# US 10,307,990 B2 · Epoxy resin composition, prepreg, resin-coated metal foil, resin sheet, laminate and multilayer board > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,307,990 B2 - Document ID: US10307990B2 - Status: Granted - Kind: B2 - Application number: 13/258,402 - Filed: 2010-02-02 - Published: 2012-01-12 - Granted: 2019-06-04 - Earliest claimed: 2009-03-26 - Assignees: Panasonic Intellectual Property Management Co., Ltd. - Applicants: Hidetaka Kakiuchi; Yoshihiko Nakamura; Shunji Araki; Yuki Miyoshi - Inventors: Hidetaka Kakiuchi; Yoshihiko Nakamura; Shunji Araki; Yuki Miyoshi - Web page: https://patentgrep.com/patent/US10307990B2 ## CPC - B32B 15/092: comprising epoxy resins - B32B 7/12: using interposed adhesives or interposed materials with bonding properties - B32B 15/14: next to a fibrous or filamentary layer - B32B 27/10: of paper or cardboard - B32B 27/12: next to a fibrous or filamentary layer - B32B 27/281: {comprising polyimides} - B32B 27/36: comprising polyesters - B32B 27/38: comprising epoxy resins - B32B 29/002: {as the main or only constituent of a layer, which is next to another layer of the same or of a different material (next to a layer of a particular substance B32B9/06; next to a bituminous or tarry layer B32B11/06; next to a water-setting substance layer B32B13/08; next to a metal layer B32B15/12; next to a glass layer B32B17/065; next to a layer formed of natural mineral fibres or particles B32B19/046; next to a wood layer B32B21/06; next to a cellulosic plastic layer B32B23/06; next to a natural or synthetic rubber layer B32B25/06; next to a synthetic resin layer B32B27/10)} - C08G 59/1488: {containing phosphorus} - C08G 59/4021: {Ureas; Thioureas; Guanidines; Dicyandiamides} - C08G 59/62: Alcohols or phenols - C08G 59/686: {containing nitrogen} - C08J 5/244: {using glass fibres} - C08J 5/249: {characterised by the additives used in the prepolymer mixture} - C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins - H05K 1/0326: {containing O} - B32B 2255/06: on metal layer - B32B 2255/10: on synthetic resin layer or on natural or synthetic rubber layer - B32B 2255/26: Polymeric coating - B32B 2260/023: Two or more layers - B32B 2260/046: Synthetic resin - B32B 2262/02: Synthetic macromolecular fibres - B32B 2262/101: Glass fibres - B32B 2307/204: Di-electric - B32B 2307/306: Resistant to heat - B32B 2307/3065: Flame resistant or retardant, fire resistant or retardant - B32B 2307/732: Dimensional properties - B32B 2457/08: PCBs, i.e. printed circuit boards - C08J 2363/00: Characterised by the use of epoxy resins; Derivatives of epoxy resins - C08K 5/49: Phosphorus-containing compounds {(C08K5/0091 takes precedence)} - H05K 2201/012: Flame-retardant; Preventing of inflammation - Y10T 428/31529: Next to metal - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract An epoxy resin composition contains a polyfunctional epoxy resin (A), a polyphenylene ether compound (B) and a phosphorus-modified curing agent (C). A polyphenylene ether (B1) having a number-average molecular weight of 500 to 3000 and an average of 1.0 to 3.0 hydroxyl groups per molecule, and an epoxy resin (B2) obtained by reacting this polyphenylene ether (B1) with an epoxy resin (D) having an average of 2.3 or fewer epoxy groups per molecule and the like, are included as the polyphenylene ether compound (B). A phosphorus-modified epoxy resin (P) is included in at least one selected from the polyfunctional epoxy resin (A), the epoxy resin (D) and a component other than the (A), (B) and (C) above. The phosphorus content is 1.5 to 4.5 mass % as a percentage of the resin solids in the epoxy resin composition. ## Claims ### Claim 1 An epoxy resin composition containing: a polyfunctional epoxy resin (A); a polyphenylene ether compound (B); a phosphorus-modified curing agent (C); and a component other than (A), (B) and (C), wherein: the polyfunctional epoxy resin (A) includes an average of 3 or more epoxy groups per molecule, the polyphenylene ether compound (B) includes an epoxy resin (B2) obtained by reacting a polyphenylene ether (B1) with an epoxy resin (D), the epoxy resin (D) having an average of 2.3 or fewer epoxy groups per molecule, and the polyphenylene ether (B1) having a number-average molecular weight of 500 to 2000 and an average of 1.0 to 3.0 hydroxyl group per molecule, at least one selected the group