KR20160046087A - Epoxy Resin Compositions for Prepreg Having Halogen Free and Flame Retardant - Google Patents
Epoxy Resin Compositions for Prepreg Having Halogen Free and Flame Retardant Download PDFInfo
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- KR20160046087A KR20160046087A KR1020140141435A KR20140141435A KR20160046087A KR 20160046087 A KR20160046087 A KR 20160046087A KR 1020140141435 A KR1020140141435 A KR 1020140141435A KR 20140141435 A KR20140141435 A KR 20140141435A KR 20160046087 A KR20160046087 A KR 20160046087A
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- epoxy resin
- prepreg
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- parts
- epoxy
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 129
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 129
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000003063 flame retardant Substances 0.000 title claims description 37
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 35
- 229910052736 halogen Inorganic materials 0.000 title abstract description 8
- 150000002367 halogens Chemical class 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims description 39
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 14
- 239000012943 hotmelt Substances 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- -1 aluminum triheylate Chemical compound 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- 239000012783 reinforcing fiber Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000009960 carding Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- WAILHVKSZMVKJB-UHFFFAOYSA-N (1-phenylcyclopenta-2,4-dien-1-yl)benzene Chemical compound C1=CC=CC1(C=1C=CC=CC=1)C1=CC=CC=C1 WAILHVKSZMVKJB-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QWJNFFYFEKXZBF-UHFFFAOYSA-N cyanocyanamide Chemical compound N#CNC#N QWJNFFYFEKXZBF-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/08—Epoxidised polymerised polyenes
Abstract
Description
본 발명은 복합재료로 사용되는 무할로겐 난연성 프리프레그용 에폭시수지 조성물에 관한 것이다. 구체적으로는 내열성이 우수한 노블락형 에폭시수지와 난연성과 부착력이 우수한 전자부품 기판용의 디싸이클로펜타디엔계 에폭시수지, 인이 함유된 포스파젠계 에폭시수지, 무기 난연제를 혼합하여 조성된 핫멜트(Hot Melt) 방식의 프리프레그용 에폭시수지 조성물로써 기계적 강도 및 난연성 등이 우수하여 항공, 자동차, 전기 전자부품, 건축분야 등 다양한 산업에 널리 사용할 수 있다.
The present invention relates to an epoxy resin composition for a halogen-free flame-retardant prepreg used as a composite material. Concretely, a novolak type epoxy resin excellent in heat resistance, a dicyclopentadiene type epoxy resin for an electronic component substrate having excellent flame retardancy and adhesion, a hotmelt prepared by mixing a phosphazene-based epoxy resin containing phosphorus and an inorganic flame retardant ) Type epoxy resin composition for prepreg, which is excellent in mechanical strength and flame retardancy, and can be widely used in various industries such as aviation, automobiles, electric / electronic parts, and construction.
복합재료로 사용되는 프리프레그(Prepreg)는 일반적으로 보강섬유인 유리섬유, 탄소섬유, 아라미드섬유에 결합재로서 열경화성수지인 에폭시수지, 불포화폴리에스테르 수지 등으로 미리 함침(含浸)시킨 시트 형태이며, 이는 복합재료의 중간 재료로서 반 경화상태로 만들어진다.The prepreg used as the composite material is generally in the form of a sheet impregnated with epoxy resin, unsaturated polyester resin or the like which is a thermosetting resin as a bonding material to glass fibers, carbon fibers and aramid fibers which are reinforcing fibers, And is made into a semi-cured state as an intermediate material of the composite material.
일반적으로 프리프레그는 용제형 프리프레그와 핫멜트 프리프레그 방식으로 제조된다. 구체적으로는 에폭시수지를 용제로 희석시킨 액상의 에폭시수지에 섬유 원단을 함침시킨 후에 용제를 건조하여 제조하는 용제형 프리프레그 보다 에폭시수지를 높은 온도에서 녹여 이형지에 코팅한 후에 코팅된 에폭시수지를 섬유 원단에 함침시키는 핫멜트 방식이 많이 사용되고 있다. 그 이유는 경화과정 중 발생되는 반응하지 않는 용제에 의한 복합재의 기포현상과 층간 박리현상 등의 불량 발생을 줄일 수 있고, 기계적 강도가 우수하며 균일한 제품의 제조가 가능하기 때문이다.Generally, prepregs are prepared by solvent type prepreg and hot-melt prepreg method. More specifically, the epoxy resin is melted at a higher temperature than the solvent type prepreg prepared by impregnating a fiber cloth into a liquid epoxy resin diluted with a solvent and then drying the solvent, The hot melt method is often used to impregnate fabrics. The reason for this is that it is possible to reduce the occurrence of defects such as bubble phenomenon of the composite material caused by the non-reactive solvent generated during the curing process and interlayer peeling phenomenon, and it is possible to manufacture a uniform product with excellent mechanical strength.
보강섬유로서 탄소섬유, 유리섬유, 아라미드섬유, 바젤트섬유를 사용한 프리프레그 중 탄소섬유 프리프레그는 탄소섬유가 갖는 특성으로 높은 비강도와 비탄성률, 낮은 비중과 난연성이며, 가볍고 단단한 복합재료의 소재로서 항공기, 자동차, 전기 전자부품, 건축분야 등 다양한 산업에 널리 응용되어 사용되고 있다.Carbon fiber prepregs in prepregs using carbon fiber, glass fiber, aramid fiber, and basel fiber as reinforcing fibers have high nose strength, nonelasticity, low specific gravity and flame retardancy, and are light and hard composite materials It is widely used in various industries such as aircraft, automobile, electric and electronic parts, and construction.
프리프레그의 제조에 사용되는 열경화성 수지로는 에폭시수지, 불포화폴리에스테르수지, 비닐에스테르수지, 페놀수지 등이 있는데, 주로 에폭시수지를 사용하여 프리프레그를 제조한다. 에폭시수지는 경화반응 중에 수축이 잘 되지 않고, 전기 및 기계적 성질이 매우 우수할 뿐만 아니라 가공성, 내수성, 내약품성, 내마모성이 우수하고, 중합도에 따라 상온에서 액체, 반고체상과 고체형태로 나누어지고, 분자구조 또는 중합하는 범위에 따라 분류하여 사용된다.Examples of the thermosetting resin used in the preparation of the prepreg include an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, and a phenol resin. A prepreg is produced mainly by using an epoxy resin. The epoxy resin has excellent workability, water resistance, chemical resistance, abrasion resistance, and is excellent in electrical and mechanical properties, is not shrunk during curing reaction, is divided into liquid, semi-solid and solid forms at room temperature, Molecular structure or range of polymerization.
