catalyst, there may be mentioned tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine, tris (2, 6-dimethoxyphenyl) phosphine, phosphonium salts such as ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, or imidazoles such as 2-methylimidazole or 2-ethyl-4-methylimidazole.
The phosphorus-containing epoxy resin (A) of the present invention is suitably used in an amount of 1.2 to 4% by weight, more suitably 2 to 3.1% by weight. The phosphorus content of the organic component in the flame-retardant resin composition containing the phosphorus-containing epoxy resin (A) is suitably from 0.5 to 4% by weight, more suitably from 1.5 to 3.5% by weight, still more suitably from 1 to 3% by weight. If the phosphorus content of the organic component in the cationic resin composition is less than 0.5 wt%, it is difficult to maintain sufficient flame retardancy, and if it exceeds 5 wt%, the heat resistance is not as expected to satisfy the increase in phosphorus content, so that it is necessary to adjust the content thereof to 0.5 to 4 wt%.
The phosphorus-containing epoxy resin (A) of the present invention has an epoxy equivalent of 200-600g/eq, more preferably 250-550g/eq, still more preferably 300-500 g/eq. If the epoxy equivalent is less than 200g/eq, the adhesive force is insufficient, while if it exceeds 500g/eq, the heat resistance is lowered, so that it is necessary to adjust it to 200-600 g/eq.
As hardeners for the compositions according to the invention, it is possible to use the customary hardeners for epoxy resins, such as, for example, various types of phenolic resins, anhydrides, amines, hydrazides or acidic polyesters. These hardeners can be used alone or in combination with one another.
For the flame retardant epoxy resin composite material containing the phosphorous epoxy resin of the present invention, an organic solvent may be used to adjust the viscosity. As usable organic solvents, amides such as N, N' -dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone or methyl ethyl ketone, alcohols such as methanol or ethanol, and aromatic hydrocarbons such as benzene or toluene can be used. One or more of these solvents may be mixed together with one another and can be blended into the epoxy resin in an amount of 30 to 80 wt%.
If desired, curing accelerators such as tertiary amines, quaternary ammonium salts, phosphines or imidazoles may be blended into the composition of the present invention.
As the filler used in the present invention, there may be mentioned an inorganic filler such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, kaolin, titanium oxide, glass powder or silica microspheres, and a pigment may be blended. As reasons for the use of conventional inorganic fillers, mention may be made of the improvement in the impact strength of the above-mentioned compositions. Also when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, even a low phosphorus content can provide suitable flame retardancy because the metal hydroxide acts as a flame retardant accelerator. When the blending ratio of the filler to the above-mentioned composition is less than 10%, the effect on impact strength cannot be expected. However, if the blending ratio exceeds 150%, the adhesive force of the composition may be reduced as a main property for the application of a wiring board. In addition, a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber or fine particles of an organic filler such as rubber or a thermoplastic elastomer may be contained in the resin composition.
The method for producing a resin sheet from the above-mentioned phosphorus-containing epoxy resin composition is exemplified by the following: however, the method of producing the resin sheet is not limited to the following description. That is, the above phosphorus-containing epoxy resin composition is coated on the surface of a support film (which cannot be dissolved by the epoxy resin composition) having a desired thickness of 5 to 100 μm, such as a polyester film or a polyimide film, and then heated and dried at 100-200 ℃ for 1 to 40 minutes to form a sheet shape. I.e. the process is commonly referred to as a casting process. If the surface of the sheet to be coated is pretreated with a release agent before being coated with the phosphorus-containing epoxy resin composition, the formed resin sheet can be easily released. The desired thickness of the formed resin sheet is 5-80 μm.
The method for producing a resin composite copper foil from the above phosphorus-containing epoxy resin composition is exemplified by the following:
as the metal foil, copper, aluminum, brass, nickel, an alloy of these metals, or a composite metal foil can be used. The desired thickness of the metal foil used is 9-70 μm. The method for producing the resin metal sheet from the flame-retardant resin composition comprising the phosphorous epoxy resin and the metal foil is not limited by the above description. That is, the resin varnish of the phosphorous epoxy resin composition, the viscosity of which has been adjusted by adding a solvent, is applied to one side of the above metal foil by, for example, a roll coater. The coated surface is then heated and dried so that the resin composition is semi-cured: (B-stage), and forming a resin layer. For semi-curing the resin composition, for example, a method of performing treatment by heating and drying at 100-200 ℃ for 1 to 40 minutes can be mentioned. The desired thickness of the resin portion of the resin composite metal is 1 to 100 μm.