consisting of the polyfunctional epoxy resin (A), the epoxy resin (D), and the component other than the (A), (B) and (C) includes a phosphorus-modified epoxy resin (P), the phosphorus content is 1.5 to 4.5 mass % as a percentage of resin solids in the epoxy resin composition, the phosphorus-modified curing agent (C) is a resultant in a reaction between a first compound and an organic phosphorus second compound of the following Formula (I); the first compound is a resultant in an etherification between at least one monomer alcohol and a condensation product, the condensation product is a resultant in a condensation between formaldehyde and a phenol compound, wherein each R independently represents hydrogen or a C1-6 hydrocarbon group, and n is an integer from 0 to 4, a solids content of the phosphorus-modified curing agent (C) falls within a range of 3.9 to 43 mass % with respect to solids mass of the polyfunctional epoxy resin (A) and the polyphenylene ether compound (B), and the polyfunctional epoxy resin (A), the polyphenylene ether compound (B) and the phosphorus-modified epoxy resin (P) are miscible. ### Claim 2 (depends on 1) The epoxy resin composition according to claim 1, wherein the polyphenylene ether (B1) has an average of 1.5 to 2.5 hydroxyl groups per molecule. ### Claim 3 (depends on 2) The epoxy resin composition according to claim 2, wherein the phosphorus-modified epoxy resin (P) is obtained by reacting an epoxy resin including a novolac epoxy resin or a bifunctional epoxy resin with a reaction product of a quinone compound and an organic phosphorus compound represented by Formula (I) below: wherein each R independently represents hydrogen or a C1-6 hydrocarbon group, and n is an integer from 0 to 4. ### Claim 4 (depends on 2) The epoxy resin composition according to claim 2, wherein the polyfunctional epoxy resin (A) includes at least one of a cresol novolac epoxy resin and a phenol novolac epoxy resin. ### Claim 5 (depends on 2) The epoxy resin composition according to claim 2, wherein the component other than (A), (B) and (C) includes the epoxy resin (D) having an average of 2.3 or fewer epoxy groups per molecule, and the solids content of the phosphorus-modified curing agent (C) is 11.05 mass % with respect to solids mass of the polyfunctional epoxy resin (A) and the polyphenylene ether compound (B). ### Claim 6 (depends on 2) The epoxy resin composition according to claim 2, further including a curing agent (E) containing no phosphorus atoms. ### Claim 7 (depends on 2) The epoxy resin composition according to claim 2, further including an inorganic filler in an amount of 35 to 350 mass % of the resin solids in the epoxy resin composition. ### Claim 8 (depends on 1) The epoxy resin composition according to claim 1, wherein the phosphorus-modified epoxy resin (P) is obtained by reacting an epoxy resin including a novolac epoxy resin or a bifunctional epoxy resin with a reaction product of a quinone compound and an organic phosphorus compound represented by Formula (1) below: wherein each R independently represents hydrogen or a C1-6 hydrocarbon group, and n is an integer from 0 to 4. ### Claim 9 (depends on 8) The epoxy resin composition according to claim 8, wherein the polyfunctional epoxy resin (A) includes at least one of a cresol novolac epoxy resin and a phenol novolac epoxy resin. ### Claim 10 (depends on 1) The epoxy resin composition according to claim 1, wherein the polyfunctional epoxy resin (A) includes at least one of a cresol novolac epoxy resin and a phenol novolac epoxy resin. ### Claim 11 (depends on 1) The epoxy resin composition according to claim 1, wherein the component other than (A), (B) and (C) includes the epoxy resin (D having an average of 2.3 or fewer epoxy groups per molecule, and the solids content of the phosphorus-modified curing agent (C) is 11.05 mass % with respect to solids mass of the polyfunctional epoxy resin (A) and the polyphenylene ether compound (B). ### Claim 12 (depends on 11) The epoxy resin composition according to claim 11, further including a curing agent (E) containing no phosphorus atoms. ### Claim 13 (depends on 12) The epoxy resin composition according to claim 12, further including an inorganic filler in an amount of 35 to 350 mass % of the resin solids in the epoxy resin composition. ### Claim 14 (depends on 11) The epoxy resin composition according