일반적으로 열경화성수지로 제조되는 프리프레그의 유기 고분자수지는 연소원이 있을 경우 열에 의해 고분자사슬이 분해되어 가연성 가스가 다량 발생되며, 발생한 열이 다시 고분자를 분해하는 연쇄반응으로 지속적인 연기가 다량 발생하고 높은 열에 의하여 화기와 화재 안전에 취약하다. 이를 방지하고자 고분자수지에 난연제로서 알루미늄 트리하이레이트와 같은 금속 수화물 무기계 난연제, 브롬 또는 염소를 함유한 할로겐화합물, 멜라민시아레이트의 질소계 화합물, 인산에스테르의 인계화합물 등을 첨가하여 난연성 복합재로 사용하고 있다. Generally, the organic polymer resin of a prepreg made of a thermosetting resin is a chain reaction in which a polymer chain is decomposed by heat and a large amount of combustible gas is generated, and heat generated again decomposes the polymer, resulting in a large amount of continuous smoke High heat is vulnerable to fire and fire safety. To prevent this, a flame retardant is added to the polymer resin as a flame retardant composite by adding a metal-based flame retardant such as aluminum triheylate, a halogen compound containing bromine or chlorine, a nitrogen-based compound of melamine cialate, have.
이와 관련한 종래기술로서, 대한민국 공개특허공보 제10-2011-0039044호(2011. 4. 15.)에 개시된 “프리프레그용 에폭시수지 조성물”은 초저온(-100℃ ~ -180℃)에서도 높은 충격강도 및 압축강도를 갖는 것으로 핫멜트 방식에 의한 제조방법을 기술하고 있으나, 조성물이 난연성보다는 일반 복합재료용 에 관한 것으로 화재 발생시 많은 가스와 연기가 발생하는 문제가 있다. 대한민국 공개특허공보 제10-2010-0040531호(2010. 4. 20.)에 개시된 “친환경성 복합재료를 적층한 난연, 내열, 내마모성, 고무변성 에폭시수지-카본섬유의 프리프레그 제조용 에폭시수지“는 할로겐 원소가 없는 인계 에폭시수지를 사용하였으나, 인계 에폭시수지가 용제에 희석된 수지로서 핫멜트 방식의 프리프레그 원료로는 사용이 어려워 프리프레그 제조가 불가능하다.As a conventional technique related thereto, the " epoxy resin composition for prepregs " disclosed in Korean Patent Laid-Open Publication No. 10-2011-0039044 (Apr. 15, 2011) And a compression strength. However, the composition is related to general composite materials rather than flame retardancy, and there is a problem that a lot of gas and smoke are generated when a fire occurs. "Epoxy resin for flame retardant, heat-resistant, abrasion-resistant, rubber-modified epoxy resin-carbon fiber prepreg laminated with environmentally friendly composite material" disclosed in Korean Patent Publication No. 10-2010-0040531 Phosphorus-free epoxy resin having no halogen element is used, but phosphorus-based epoxy resin is diluted in a solvent and is difficult to use as a hot-melt type prepreg raw material, making prepreg manufacture impossible.
또한 대한민국 공개특허공보 제10-2011-0078652호(2011. 7. 7.)에 개시된 “프리프레그용 강화섬유 속의 개섬방법 및 그에 의해 제조된 프리프레그”는 섬유 제조시 부여된 유제를 고온에서 제거한 후에 개섬시킴으로써 개섬 효과가 증진된 프리프레그용 강화섬유 속의 개섬방법으로서 에폭시수지 조성물보다는 제작 공정을 개선한 것이다. 대한민국 공개특허공보 제10-2005-0043623호(2005. 5. 11.)에 개시된 “수지조성물 및 그것을 사용한 프리프레그 및 적층판”은 할로겐 프리이며 0.2㎜ 이하의 두께에서도 충분한 난연성을 갖고, 또한 충분한 내습성이나 흡습 땜납 내열성을 갖는 적층판을 제공하는 것으로 난연성 프리프레그에 대해 자세하게 기술되어 있으나, 에폭시수지를 용제로 희석하여 사용하는 용제형 프리프레그의 제작에 적합한 것이다. "Opening method in reinforcing fiber for prepreg and prepreg produced therefrom" disclosed in Korean Patent Laid-Open Publication No. 10-2011-0078652 (July 7, 2011) is a method of removing The carding method in the reinforcing fiber for prepreg in which the carding effect is enhanced by carding later is improved rather than the epoxy resin composition. "Resin composition and prepreg and laminate using the resin composition" disclosed in Korean Patent Laid-Open Publication No. 10-2005-0043623 (2005. 5. 11) are halogen-free and have sufficient flame retardancy even at a thickness of 0.2 mm or less, The flame-retardant prepreg is described in detail, but it is suitable for producing a solvent-type prepreg in which an epoxy resin is diluted with a solvent.
또한 대한민국 공개특허공보 특2001-0071882호(2001. 7. 31.)에 개시된 “난연성 수지 조성물”은 포스파젠에 작용기가 있는 물질을 일부 염소와 치환 반응시켜 포스파젠이 서로 가교 결합에 의해 폴리머를 만든 난연제, 즉 포스파젠 고분자를 열가소성수지와 일정비율로 조성하여 난연성을 갖는 난연성 수지조성물에 관한 것으로 수지의 종류가 열가소성 수지인 점에서 큰 차이가 있다. 대한민국 공개특허공보 특2002-0068400호(2002. 8. 27.)에 개시된 “에폭시수지 조성물 및 전자 부품”은 포스파젠 화합물을 에폭시수지에 배합하여 전자 부품용 소자를 밀봉함으로써 내열성, 내습성, 내열 충격성 등의 물성이 우수한 전자 부품을 만드는 것으로 포스파젠을 사용한 것에 불과할 뿐이다. A "flame retardant resin composition" disclosed in Korean Patent Laid-Open Publication No. 2001-0071882 (2001. 7. 31.) discloses that a substance having a functional group in phosphazene is subjected to a substitution reaction with a part of chlorine to cause the phosphazene to cross- The present invention relates to a flame retardant resin composition comprising a flame retardant, that is, a phosphazene polymer blended with a thermoplastic resin at a predetermined ratio, and has a large difference in that the resin is a thermoplastic resin. "Epoxy Resin Composition and Electronic Component" disclosed in Korean Patent Publication No. 2002-0068400 (Aug. 27, 2002) discloses an epoxy resin composition containing a phosphazene compound in an epoxy resin and sealing the electronic component element, thereby exhibiting heat resistance, moisture resistance, It is merely the use of phosphazene to make electronic parts having excellent physical properties such as impact resistance.