The prepreg prepared from the above phosphorous epoxy resin composition is described as follows:
as the sheet-type substrate, woven or nonwoven fabrics of inorganic fibers such as glass fibers or organic fibers such as polyester, polyamine, polyacrylic acid, polyimide or Kebler may be used, however, they are not limited thereto. The method of producing the prepreg from the flame-retardant resin composition comprising the phosphorous epoxy resin and the matrix is not limited by the above description. The prepreg can be obtained, for example, by immersing the substrate in a resin varnish of the epoxy resin composition, the viscosity of which is adjusted by adding a solvent thereto, and then semi-hardening the resin component by heating and drying (B-stage). For example, it may be dried by heating at 100 ℃ and 200 ℃ for 1 to 40 minutes. The desired resin content in the solid prepreg is 30 to 80 wt.%.
The method for producing a laminate using the above resin sheet, resin composite metal foil and prepreg is explained as follows:
in the case of producing a laminate using prepregs, one or more prepregs are laminated, and then a metal foil is mounted on one side or both sides of the laminated prepregs, and the prepregs are molded into one body by hot press molding. As the metal foil, copper, aluminum, brass, nickel, an alloy of the metals, or a composite metal foil may be used. As the heat-pressing conditions of the laminate, suitable curing conditions should be selected for the above epoxy resin composition. If the pressing pressure is too low, voids may exist in the laminate and the electrical properties thereof may be degraded, and it is necessary to press the sheet by satisfying the molding pressure. For example, each molding condition can be set as follows, i.e., temperature: 160 ℃ and 220 ℃, pressure: 49.0-490.3N/cm2(5-50kgf/cm2) And hot pressing time: 40-240 minutes. In addition, a combination-type printed wiring board can be produced by using the obtained single-layer laminate as an inner layer material. In this case, a circuit pattern is first formed on the surface of the laminate by a superposition method or a subtractive method, then the surface on which the circuit is formed is treated with an acid, and finally it is treated to a black oxide, thus obtaining an inner layer material. An insulating layer is formed using a resin sheet, a resin composite metal foil, or a prepreg on one side or both sides of the inner layer material on which the circuit surface is formed, and then a conductive layer is formed on the surface of the insulating layer, thereby obtaining a combination-type printed wiring board. In the case of forming the insulating layer using a resin sheet, a laminate is formed by placing the resin sheet on the circuit-forming surface of the multi-inner-layer material, or by placing the resin sheet between the circuit-forming surface of the inner-layer material and the metal foil. The resulting laminate is then molded into one by hot press molding with the cured resin sheet as the insulating layer, and then a multilayer inner layer material can be obtained from the inner layer material, the metal foil as the conductive layer, and the cured resin sheet as the insulating layer. As the metal foil, the same material used in the laminate, which is used as the inner layer material, may be used. In addition, the hot press molding is performed by the same conditions as those for forming the inner layer material. In the case of forming an insulating layer by coating a resin on a laminate, the insulating layer is formed on the inner sideAfter the phosphorus-containing epoxy resin compound or the flame-retardant epoxy resin composition containing a phosphorus-containing epoxy resin is applied to the circuit-forming surface of the outermost layer of the layer material suitably to a thickness of 5 to 100 μm, it is heated and dried at 100-200 ℃ for 1 to 90 minutes, and then molded into a sheet shape. The sheet may be formed by a process commonly referred to as a casting process. The desired thickness of the laminate after drying is 5-80 μm. With respect to the surface of the multilayer laminate formed as described above, a printed circuit board can be produced by forming via holes or circuit patterns by an additive method or a subtractive method. When the above process is repeated using the printed circuit board as an inner layer material, a more complicated multilayer circuit board can be produced. In addition, in the case of forming the insulating layer using the resin composite metal foil, the laminate is formed by placing the foil on the circuit pattern formation surface of the inner layer material so that the resin layer of the resin composite metal faces the circuit pattern formation surface of the inner layer material. The laminate thus obtained was molded integrally by hot press molding, so that the cured resin layer of the resin composite metal foil became an insulating layer and the outer metal foil became a conductive layer. The hot press molding is performed by the same conditions as those for forming the inner layer material. In the case of forming the insulating layer using a prepreg, one prepreg or a laminate containing a plurality of prepregs is placed on the circuit pattern formation surface of the inner layer material, and a metal foil is placed on the outer surface. The resulting laminate is then molded into one piece by hot press molding, with the cured prepreg serving as the insulating layer and the outer metal foil serving as the conductive layer. As the metal foil, the same material as used in the laminate (which is used as the inner layer laminate) can be used. The hot press molding is performed by the same conditions as those for forming the inner layer material. With respect to the surface of the multilayer laminate formed as described above, via holes or circuit patterns are formed by an additive method or a subtractive method, and then a printed circuit board can be produced. When the above process is repeated using the printed circuit board as an inner layer material, a more complicated multilayer circuit board can be produced.