to claim 11, further including an inorganic filler in an amount of 35 to 350 mass % of the resin solids in the epoxy resin composition. ### Claim 15 (depends on 1) The epoxy resin composition according to claim 1, further including a curing agent (E) containing no phosphorus atoms. ### Claim 16 (depends on 15) The epoxy resin composition according to claim 15, further including an inorganic filler in an amount of 35 to 350 mass % of the resin solids in the epoxy resin composition. ### Claim 17 (depends on 1) The epoxy resin composition according to claim 1, further including an inorganic filler in an amount of 35 to 350 mass % of the resin solids in the epoxy resin composition. ### Claim 18 (depends on 1) A prepreg, obtained by drying a base material that has been impregnated with the epoxy resin composition according to claim 1. ### Claim 19 (depends on 1) A resin-coated metal foil, obtained by drying a metal foil that has been coated with the epoxy resin composition according to claim 1. ### Claim 20 (depends on 1) A resin sheet, obtained by drying an organic film that has been coated with the epoxy resin composition according to claim 1. ### Claim 21 (depends on 1) A laminate, comprising a desired number of at least one selected from a prepreg obtained by drying a base material that has been impregnated with the epoxy resin composition according to claim 1, a resin-coated metal foil obtained by drying a metal foil that has been coated with the epoxy resin composition according to claim 1 and a resin sheet obtained by drying an organic film that has been coated with the epoxy resin composition according to claim 1, which have been stacked, heated, pressed and laminate molded. ### Claim 22 (depends on 1) A multilayer board, comprising at least one selected from a prepreg obtained by drying a base material that has been impregnated with the epoxy resin composition according to claim 1, a resin-coated metal foil obtained by drying a metal foil that has been coated with the epoxy resin composition according to claim 1 and a resin sheet obtained by drying an organic film that has been coated with the epoxy resin composition according to claim 1, which have been laid over an inner-layer circuit board, and heated, pressed and laminate molded. ### Claim 23 (depends on 1) The epoxy resin composition according to claim 1, wherein an epoxy equivalent of the phosphorus-modified epoxy resin (P) is 200 g/eq to 600 g/eq. ### Claim 24 (depends on 1) The epoxy resin composition according to claim 1, wherein the epoxy resin (B2) has an average of 2.3 or fewer epoxy groups per molecule. ### Claim 25 (depends on 1) The epoxy resin composition according to claim 1, wherein the polyfunctional epoxy resin (A) includes the phosphorus-modified epoxy resin (P). ### Claim 26 (depends on 1) The epoxy resin composition according to claim 1, wherein: the polyfunctional epoxy resin (A) includes the phosphorus-modified epoxy resin (P), and the phosphorus-modified epoxy resin (P) is obtained by reacting an epoxy resin including a novolac epoxy resin or a bifunctional epoxy resin with a reaction product of a quinone compound and an organic phosphorus compound represented by Formula (1) below: wherein each R independently represents hydrogen or a C1-6 hydrocarbon group, and n is an integer from 0 to 4. ### Claim 27 (depends on 1) The epoxy resin composition according to claim 1, wherein: the polyfunctional epoxy resin (A) includes the phosphorus-modified epoxy resin (P) and an epoxy resin including no phosphorous atoms, and the epoxy resin including no phosphorous atoms includes a cresol novolac epoxy resin. ### Claim 28 (depends on 1) The epoxy resin composition according to claim 1, wherein: the epoxy resin (D) includes the phosphorus-modified epoxy resin (P), and the phosphorus-modified epoxy resin (P) includes a bifunctional phosphorous-modified epoxy resin. ### Claim 29 (depends on 1) The epoxy resin composition according to claim 1, wherein: the component other than the (A), (B) and (C) includes the phosphorus-modified epoxy resin (P), and the phosphorus-modified epoxy resin (P) includes a bifunctional phosphorous-modified epoxy resin. ### Claim 30 (depends on 1) The epoxy resin composition according to claim 1, further containing: a curing agent (E) including no phosphorus atoms; and a solvent, wherein the solvent includes N, N-dimethylformamide.