대한민국 등록특허 10-0789564(2007. 12. 30.)에 개시된 “비할로겐 난연성 에폭시수지 조성물 및 이를 이용하여 제조된 수지 부착 동박”에는 접착력이 우수하며 난연성이 우수한 동박 접착용 에폭시수지로서 고강도 탄소복합체나 난연성 프리프레그용 에폭시수지 조성물로는 적합하지 않다. 또한 경화제와 촉진제, 포스파젠화합물을 디메틸포름아마이드(DMF)에 용해한 후에 노블락 에폭시수지와 인계 에폭시수지를 넣고 제조하는 방법으로서 디메틸포름아마이드를 사용하지 않는 핫멜트 프리프레그용 에폭시수지로 사용하기 어렵고, 디메틸포름아마이드를 접착제로 사용할 경우 용제를 제거해야 하는 문제점이 남아 있으며, 인계 에폭시수지를 국도화학 KDP550을 사용하였으나 본 발명에서의 인계 에폭시수지는 포스파젠에 에폭시수지를 반응한 포스파젠 인계 에폭시수지로 에폭시수지의 구조와 당량에 커다란 차이가 있다."Non-halogen flame retardant epoxy resin composition and resin-coated copper foil produced using the same" disclosed in Korean Patent No. 10-0789564 (Dec. 30, 2007), an epoxy resin for a copper foil having excellent adhesive strength and excellent flame retardancy, Or an epoxy resin composition for a flame retardant prepreg. In addition, it is difficult to use epoxy resin for hot-melt prepreg which does not use dimethylformamide by dissolving hardener, accelerator and phosphazene compound in dimethylformamide (DMF), then adding novolak epoxy resin and phosphorus epoxy resin, When formamide is used as an adhesive, there is a problem to remove the solvent, and phosphorus-based epoxy resin is used as KDP 550. However, the phosphorus-based epoxy resin used in the present invention is a phosphazene-based epoxy resin reacted with phosphazene, There is a large difference in structure and equivalence of the resin.
따라서 상기와 같이 종래의 프리프레그 경우 사용되는 에폭시수지가 내열성과 난연성이 낮아 복합재로 사용할 경우 열에 약한 문제가 있어 이를 보완한 다른 형태로서 기계적 강도 및 난연성이 우수한 핫멜트 방식의 프리프레그용 에폭시수지 조성물의 출현을 간절히 희망하고 있는 실정이다.
Therefore, the epoxy resin used in the conventional prepregs is low in heat resistance and flame retardancy, and thus has a weak heat problem when it is used as a composite material. Another type of epoxy resin is a hot-melt type epoxy resin composition for prepregs excellent in mechanical strength and flame retardancy It is a reality that hopes for appearance.
본 발명은 상기의 문제점을 해소하기 위하여 안출된 것으로서, 핫 멜트 방식에 적합한 에폭시수지 조성물로 할로겐 프리 포스파젠 인계 에폭시수지와 노블락형 에폭시수지, 디싸이클로펜타디엔계 에폭시수지와 무기계 난연 필러를 사용한 프리프레그용 에폭시수지 조성물로 할로겐이 함유되지 않아 친환경적이며, 난연성이 우수하고, 기계적 강도 등이 우수한 무할로겐 난연성 프리프레그용 에폭시수지 조성물의 제공을 그 과제로 한다.
DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-described problems, and it is an object of the present invention to provide an epoxy resin composition suitable for a hot melt system, which comprises a halogen-free phosphazene phosphorus epoxy resin, a novolak epoxy resin, a diphenylcyclopentadiene epoxy resin, An epoxy resin composition for a legless halogen-free flame-retardant prepreg which is free from halogen and is eco-friendly, excellent in flame retardancy, and excellent in mechanical strength.
본 발명은 주제와 경화제로 이루어진 프리프레그용 에폭시수지 조성물에 있어서, 상기 주제는 a) 에폭시 당량이 170~190인 페놀 노볼락형 에폭시수지 10~20중량부; b) 2개 이상의 에폭시기를 가지는 비스페놀 A형 에폭시수지 15~20중량부; c) 에폭시 당량이 320~400인 포스파젠계 에폭시수지 20~35중량부; d) 에폭시 당량이 250~270인 디사이클로펜타디엔계 에폭시수지 15~20중량부를 포함하여 이루어지고,The present invention provides an epoxy resin composition for a prepreg comprising a subject and a curing agent, wherein the subject is a) 10 to 20 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 170 to 190; b) 15 to 20 parts by weight of a bisphenol A type epoxy resin having two or more epoxy groups; c) 20 to 35 parts by weight of a phosphazene-based epoxy resin having an epoxy equivalent of 320 to 400; d) 15 to 20 parts by weight of a dicyclopentadiene epoxy resin having an epoxy equivalent of 250 to 270,
상기 경화제는 a) 에폭시 당량이 160~196으로 상온에서 액상인 비스페놀 A형 에폭시수지 15~20중량부; b) 입경이 1~20㎛인 디시안디아마이드 2~15중량부; c) 무기난연제 5~10중량부를 포함하여 이루어지되, 상기 주제와 경화제는 65~75중량% : 25~35중량%의 비율로 혼합되는 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물을 제공한다.A) 15 to 20 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of 160 to 196 and a liquid at room temperature; b) 2 to 15 parts by weight of dicyandiamide having a particle diameter of 1 to 20 占 퐉; c) an inorganic flame retardant, and 5 to 10 parts by weight of an inorganic flame retardant, wherein the mixture is mixed in a ratio of 65 to 75% by weight and 25 to 35% by weight of a curing agent. do.
또한 본 발명은 상기 2개 이상의 에폭시기를 가지는 비스페놀 A형 에폭시수지가 상온에서 액상 또는 고상 중 1종 이상인 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물을 제공한다.The present invention also provides an epoxy resin composition for a halogen-free flame-retardant prepreg, wherein the bisphenol A epoxy resin having two or more epoxy groups is at least one of liquid or solid at room temperature.