The compositions of the invention and the laminates obtained using the compositions were evaluated for their characteristics. The results show that a prepreg obtained by immersing a phosphorus-containing resin composition in the above composition, wherein the phosphorus-containing resin composition is prepared by reacting a phosphorus-containing organic compound (B) with at least one epoxy resin (C) selected from the group consisting of formula 1, formula 2, and formula 3 such that the content of the epoxy resin (C) is 20 to 45 wt%, the organic compound (B) is obtained by reacting 1.01 to 2mol of an organic phosphorus compound (B) having one active hydrogen atom bonded to a phosphorus atom with 1mol of the quinone compound, and a laminate obtained by curing the prepreg, which does not contain a halogenated compound, exhibits excellent flame retardancy, and does not dissociate halogen at high temperature, and further has good adhesion and excellent heat resistance.
Examples
The present invention can be more easily explained by examples and comparative examples, which, however, should not be construed to limit the scope of the claims of the present invention.
In the examples and comparative examples, flame retardancy was tested based on UL (underwriters laboratories) standards. The peel strength of the copper composite laminate was tested based on JISC64815.7 standard, and the peel strength (layer-to-layer) of the laminate was tested based on JIS C64815.7, in which the adhesive strength was tested by peeling one prepreg from the other 3 prepregs.
The onset temperature and glass transition temperature of the thermal weight loss were measured by an Exster 6000 (product of Seiko Instrument Co., Ltd. Tokyo, Japan).
Synthesis (1)
To a 4-neck separable glass flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tee were charged 212 parts by weight of HCA and 470 parts of toluene as a solvent, and the mixture was heated to dissolve HCA in the solvent. Then, 100 parts by weight of 1, 4-naphthoquinone was carefully added to the solution stepwise to prevent the reactants from rapidly increasing in temperature due to the heat of reaction. Wherein the molar ratio of HCA as phosphorus compound to 4-naphthoquinone is 1.56: 1. After completion of the reaction, 300 parts of the solvent was recovered, and then 160 parts of EPPN-501H (trifunctional epoxy resin, epoxy equivalent: 165g/eq, Nihon Kayaku Co., Ltd., product of Ltd. Tokyo, Japan) and 328 parts by weight of Epotohto YDG-414 (trifunctional epoxy resin, epoxy equivalent: 187g/eq, product of Tohto Kasei Co., Ltd. Tokyo Japan) were added, and the solvent was again recovered by heating under a nitrogen atmosphere at normal pressure with continuous stirring. Thereafter, 200 parts by weight of Epotohto ZX-1027 (hydroquinone type epoxy resin, epoxy equivalent: 187g/eq, product of Tohto Kasei Co., Ltd. Tokyo Japan) was added, and the temperature was raised to 120 ℃ to dissolve the resin. 0.31 part of triphenylphosphine as a catalyst was added and reacted at 160 ℃ for 4 hours. The required content of the epoxy resin represented by the general formulae 1, 2 and 3 was 20% by weight. The epoxy equivalent of the obtained epoxy resin was 401.5g/eq, and the phosphorus content was 3.01% by weight.
Synthesis (2)
The synthesis (1) was repeated except that 130 parts by weight of HCA, 94 parts by weight of 1, 4-naphthoquinone, 400 parts by weight of xylene as a solvent, 350 parts by weight of EPPN-501H, 250 parts by weight of ZX-1355(1, 4-dihydroxynaphthalene type epoxy resin, epoxy equivalent: 145g/eq, product of Tohto Kasei Co., Ltd. Tokyo, product of Japan) and 176 parts by weight of YDH-170 (bisphenol F type epoxy resin, epoxy equivalent: 145g/eq, product of Tohto Kasei Co., Ltd. Tokyo, product of Japan) as epoxy resins were used, and 0.22 parts by weight of triphenylphosphine as a catalyst. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.02: 1. The required epoxy resin content was 42.6 wt%. The epoxy equivalent of the obtained epoxy resin was 273.5g/eq, and the phosphorus content was 1.85% by weight.
Synthesis (3)
The synthesis (1) was repeated except that 155 parts by weight of HCA, 55 parts by weight of 1, 4-benzoquinone, 220 parts by weight of dioxane as a solvent, 55 parts by weight of YH-434 (tetrafunctional epoxy resin, epoxy equivalent: 129g/eq, Tohto Kasei co., ltd.tokyo, product of Japan), 350 parts by weight of ZX-1201 (bisphenol fluorene type epoxy resin, epoxy equivalent: 260g/eq, Tohto Kasei co., ltd.tokyo, product of Japan) and 385 parts by weight of YD-128 (bisphenol a type epoxy resin, epoxy equivalent: 187g/eq co, product of Tohto Kasei co., ltd.tokyo, product of Japan) as an epoxy resin, and 0.21 parts by weight of triphenylphosphine as a catalyst were used. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.41: 1. The required epoxy resin content was 35.0 wt%. The epoxy equivalent of the obtained epoxy resin was 391.5g/eq, and the phosphorus content was 2.20% by weight.