또한 본 발명은 상기 에폭시 당량이 320~400인 포스파젠계 에폭시수지가 인 함량 2~4중량%, 용융온도 80℃, 점도 1000-2000CPS인 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물을 제공한다.The epoxy resin composition for a halogen-free flame-retardant prepreg according to the present invention is characterized in that the phosphazene-based epoxy resin having an epoxy equivalent of 320 to 400 has a phosphorus content of 2 to 4 wt%, a melting temperature of 80 DEG C, and a viscosity of 1000 to 2000 CPS. to provide.
마지막으로 본 발명은 상기 무기 난연제가 인(P) 함량 11.1중량%, 질소(N) 함량 6.5중량%, 비중 1.8, 물에 대한 용해도 0.4g/100㎖, 분해온도 220℃ 이상의 흰색 파우더인 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물을 제공한다.
Finally, the present invention is characterized in that the inorganic flame retardant is a white powder having a phosphorus (P) content of 11.1 wt%, a nitrogen (N) content of 6.5 wt%, a specific gravity of 1.8, a solubility in water of 0.4 g / 100 mL, Halogen-free flame-retardant prepreg.
본 발명에 의한 무할로겐 난연성 프리프레그용 에폭시수지 조성물은 핫멜트 방식으로 제조되므로 프리프레그용 에폭시수지의 필름 이형성과 상온 저장 안정성을 개선할 수 있다.Since the epoxy resin composition for a halogen-free flame-retardant prepreg according to the present invention is produced by a hot-melt method, it is possible to improve a film release property and storage stability at room temperature of an epoxy resin for prepreg.
또한 고온에서 경화성이 우수한 에폭시수지 조성물과 종래 할로겐 에폭시수지의 유독 가스 발생과 인체에 유해한 독성 물질을 포함한 프리프레그를 할로겐 원소가 없는 친환경적인 원료로 대체하여 핫멜트 방식의 난연성 프리프레그용 에폭시수지 조성물을 제공함으로써, 안전하고 친환경적이므로 다양한 산업 분야에서 복합재로 광범위하게 활용할 수 있게 된다.
In addition, an epoxy resin composition for a hot-melt type flame-retardant prepreg is prepared by replacing an epoxy resin composition having excellent curability at a high temperature and a prepreg containing toxic gases and toxic substances harmful to the human body of the conventional halogen epoxy resin by an eco- By making it safe and eco-friendly, it can be widely used as a composite material in various industries.
본 발명에 의한 무할로겐 난연성 프리프레그용 에폭시수지 조성물은 주제와 경화제로 이루어지는데, 이하에서 이에 대하여 상세히 설명하기로 한다.
The epoxy resin composition for a halogen-free flame-retardant prepreg according to the present invention comprises a base and a curing agent, which will be described in detail below.
(1) 주제(1) Subject
1) 페놀 노볼락형 에폭시수지1) Phenol novolak type epoxy resin
무할로겐 난연성 프리프레그용 에폭시수지 조성물의 기계적 특성과 내열성을 향상하고자 기계적 강도 및 난연성이 우수한 페놀 노블락형 에폭시수지를 사용하는데, 그 종류로서는 국도화학(주)의 YDPN 638(에폭시당량 170-190)을 10 ~ 20중량부 사용하는 것이 바람직하다. 그 사용량이 20중량부를 초과할 경우 복합재의 신율이 적고 충격에 쉽게 깨지는 현상이 발생할 수 있으며, 10중량부 미만일 경우 복합재의 기계적 강도가 약해지는 경향이 있고, 가장 적절한 사용량은 12 ~ 14중량부이다.
A phenolic novolak type epoxy resin excellent in mechanical strength and flame retardancy is used to improve the mechanical properties and heat resistance of the epoxy resin composition for halogen-free flame-retardant prepreg. YDPN 638 (epoxy equivalent 170-190) of Kukdo Chemical Co., Is used in an amount of 10 to 20 parts by weight. If the amount is more than 20 parts by weight, the elongation of the composite material may be small and the impact may be easily broken. If the amount is less than 10 parts by weight, the mechanical strength of the composite material tends to be weak, and the most suitable amount is 12 to 14 parts by weight .
2) 비스페놀 A형 에폭시 수지2) Bisphenol A type epoxy resin
먼저 에폭시수지는 분자 내에 2개 이상의 에폭시기를 가지는 화합물로서 경화물의 내열성, 굴곡강도, 압축강도 등 기계적 물성이 우수한 2관능의 에폭시수지를 사용할 수 있다. 또한 경화물의 우수한 기계적 물성을 유지하기 위해서 방향족계 에폭시수지의 사용이 바람직하다.First, an epoxy resin is a compound having two or more epoxy groups in a molecule, and a bifunctional epoxy resin having excellent mechanical properties such as heat resistance, bending strength and compressive strength of a cured product can be used. In addition, the use of aromatic epoxy resin is preferred in order to maintain excellent mechanical properties of the cured product.
에폭시수지는 2개 이상의 에폭시기를 가지며, 상온에서 액상인 방향족계 에폭시수지와 상온에서 고상인 에폭시수지로 단독으로 사용할 수 있으며, 2종 이상을 조합하여 사용할 수도 있다. 2개 이상의 에폭시기를 갖는 에폭시수지로는 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시수지 등이 있다.The epoxy resin may be used alone as an aromatic epoxy resin having two or more epoxy groups and being liquid at room temperature and a solid epoxy resin at room temperature, or a combination of two or more thereof may be used. Examples of epoxy resins having two or more epoxy groups include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins.
에폭시수지 중 상온에서 액상인 비스페놀A형 에폭시수지는 에폭시당량이 180∼200범위의 것이 바람직한데, 그 종류로는 국도화학(주)의 YD-128(에폭시당량 184∼190), YD-128M(에폭시당량 180∼196), YDF-170(에폭시당량 160∼180), 금호P&B 에폭시수지 KER-828(에폭시당량 184∼190) 등이 있다.The epoxy equivalent of the bisphenol A type epoxy resin, which is liquid at normal temperature in the epoxy resin, is preferably in the range of 180 to 200, and examples thereof include YD-128 (epoxy equivalents 184 to 190) and YD-128M Epoxy equivalent weight 180-196), YDF-170 (epoxy equivalent 160-180), Kumho P & B epoxy resin KER-828 (epoxy equivalent 184-190).
또한 상온에서 고상인 비스페놀 A형 에폭시수지로는 에폭시 당량이 높고 용융온도가 서로 달라 에폭시 당량과 용융온도에 따라 용융온도가 120℃ 미만인 것이고, 그 종류로는 국도화학(주) YD-011(에폭시당량 400-500), YD-014(에폭시당량 900-1000), YD-019(에폭시당량 2500-3100), 금호P&B 에폭시수지 KER-3001(에폭시당량 450-500), KER-3004 (에폭시당량 847-980), KER-7007(에폭시당량 1700-1950) 등이 있다The bisphenol A type epoxy resin, which is solid at room temperature, has a high epoxy equivalent and a melting temperature different from each other, and has a melting temperature lower than 120 ° C according to the epoxy equivalent and the melting temperature. Examples of the epoxy resin include YD-011 (epoxy YD-019 (epoxy equivalent: 2500-3100), Kumho P & B epoxy resin KER-3001 (epoxy equivalent: 450-500), KER-3004 (epoxy equivalent: 847 -980), KER-7007 (epoxy equivalent 1700-1950), and the like
상기 액상 및 고상인 비스페놀 A형 에폭시수지의 사용량은 15~20중량부가 바람직하며 프리프레그 제조의 경우 수지의 용융온도가 낮고, 상온에서 프리프레그의 표면 끈적거림이 적으므로 필름이형성이 우수하다. 사용량이 20중량부를 초과하면 난연성 수지의 조성이 낮아 난연성이 저하되며 에폭시수지의 용융온도가 높고 경화제와 혼합하는 온도가 높아져 수지의 겔화 위험성이 높아지며, 15중량부 미만인 경우 수지의 용융온도가 낮아지며 상온에서 프리프레그의 표면 끈적거림이 심하며 필름 이형성이 나빠진다. The amount of the liquid and solid bisphenol A epoxy resin used is preferably 15 to 20 parts by weight. In the preparation of the prepreg, the melting temperature of the resin is low and the surface stickiness of the prepreg is small at room temperature. When the amount is more than 20 parts by weight, the composition of the flame retardant resin is low and the flame retardancy is lowered. The melting temperature of the epoxy resin is high and the temperature at which the epoxy resin is mixed with the resin becomes high and the risk of gelation of the resin becomes high. When the amount is less than 15 parts by weight, The surface stickiness of the prepreg is severe and the film releasability is deteriorated.
여러 장의 프리프레그를 적층할 경우에 상호 접착을 양호하게 하기 위해 액상과 고상의 것을 적절하게 혼합하는데, 상온에서 표면 끈끈함이 적고 필름이형성이 좋은 수지 혼합비율로 액상 및 고상인 비스페놀 A형 에폭시수지 비율을 1 : 1~2로 혼합하여 사용하며, 바람직하게는 수지 점도와 프리프레그의 표면 상태 및 필름이형성을 고려해서 혼합비율은 1 : 1.5가 적합하다.
When a plurality of prepregs are laminated, a liquid phase and a solid phase are appropriately mixed so as to make mutual adhesion favorable. A liquid phase and a solid bisphenol A type epoxy resin having a low surface stickiness at room temperature and a good film- Ratio is 1: 1 to 2, and the mixing ratio is preferably 1: 1.5 in consideration of the resin viscosity, the surface state of the prepreg, and the film formation.
3) 인계 에폭시수지3) Phosphorous epoxy resin
난연제로서는 난연 특성이 우수한 할로겐형 난연제가 있는데, 이는 소각할 경우 다이옥신 발생 가능성이 제기된 이후 환경유해성 논란이 지속되고 있다. 비할로겐계 난연제로 가장 주목 받는 것은 인계 난연제로서, 구체적으로는 적인, 포스페이트, 포스포네이트, 포스피네이트, 포스핀옥사이드, 포스파젠과 인산에스테르계열의 화합물이 알려져 있다. 그 중 적인계 난연제는 가공 중 유독물질로 알려진 포스핀(PH3)의 발생 가능성으로 인해 표면 처리한 것이 사용되며, 경화 색상이 나빠 주로 내장부품에 한정 사용된다. 일반적인 인계 난연제는 인산에스테르 화합물로서, 화학구조가 안정하고 가소성을 부여하는 효과가 있으므로 난연 수지의 가공을 용이하게 하고 상용성과 내후성이 양호하나 내열성이 저하되는 단점이 있다. As a flame retardant, there is a halogen type flame retardant having excellent flame retarding property, and after the possibility of dioxin generation is raised by incineration, controversy about environment hazard continues. As a non-halogen flame retardant, phosphorus flame retardants are most noteworthy, and specific compounds such as phosphates, phosphonates, phosphinates, phosphine oxides, phosphazenes and phosphate esters are known. Among these flame retardants, surface treatment is used due to the possibility of phosphine (PH3), which is known as toxic substance during processing, and it is mainly used for internal parts because of poor hardening color. The general phosphorus flame retardant is a phosphoric acid ester compound, which has a chemical structure stable and has an effect of imparting plasticity, so that it is easy to process the flame retardant resin and has good compatibility and weatherability but has a low heat resistance.
인계 에폭시수지는 용제로 희석시킨 국도화학(주) 상품명 KDP-550MC65, KDP-555MC80이 있는데, 이는 용제형 프리프레그 제조에는 적합하나 핫멜트형 프리프레그 제조에는 적합하지 않다. 본 발명에서는 인계 에폭시수지로서 포스파젠계 화합물인 10-(2,5-Dihydroxyphenyl)-10H-9-oxa-phospha-phenathrene-10-oxide를 액상인 비스페놀 A형 에폭시수지(에폭시당량 184∼190)와 반응시켜 에폭시수지화한 켐필드(주) 제품명 EM-68(에폭시당량 320~400, 인 함량 2~4중량%, 용융온도 80℃, 점도 1000-2000CPS)을 20 ~ 35중량부 사용하였으며, 적절하게는 28중량부 사용하였다. 인계 에폭시수지가 20중량부 미만일 경우 난연 효과가 적으며, 35중량부를 초과하는 경우에는 난연 효과는 상승하나 에폭시수지 가격 상승과 수지 점성이 높아져 프리프레그의 표면 끈적거림이 심하게 되므로 프리프레그로 적절한 사용량은 28중량부이다.