Synthesis (4)
Synthesis (1) was repeated except that 141 parts by weight of HCA, 83 parts by weight of 1, 4-naphthoquinone, 315 parts by weight of toluene as a solvent, 100 parts by weight of YDPN-638 (phenol varnish type epoxy resin, epoxy equivalent: 178g/eq, corresponding to the bifunctional component of formula 3, whose content was 22% by weight, products of Tohto Kasei Co., Ltd. Tokyo Japan) and 325 parts by weight of ZX-1251 (biphenyl type epoxy resin, epoxy equivalent: 158g/eq, products of Tohto Kasei Co., Ltd. Tokyo, Japan) as an epoxy resin, and 0.22 parts by weight of triphenylphosphine as a catalyst were used. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.25: 1. The required epoxy resin content was 34.5 wt%. The epoxy equivalent of the obtained epoxy resin was 303.5g/eq, and the phosphorus content was 2.00% by weight.
Synthesis (5)
Synthesis (1) was repeated except that 141 parts by weight of HCA, 92 parts by weight of 1, 4-naphthoquinone, 320 parts by weight of toluene as a solvent, 467 parts by weight of YDPN-638 and 300 parts by weight of YDF-170 as an epoxy resin, and 0.23 parts by weight of triphenylphosphine as a catalyst were used. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.12: 1. The required epoxy resin content was 40.3 wt%. The epoxy equivalent of the obtained epoxy resin was 320.1g/eq, and the phosphorus content was 2.00% by weight.
Synthesis (6)
Synthesis (1) was repeated except that 270 parts by weight of HCA, 100 parts by weight of 1, 4-naphthoquinone, 580 parts by weight of toluene as a solvent, 100 parts by weight of Epotohto ZX-1201, 100 parts by weight of Epotohto ZX-1355, 60% by weight of Epotohto YH-434 and 370 parts by weight of YDPN-638 as an epoxy resin, and 0.33 parts by weight of triphenylphosphine as a catalyst were used. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.98: 1. The required epoxy resin content was 28.1 wt%. The epoxy equivalent of the obtained epoxy resin was 584.7g/eq, and the phosphorus content was 3.83% by weight.
Synthesis (7)
The synthesis of (1) was repeated except that 90 parts by weight of HCA, 65 parts by weight of 1, 4-naphthoquinone, 200 parts by weight of toluene as a solvent, 300 parts by weight of Epotohto ZX-1355 and 545 parts by weight of YDPN-638 as an epoxy resin, and 0.16 parts by weight of triphenylphosphine as a catalyst were used. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.02: 1. The required epoxy resin content was 42.0 wt%. The epoxy equivalent of the obtained epoxy resin was 235.1g/eq and the phosphorus content was 1.28% by weight.
Synthesis (8)
Synthesis (1) was repeated except that 141 parts by weight of HCA, 55 parts by weight of 1, 4-naphthoquinone, 300 parts by weight of toluene, 814 parts by weight of Epotohto YDCN-701 (cresol novolak type epoxy resin, epoxy equivalent: 200g/eq, product of Tohto Kasei Co., Ltd. Tokyo, Japan) was used as the epoxy resin, and 0.16 parts by weight of triphenylphosphine was used as the catalyst. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.75: 1. The required epoxy resin content is not used. The epoxy equivalent of the obtained epoxy resin was 322.0g/eq, and the phosphorus content was 1.86% by weight.
Synthesis (9)
789 parts by weight of Epotohto YDPN-638 and 211 parts by weight of HCA were poured into the same flask as in Synthesis (1) and heated to be molten. 0.21 part by weight of triphenylphosphine was used as catalyst. In this example, the amount of quinone compound and epoxy resin required was 17.4 wt%. The epoxy equivalent of the obtained epoxy resin was 291.2g/eq, and the phosphorus content was 3.00% by weight.
Synthesis (10)
The synthesis (1) was repeated except that 220 parts by weight of HCA, 95 parts by weight of 1, 4-naphthoquinone, 500 parts by weight of toluene as a solvent, 185 parts by weight of Epotohto YD-128 and 500 parts by weight of Epotohto YDF-170 as epoxy resins, and 0.32 parts by weight of triphenylphosphine as a catalyst were used. Wherein the molar ratio of the phosphorus compound to the quinone compound is 1.70: 1. The required epoxy resin content was 50.0 wt%. The epoxy equivalent of the obtained epoxy resin was 428.1g/eq, and the phosphorus content was 3.12% by weight.
Examples 1-12, 16, comparative examples 1-7.