The phosphorus-based epoxy resin is KDP-550MC65 and KDP-555MC80, which are diluted with a solvent, and are suitable for preparing a solvent type prepreg, but are not suitable for producing a hot melt type prepreg. In the present invention, 10- (2,5-Dihydroxyphenyl) -10H-9-oxa-phospha-phenathrene-10-oxide, which is a phosphazene compound as a phosphorus-based epoxy resin, is dissolved in a liquid bisphenol A type epoxy resin (epoxy equivalent 184 to 190) 20 to 35 parts by weight of EM-68 (epoxy equivalent: 320 to 400, phosphorus content: 2 to 4% by weight, melting temperature: 80 캜, viscosity: 1000 to 2000 CPS) Suitably 28 parts by weight were used. When the phosphorus-based epoxy resin is less than 20 parts by weight, the flame retardant effect is small. If the phosphorus-based epoxy resin is more than 35 parts by weight, the flame retardant effect is increased, but the epoxy resin price increases and the resin viscosity increases. Thus, the surface stickiness of the prepreg becomes severe, Is 28 parts by weight.
4) 디싸이클로펜타디엔계 에폭시수지4) Dicyclopentadiene-based epoxy resin
프리프레그의 접착력 향상과 고온 난연 효과를 증진시키고자 디싸이클로펜타디엔계 에폭시수지를 사용하는데, 그 종류로는 국도화학(주)의 YDCP-130(에폭시당량 250-270)을 10 ~ 15중량부, 바람직하게는 12중량부 사용하였다. 그 사용량이 15중량부를 초과하면 프리프레그 표면의 끈적거림이 적고 딱딱하여 프리프레그를 감아 사용할 때 크랙 발생이 나타날 수 있고 프리프레그의 단가 상승요인이 되며, 10중량부 이하이면 고온에서 접착력과 경화속도가 늘어지고 난연 효과가 떨어진다.
A dicyclopentadiene epoxy resin is used to improve the adhesive strength of the prepreg and the high temperature flame retardant effect, and 10-15 parts by weight of YDCP-130 (epoxy equivalents: 250-270) of Kukdo Chemical Co., Ltd. , Preferably 12 parts by weight. If the amount is more than 15 parts by weight, the surface of the prepreg is less tacky and hard, and when the prepreg is rolled up, cracks may be generated and a factor of raising the unit price of the prepreg may be. If the amount is less than 10 parts by weight, And the flame retarding effect is reduced.
(2) 경화제(2) Hardener
1) 에폭시수지1) Epoxy resin
잠재성 경화제로서 사용되는 디시안디아미드(dicyanamide)는 백색의 결정이므로 이를 용해하거나 분산시켜 사용하는 것이 바람직한데, 이를 위하여 상온에서 액상인 비스페놀A형 에폭시수지(에폭시당량이 180∼200)를 사용한다. 그 종류로는 국도화학(주)의 YD-128(에폭시당량 184∼190), YD-128M(에폭시당량 180∼196), YDF-170(에폭시당량 160∼180), 금호P&B 에폭시수지 KER-828(에폭시당량 184∼190) 등이 있다. 상기 비스페놀A형 에폭시수지의 사용량은 15 ~20중량부가 바람직하다.
The dicyanamide used as a latent curing agent is preferably a white crystal. Therefore, it is preferable to dissolve or disperse the dicyanamide. For this purpose, a bisphenol A type epoxy resin (epoxy equivalence of 180 to 200) which is liquid at room temperature is used . YD-128 (epoxy equivalent 184-190), YD-128M (epoxy equivalent 180-196), YDF-170 (epoxy equivalent 160-180), Kumho P & B epoxy resin KER-828 (Epoxy equivalents 184 to 190). The amount of the bisphenol A type epoxy resin is preferably 15 to 20 parts by weight.
2) 디시안디아미드(dicyanamide)2) Dicyanamide
경화제는 시중에 알려진 잠재성 경화제로서 디시안디아미드를 비스페놀 Ａ형 에폭시수지에 용해시켜 경화되도록 하는데, 액상 상태의 경화제로 제조하여 프리프레그의 에폭시수지 조성물이 프리프레그 형태로 사용될 수 있도록 상기 주제와 80℃에서 10분간 혼합하여 프리프레그의 제조에 사용하였다.The curing agent is a known latent curing agent which is dissolved in a bisphenol A type epoxy resin as a latent curing agent, which is known in the art. The curing agent is prepared from a curing agent in a liquid state, and the epoxy resin composition of the prepreg can be used in a prepreg form. Lt; 0 > C for 10 minutes to prepare a prepreg.
디시안디아미드는 상온에서 고상으로 입자크기가 1 ~ 20㎛이고, 용제인 디메틸포름마이드(DMF)에 녹여 사용할 수 있으나, 본 발명은 핫멜트 방식의 프리프레그로 용제를 사용할 수 없기 때문에 디시안디아미드를 액상인 비스페놀 Ａ형 에폭시수지(국도화학 YD-128, 에폭시당량 184∼194)에 혼합 분산시켜 밀링 가공기인 삼본밀로 2회 가공하여 사용하였다.The dicyandiamide can be used in the form of a solid phase at room temperature at a particle size of 1 to 20 탆 and dissolved in dimethylformamide (DMF) as a solvent. However, since the present invention can not use a solvent as a hot-melt type prepreg, Dispersed in a liquid bisphenol A type epoxy resin (KODO CHEMICAL YD-128, epoxy equivalents 184 to 194), and processed by using a triple mill, a milling machine, twice.
디시안디아미드의 사용량은 2 내지 15중량부, 바람직하게는 5 ~ 10중량부이다. 상기 디시안이미드의 사용량이 2중량부 미만이면, 경화반응이 완결되지 않아 에폭시수지 조성물의 유리전이온도가 저하되어 경화가 늦고 복합재의 물성이 저하될 우려가 있으며, 15중량부를 초과하면, 반응에 참여하지 않은 미반응 디시안디아미드가 잔류하여 에폭시 수지 조성물의 기계적 물성을 저하시킬 우려가 있다.
The amount of dicyandiamide to be used is 2 to 15 parts by weight, preferably 5 to 10 parts by weight. If the amount of the dicyanimide used is less than 2 parts by weight, the curing reaction may not be completed and the glass transition temperature of the epoxy resin composition may be lowered and the curing may be delayed to deteriorate the physical properties of the composite. If the amount exceeds 15 parts by weight, The unreacted dicyandiamide not participating remains in the epoxy resin composition, which may deteriorate the mechanical properties of the epoxy resin composition.