*Preparation of prepregs
For examples 1 to 12, 16 and comparative examples 1 to 7, resin varnishes shown in tables 1, 2 and 3 were prepared, glass cloth (a product of Nitto Spinning co., Ltd; model 7268; product No. H258, japan, tokyo) was immersed in these resin varnishes, and heated at 155 ℃ for 5 minutes, and finally dried, thereby obtaining prepreg samples.
In these tables, the term [ Dicy ] is dicyandiamide (a product of Nihon Carbide co., ltd., tokyo, japan), [ PSM4357] is phenol novolak (a product of Gunei Chemicals co., ltd.; product number PSM4357, kawasaki), and [2E4MZ ] is 2-ethyl-4-methylimidazole (imidasol) (a product of Shikoku Kasei co., ltd., tokyo, japan, product number 2E4MZ), and [ aluminum hydroxide ] is a product of Sumitomo Chemicals co., ltd., tokyo, japan, product number CL-310; [ magnesium hydroxide ] is a first chemical grade reagent, [ wollastonite ] is a product of Kinseimatec Co., Ltd., product number FPW-800, and [ XER-91] is a fine particle of bridged NBR (acrylonitrile butadiene rubber), product number XER-91.
*Preparation of the inner layer Material
The prepreg for the inner layer material was prepared by the above method.
Three prepregs were laminated, and 18 μm thick copper foils (product of Furukawa Circuit Foil co., ltd., tokyo, japan, product number GT Foil) were placed on both sides of the laminate to form a laminate.
By passing at 392N/cm2(40kgf/cm2) And hot-pressed at 170 c for 120 minutes, and the resulting laminate was molded into a laminate for an inner layer material. Circuit patterns were formed on both sides of the laminate by subtractive methods to obtain via holes. Further, the surface of the circuit was treated with an acid and treated into black oxide, thereby producing a printed wiring board for an inner layer material.
*Preparation of multilayer sheets
On both sides of the above printed circuit board (for inner layer material), one sheet of the above prepreg was laminated to a prepreg-laminate, and then one sheet of copper foil 18 μm thick was laminated on each side thereof, thereby producing a laminate.
Each side of the laminate was etched thoroughly, each of the above prepregs was placed on both etched sides of a prepreg etched laminate, and each of 18 μm thick copper foils was laminated on each outer side of the etched laminate to prepare a multilayer board product for characterizing its flame retardancy.
By passing at 392N/cm2(40kgf/cm2) And hot-pressing at 170 ℃ for 120 minutes, and molding the resulting laminate into a multilayer board.
Example 13
*Preparation of resin composite copper foil
Resin varnishes shown in table 2 were prepared for example 13 and coated on one side of an 18 μm thick copper foil (product of Furukawa Electric Industries co., ltd., tokyo, japan, trademark GT foil), followed by heating at 160 ℃ for 10 minutes to evaporate the solvent contained therein to dryness, to obtain a resin composite copper foil having a resin portion thickness of 60 μm.
*Preparation of the inner layer Material
The inner layer material obtained in example 1 was used.
*Preparation of multilayer sheets
The inner layer material obtained in example 1 was used.
The inner layer and the above resin composite copper foil are placed to form a laminate such that each resin layer side of the latter two sheets faces both sides of the circuit pattern forming surface.
Each side of the laminate above was etched completely, each of the above prepregs was mounted on both etched sides of the prepreg etched laminate, and then each copper foil 18 μm thick was laminated on each outer side of the etched laminate to prepare a plate product for characterizing its flame retardancy.
Passing through at 98N/cm2(10kgf/cm2) Hot pressing at 170 ℃ for 120 minutes, molding the resulting laminate, and obtaining a multilayer board.
Example 14
*Preparation of resin sheet
In example 14, the resin varnish shown in table 2 was prepared and coated on the surface of a polyethylene terephthalate film, the surface of which was coated with a release agent by a bar coater. The solvent was then evaporated to dryness by heating at 160 ℃ for 10 minutes. The polyethylene terephthalate film was removed, and a resin sheet having a thickness of 160 μm was obtained when the film was removed.
*Preparation of the inner layer Material
The inner layer material obtained in example 1 was used.
*Preparation of multilayer sheets
A circuit-forming inner layer material is placed on both sides of the resin sheet to form a laminate. A resin sheet and an 18 μm thick copper foil (product of Furukawa Electric Industries co., ltd., tokyo, japan, trademark GT foil) were placed on the outer surface to form a laminate.
A laminate article was prepared in the same manner as described in example 13, except that the resin sheet of example 10 was used, to characterize its flame retardancy.
Passing through at 98N/cm2(1Okgf/cm2) Hot pressing at 170 ℃ for 120 minutes, and molding the resulting board product into a multilayer board.
Example 15
*Preparation of the inner layer Material
The inner layer material obtained in example 1 was used.
*Preparation of multilayer sheets
In example 15, resin varnishes shown in table 2 were prepared and coated on the surface of the above inner layer material, on which a circuit pattern was formed by a bar coater. Then it was evaporated to dryness by heating at 160 ℃ for 10 minutes. An 18 μm thick copper foil (product of Furukawa Electric Industries Co., Ltd., Tokyo, Japan, trademark GT foil) was placed on the outer surface, passing through the hole at 98N/cm2(10kgf/cm2) Was hot-pressed at 170 ℃ for 120 minutes, and was molded into a multilayer board. Both sides of the panel were thoroughly etched to characterize their flame retardancy according to the method described in example 13.
TABLE 1
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Proportioning | ||||||||
| Synthesis of resin part of (1) | 100 | |||||||
| Synthesis of resin part of (2) | 100 | |||||||
| Synthesis of resin portion of (3) | 100 | 100 | ||||||
| Synthesis of resin portion of (4) | 100 | |||||||
| Synthesis of resin portion of (5) | 100 | 100 | 100 | |||||
| Synthesis of resin portion of (6) | ||||||||
| Synthesis of resin portion of (7) | ||||||||
| YD-128 | 11.1 | |||||||
| YDCN-704 | 80 | |||||||
| Dicy | 2.62 | 3.84 | 2.68 | 3.46 | 3.28 | 3.9 | 2.68 | 7.34 |
| PSM4357 | ||||||||
| 2E4MZ | 0.01 | 0.05 | 0.3 | 0.1 | 0.05 | 0.06 | 0.3 | 0.18 |
| DMF | 60.3 | 61 | 60.5 | 61 | 61 | 67.5 | 78 | |
| Magnesium hydroxide | 150 | |||||||
| Aluminum hydroxide | ||||||||
| Wollastonite | 30 | |||||||
| XER91 | ||||||||
| Resins of the examples | ||||||||
| P content (wt%) in the phosphorus-containing epoxy resin (A) | 3.01 | 1.85 | 2.2 | 2 | 2 | 2 | 2.2 | 2 |
| Required epoxy resin (wt%) | 20 | 42.6 | 35 | 34.7 | 40.3 | 40.3 | 35 | 40.3 |
| The mole ratio of the phosphorus compound to 1mol of the quinone compound | 1.56 | 1.02 | 1.41 | 1.25 | 1.12 | 1.12 | 1.41 | 1.12 |
| Characterization of the laminates | ||||||||
| Flame retardancy UL-94 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Peel strength (kN/m) | 1.3 | 1.5 | 1.5 | 1.3 | 1.3 | 1.4 | 1.4 | 1.2 |
| Peel Strength (layer to layer) (kN/m) | 1.1 | 1.2 | 1.2 | 1 | 1 | 1.1 | 1.1 | 0.9 |
| Starting temperature (. degree. C.) of thermal decomposition | 322.8 | 351.0 | 333.4 | 329.8 | 338 3 | 328.8 | 250/333.4 | 331.5 |
| Tg(℃) | 134 | 152 | 142 | 135 | 138 | 142 | 142 | 138 |
| P content (wt%) in the epoxy resin composition (a) | 2.93 | 1.78 | 2.14 | 1.93 | 1.94 | 1.74 | 1.65 | 0.59 |
| Bromine content (wt%) in the epoxy resin composition (a) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
*The required epoxy resin: represented by general formulae 1, 2 and 3
*The starting temperature of the process of example 7,
thermal decomposition of Al (OH)3The initial temperature of (a) is 250 DEG C
The thermal decomposition temperature of the resin to be tested was 333 deg.C
*YDCN-704: tohto Kasei Co., Ltd, o-cresol type epoxy resin having an epoxy equivalent of 205g/eq
TABLE 2
| Examples | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 |
| Proportioning | ||||||||
| Synthesis of resin part of (1) | 100 | 100 | 100 | |||||
| Synthesis of resin part of (2) | 100 | |||||||
| Synthesis of resin portion of (3) | ||||||||
| Synthesis of resin portion of (4) | ||||||||
| Synthesis of resin portion of (5) | 100 | |||||||
| Synthesis of resin portion of (6) | 100 | 100 | ||||||
| Synthesis of resin portion of (7) | 100 | |||||||
| YD-128 | 4.4 | |||||||
| YDCN-704 | ||||||||
| Dicy | 3.84 | 1.8 | 4.47 | 2.62 | 2.62 | 2.62 | 2.1 | |
| PSM4357 | 34.6 | |||||||
| 2E4MZ | 0.05 | 0.06 | 0.05 | 0.02 | 0.01 | 0.01 | 0.01 | 0.04 |
| DMF | 67 | 79.1 | 61 | 67 | 62.4 | 130.7 | 42.1 | |
| Magnesium hydroxide | ||||||||
| Aluminum hydroxide | 11 | |||||||
| Wollastonite | ||||||||