3) 무기 난연제3) Inorganic flame retardant
본 발명에 사용되는 무기 난연제로는 인(P) 함량 11.1중량%, 질소(N) 함량 6.5중량%, 비중 1.8, 물에 대한 용해도 0.4g/100㎖, 분해온도 220℃ 이상의 흰색 파우더로서 (주)유니버샬컴텍에서 판매되는 제품명 UCT-12-254를 4~6중량부 사용하고, 가장 적절하게는 주제와 경화제의 점도 증가로 인해 5중량부 사용이 적절하다. The inorganic flame retardant used in the present invention is a white powder having a phosphorus (P) content of 11.1 wt%, a nitrogen (N) content of 6.5 wt%, a specific gravity of 1.8, a solubility in water of 0.4 g / 100 mL, ) 4 to 6 parts by weight of UCT-12-254, a product sold by Universal Comtech, and most suitably 5 parts by weight due to the increase in the viscosity of the composition and the curing agent.
핫멜트 방식에 의한 프리프레그의 제조는 통상 제조되는 방법으로 주제와 경화제를 65~75 : 25~35중량%의 비율로 혼합하여 온도가 70~80℃ 사이에서 코팅된 이형지에 일정 두께로 코팅한 후에 코팅된 이형지 사이에 섬유 원단과 로빙사를 함침시켜 제조한다. 상기 주제와 경화제의 혼합비율에서 주제의 혼합비율이 75중량%를 초과하면 경화제의 양이 적어 프리프레그의 경화시 경화시간이 길어지며 경화물이 무르게 되어 기계적 강도가 약해지며, 65중량% 미만이면 경화제의 양이 증가하여 상온에서 프리프레그의 저장 안정성이 떨어지며 프리프레그 경화시간이 짧아 급경화와 크랙발생 요인 된다.The preparation of the prepreg by the hot-melt method is carried out by mixing the base and the curing agent at a ratio of 65 to 75: 25 to 35% by weight and coating the release paper coated at a temperature of 70 to 80 ° C to a predetermined thickness The fabric is prepared by impregnating the fabric with a cloth and roving yarn between the coated release sheets. When the mixing ratio of the subject and the curing agent is more than 75% by weight, the amount of the curing agent is small, and the curing time of the prepreg is long, and the cured product is weakened to weaken the mechanical strength. When the mixing ratio is less than 65% The storage stability of the prepreg at room temperature is lowered due to an increase in the amount of the curing agent, and shortening of the prepreg curing time leads to rapid curing and cracking.
이하 실시예 및 비교예를 들어 본 발명을 좀 더 상세하게 설명하지만 본 발명이 이들 예로만 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
[제조예 1] 주제 및 경화제의 제조[Preparation Example 1] Preparation of a base and a curing agent
1-1 주제의 제조Manufacture of 1-1 subject
우선 반응기의 청결상태, 밸브의 상태, 콘덴서의 냉각수 및 반응기 4구 플라스크의 질소를 확인하였다. 반응기에 질소를 넣어주면서 에폭시 당량이 170-190인 페놀노볼락형 에폭시 수지(국도화학 YDPN-638) 11.46g을 넣고 온도를 90℃로 올려 녹여주면서 에폭시 당량이 400-500인 고상의 비스페놀A형 에폭시수지(국도화학 YD-011) 5.57g과 에폭시 당량이 900-1000인 고상의 비스페놀A형 에폭시수지(국도화학 YD-014) 11.3g 넣고 녹여준다. 이들 에폭시수지의 녹은 상태를 확인한 후에 에폭시당량이 320-400인 포스파젠계 난연 에폭시수지(상품명 EM-68) 28.64g과 디싸이클로펜타디엔계 에폭시수지(에폭시당량 250-270, 국도화학 YDCP-130) 12.73g 넣고 잘 혼합하여 녹여주어 주제를 제조하였다.
First, the cleanliness of the reactor, the state of the valve, the cooling water of the condenser and the nitrogen in the reactor four-necked flask were checked. 11.46 g of a phenol novolac epoxy resin having an epoxy equivalent of 170-190 (Yuko Chemical Co., Ltd., YDPN-638) was added to the reactor while nitrogen was added to the reactor, and the temperature was raised to 90 ° C to prepare a solid bisphenol A type epoxy resin having an epoxy equivalent of 400-500 5.57 g of an epoxy resin (National Chemical Industries YD-011) and 11.3 g of a solid bisphenol A type epoxy resin having an epoxy equivalent of 900 to 1000 (National Chemical Co., Ltd. YD-014). After confirming the molten state of these epoxy resins, 28.64 g of a phosphazene-based flame retardant epoxy resin having an epoxy equivalent of 320-400 (trade name EM-68) and 28.64 g of a dicyclopentadiene-based epoxy resin (epoxy equivalence 250-270, Kukdo Chemical YDCP-130 ), 12.73 g, and the mixture was well mixed to prepare a subject.
1-2 경화제의 제조 1-2 Preparation of Curing Agent
수지를 혼합할 수 있는 교반기에 에폭시 당량이 180-200인 액상의 비스페놀A형 에폭시수지(국도화학 YD-128) 18.22g에 잠재성 경화제로서 디시안디아미드 7.32g과 무기 난연제로서 (주)유니버샬켐텍의 제품(UCT-12-254) 4.76g을 넣고 혼합한 후에 잘 분산 가공할 수 있도록 삼본밀에 넣고 2회 분산을 실시하여 경화제를 제조하였다.
In a stirrer capable of mixing the resin, 18.22 g of a liquid bisphenol A type epoxy resin (KODO CHEMICAL YD-128) having an epoxy equivalent of 180-200, 7.32 g of dicyandiamide as a latent curing agent, (UCT-12-254) were added, mixed, and dispersed twice in a triple mill so as to be well dispersed, to prepare a curing agent.
[실시예 1][Example 1]
무할로겐 난연성 프리프레그용 에폭시수지 조성물의 제조Preparation of epoxy resin composition for halogen-free flame-retardant prepreg
상기 1-1에서 제조된 주제 69.7g을 온도가 80℃가 되게 하고, 상기 1-2에서 제조된 경화제 30.3g을 온도가 80℃ 넘지 않도록 주의하면서 교반기에 혼합하여 10분간 교반한 후에 바로 포장하여 무할로겐 난연성 프리프레그용 에폭시수지 조성물을 제조하였다.