| XER91 | 3.6 | 120 | ||||||
| Resins of the examples | ||||||||
| P content (wt%) in the phosphorus-containing epoxy resin (A) | 1.85 | 2 | 3.83 | 1.28 | 3.01 | 3.01 | 3.01 | 3.83 |
| Required epoxy resin (wt%) | 42.6 | 40.3 | 28.1 | 42 | 20 | 20 | 20 | 28.1 |
| The mol ratio of the phosphorus compound to 1mol of the quinone compound | 1.02 | 1.12 | 1.98 | 1.02 | 1.56 | 1.56 | 1.56 | 1.98 |
| Characterization of the laminates | ||||||||
| Flame retardancy UL-94 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Peel strength (kN/m) | 14 | 1.1 | 1.5 | 1.1 | 1.3 | 1.5 | 1.3 | 1.7 |
| Peel Strength (layer to layer) (kN/m) | 1.1 | 0.9 | 1.1 | 0.9 | - | - | 1 | 1.3 |
| Starting temperature (. degree. C.) of thermal decomposition | 341.0 | 339.5 | 335.8 | 323.3 | 322.8 | 322.8 | 322.8 | 331.0 |
| Tg(℃) | 152 | 129 | 132 | 156 | 132 | 129 | 134 | 134 |
| P content in epoxy resin composition (a) (wt%) | 1.61 | 1.48 | 3.76 | 1.22 | 2.83 | 1.35 | 2.93 | 3.6 |
| Bromine content (wt%) in the epoxy resin composition (a) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
TABLE 3
| Comparative example | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Proportioning | |||||||
| Synthesis of resin portion of (5) | 100 | 100 | |||||
| Synthesis of resin portion of (8) | 100 | ||||||
| Synthesis of resin portion of (9) | 100 | ||||||
| Synthesis of the resin portion of (10) | 100 | ||||||
| YDB-500 | 90 | 94 | |||||
| YDCN-704 | 10 | 80 | 80 | ||||
| YDB-400 | 6 | ||||||
| Dicy | 238 | 3.26 | 3.61 | 2.45 | 7.34 | 7.34 | |
| PSM4357 | 22.39 | ||||||
| 2E4Mz | 0.06 | 0.1 | 0.4 | 0.5 | 0.18 | 0.18 | 0.06 |
| DMF | 60 | 61 | 61 | 60 | 110 | 222 | |
| Magnesium hydroxide | 190 | ||||||
| Wollastonite | |||||||
| XER91 | |||||||
| Resins of the examples | |||||||
| P content (wt%) in the phosphorus-containing epoxy resin (A) | - | 1.86 | 3 | 3.12 | 2 | 2 | - |
| Required epoxy resin (wt%) | 0 | 0 | 17.4 | 50 | 40.3 | 40.3 | 0 |
| The molar ratio is as follows: phosphorus compound and 1mol of quinone compound | - | 1.75 | - | 1.70 | 1.12 | 1.12 | - |
| Characterization of the laminates | |||||||
| Flame retardancy UL-94 | V-0 | V-1 | V-0 | V-0 | V-1 | V-0 | V-0 |
| Peel strength (kN/m) | 1.5 | 1.1 | 1.1 | 1.3 | 1.3 | 0.9 | 1.3 |
| Peel Strength (layer to layer) (kN/m) | 1.1 | 0.4 | 0.5 | 0.7 | 1 | 0.5 | 1 |
| Starting temperature (. degree. C.) of thermal decomposition | 301.3 | 325.8 | 335.6 | 325.2 | 334.5 | 331.6 | 314 |
| Tg(℃) | 132 | 128 | 110 | 98 | 138 | 138 | 133 |
| P content (wt%) in the epoxy resin composition (a) | 0 | 1.8 | 2.88 | 3.03 | 1.1 | 0.59 | 0 |
| Bromine content (wt%) in the epoxy resin composition (a) | 18.9 | 0 | 0 | 0 | 0 | 0 | 18.9 |
*YDB-500: a product of Tohto Kasei co., ltd., brominated bisphenol a type epoxy resin, epoxy equivalent: 500g/eq, bromine content: 21 wt.%
*YDB-400: a product of Tohto Kasei co., ltd., brominated bisphenol a type epoxy resin, epoxy equivalent: 400g/eq, bromine content: 49 wt.%
As is apparent from the characterization in Table 3, even if the phosphorous epoxy resin using some technical features of the present invention is used, if the content of at least one epoxy resin (C) selected from the group consisting of formula 1, formula 2 and formula 3 is less than 20% by weight or more than 40% by weight, good adhesion and heat resistance are not provided. In addition, the composition using the reaction product of the organic phosphorus compound (b) and the epoxy resin without quinone gives poor adhesion and low heat resistance. The composition of the invention not only has higher glass transition temperature, but also has higher thermal decomposition temperature than the conventional bromine-containing epoxy resin-based flame retardant. This means that the product of the invention has more excellent heat resistance during long-term use.
As described above, although the flame retardant epoxy resin composition comprising the phosphorous epoxy resin of the present invention does not contain halogen, it still exhibits excellent flame retardant properties and provides good heat resistance and adhesion, and thus it is very suitable for printed wiring applications based on copper-clad laminates.
Claims (12)
1. A phosphorus-containing epoxy resin composition comprising an epoxy resin composition (a) containing a phosphorus-containing epoxy resin (A) and a hardener, wherein the phosphorus-containing epoxy resin (A) is a phosphorus-containing resin composition prepared by reacting a phosphorus-containing organic compound (B) with at least one epoxy resin (C) selected from the group consisting of general formula 1, general formula 2 and general formula 3, wherein the content of the epoxy resin (C) is 20 to 45% by weight in 100% by weight of the phosphorus-containing epoxy resin (A), the organic compound (B) is obtained by reacting 1.01 to 2mol of 3, 4, 5, 6-dibenzo-1, 2-oxyphosphite (hexacyclic) -2-oxide with 1mol of a quinone compound,
wherein R is1Is a hydrogen atom and/or a phenyl group, m is an integer including 0,
wherein R is2Is a hydrogen atom and/or a phenyl group, n is an integer including 0,
wherein R is3Is a hydrogen atom and/or a phenyl group, l is an integer including 0,
and X is-CH2-、-O-、-CO-、-SO2-、-S-、-CH(C6H5)-、-C(C6H5)2-, bond or formula (4):
2. the phosphorus-containing epoxy resin composition according to claim 1, wherein the phosphorus content in the phosphorus-containing epoxy resin (A) is 1.2 to 4% by weight, and the epoxy equivalent is 200g/eq to 600 g/eq.
3. A phosphorus-containing epoxy resin composition according to claim 1 or 2, wherein the quinone compound is 1, 4-benzoquinone and/or 1, 4-naphthoquinone.
4. A flame-retardant epoxy resin composition, characterized in that the phosphorus in the resin composition is derived from the phosphorus-containing epoxy resin composition according to any one of claims 1 to 3, wherein the phosphorus content in the epoxy resin composition (a) containing the phosphorus-containing epoxy resin (A) and the hardener is 0.5 to 4% by weight.
5. A flame retardant epoxy resin composition comprising the phosphorus-containing epoxy resin composition as claimed in any one of claims 1 to 3, wherein 10 to 150 parts by weight of an inorganic filler is added to 100 parts by weight of the epoxy resin composition (a) of claim 4 and the solid of the phosphorus-containing epoxy resin.
6. The flame retardant epoxy resin composition comprising a phosphorus-containing epoxy resin according to claim 5, wherein the inorganic filler is at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, talc, calcined talc, kaolin, titanium oxide, glass powder and silica microspheres.
7. A resin sheet prepared by molding the phosphorus-containing epoxy resin composition or the phosphorus-containing epoxy resin according to any one of claims 1 to 6 into a sheet form.
8. A resin-bearing composite metal foil prepared by coating the phosphorus-containing epoxy resin composition or the flame-retardant epoxy resin composition of phosphorus-containing epoxy resin according to any one of claims 1 to 6 on a metal foil.
9. A prepreg prepared by impregnating the phosphorous epoxy resin composition or the flame retardant epoxy resin composition comprising the phosphorous epoxy resin according to any one of claims 1 to 6 on a metal foil into an inorganic or organic sheet-type matrix.
10. A laminate prepared by molding at least one material selected from the resin sheet of claim 7, the resin composite metal foil of claim 8, or the prepreg of claim 9.
11. A multilayer sheet prepared by molding a laminate containing at least one layer of at least one material selected from the resin sheet of claim 7, the resin composite metal foil of claim 8, or the prepreg of claim 9.
12. A multilayer sheet prepared by coating a laminate with at least one phosphorus-containing epoxy resin composition or phosphorus-containing epoxy resin according to any one of claims 1 to 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000104284A JP4588834B2 (en) | 2000-04-06 | 2000-04-06 | Phosphorus-containing epoxy resin composition, flame-retardant resin sheet using the phosphorus-containing epoxy resin, metal foil with resin, prepreg and laminate, multilayer board |
| JP104284/2000 | 2000-04-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1040410A1 HK1040410A1 (en) | 2002-06-07 |
| HK1040410B true HK1040410B (en) | 2006-07-28 |
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