69.7 g of the subject prepared in 1-1 above was heated to 80 ° C and 30.3 g of the curing agent prepared in 1-2 above were mixed in a stirrer with care not to exceed 80 ° C and stirred for 10 minutes and immediately packed Halogen-free flame-retardant prepregs.
[실시예 2] 내지 [실시예 5][Examples 2 to 5]
실시예 1과 비교하여 [표 1]과 같이, 주제와 경화제의 첨가량을 약간씩 달리하였을 뿐 나머지는 동일한 방법으로 하여 무할로겐 난연성 프리프레그용 에폭시수지 조성물을 제조하였다.
The epoxy resin composition for a halogen-free flame-retardant prepreg was prepared in the same manner as in Example 1 except that the amounts of the epoxy resin and the curing agent were varied slightly, as shown in Table 1.
[비교예 1] 내지 [비교예 2][Comparative Example 1] to [Comparative Example 2]
실시예 1과 비교하여 [표 1]과 같이, 주제와 경화제의 첨가량을 약간씩 달리하였고, 인계 에폭시수지로서 EM-68 대신에 국도화학 KDP550을 사용하였을 뿐 나머지는 동일한 방법으로 하여 프리프레그용 에폭시수지 조성물을 제조하였다.
Compared with Example 1, the addition amount of the curing agent was slightly different from that of Example 1, and KDP550 was used instead of EM-68 as the phosphorus epoxy resin. In the same manner, the epoxy resin for prepreg To prepare a resin composition.
[실험예] 프리프레그의 제조 [Experimental Example] Preparation of prepreg
프리프레그는 일반적인 핫멜트 방식에 의하여 통상적으로 제조되는 방법을 적용하는데, 주제와 경화제를 각각 다르게 하여 제조된 실시예 1 내지 5 및 비교예 1, 2의 프리프레그용 에폭시수지 조성물을 온도 80℃에서 녹여서 코팅된 이형지에 일정량(125g/㎡) 두께로 코팅한 후에 코팅된 이형지 사이에 섬유 원단 또는 로빙사를 함침시켜 제조하였다.
Prepregs are prepared by a common hot melt method. The epoxy resin compositions for prepregs of Examples 1 to 5 and Comparative Examples 1 and 2, prepared by differently mixing the epoxy resin and the epoxy resin, at a temperature of 80 ° C (125g / m < 2 >) in thickness on a coated release paper, followed by impregnation of the fabric or roving yarn between the coated release paper.
<시험방법><Test Method>
상기 실시예 1 내지 5 및 비교예 1, 2에서 얻은 프레프레그용 에폭시수지 조성물에 대하여 다음과 같이 여러 가지 항목의 시험을 실시하였고, 그 시험결과를 하기 [표 2]에 나타내었다.The epoxy resin compositions for prepregs obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were subjected to various tests as follows. The results of the tests are shown in Table 2 below.
1) 점도측정 1) Viscosity measurement
블록필드 점도계(LVF형 저점도용 #4번, 60 RPM)를 이용하여 80℃에서 프레프레그용 에폭시수지 조성물의 점도를 측정하였다.
The viscosity of the epoxy resin composition for prepreg was measured at 80 캜 using a block field viscometer (LVF type # 4 and 60 RPM for low viscosity).
2) 표면 TACKY 2) Surface TACKY
두께 200㎛ PET 필름에 프레프레그용 에폭시수지 조성물을 코팅한 후에 지촉(指燭)건조를 측정하였고, 그 결과는 1 불량, 3 보통, 5 양호 - Tacky 없음을 나타낸다.
The epoxy resin composition for the prepreg was coated on a 200 μm thick PET film, and then dried for 1 minute, 3 normal, 5 good - no tacky.
3) 필름이형성 3) film formation
두께 200㎛ 이형지에 프레프레그용 에폭시수지 조성물을 코팅한 후 프리프레그용 이형필름을 접착한 다음 탈형 정도를 측정하였고, 그 결과는 1 불량, 3 보통, 5 양호 - Tacky 없음을 나타낸다.
The epoxy resin composition for a prepreg was coated on a 200 탆 thick release paper, and then a releasing film for prepreg was adhered to measure the degree of de-molding. The result was 1 poor, 3 moderate, and 5 good-no tacky.
4) 유리전이온도4) Glass transition temperature
프레프레그용 에폭시수지 조성물을 시차주사열량계(DSC, Differential Scanning Calorimetry)에 의하여 유리전이온도를 측정하였다.
The glass transition temperature of the epoxy resin composition for prepregs was measured by differential scanning calorimetry (DSC).
5) 인장강도5) Tensile strength
측정방법은 ASTM D3039-95에 의거 탄소섬유(토레이 12k Carbon UD)와 수지함량 33-37%의 프리프레그를 제조하여 온도 조절과 Vacuum이 가능한 오븐에서 성형온도 80℃에서 30분간, 135℃에서 1시간 30분간 유지하여 경화시킨 후 ASTM D3039-95로 시편제작 측정하였다.
For the measurement, a carbon fiber (Toray 12k Carbon UD) and a prepreg having a resin content of 33-37% were prepared in accordance with ASTM D3039-95. The prepreg was molded in an oven capable of temperature control and vacuuming at a molding temperature of 80 ° C for 30 minutes, After curing for 30 minutes, test specimens were prepared according to ASTM D3039-95.
6) 연소시간 : 시편을 알코올램프로 가열하여 화염을 발생시킨 후에 가열을 중단하여 화염이 꺼지는 시간을 측정하였다.
6) Burning time: After the flame was generated by heating the specimen with an alcohol lamp, the heating was stopped and the flame-off time was measured.
7) 난연성7) Flammability
난연성측정은 UL-94 측정방법으로 측정하였다
The flame resistance was measured by UL-94 measurement method
(시험결과 분석)(Analysis of Test Results)
본 발명에 의한 적절한 수치한정범위인 실시예 1 내지 3의 무할로겐 난연성 프리프레그용 에폭시수지 조성물은 실시예 4, 5 및 비교예 1, 2의 에폭시수지 조성물보다 보다 점도, 표면 Tacky, 필름 이형성, 유리전이온도, 인장강도의 항목에서 우수함을 알 수 있고, 특히 연소시간이 짧을 뿐만 아니라 난연성에서도 우수한 특성을 나타내었다. The epoxy resin compositions for halogen-free flame-retardant prepregs of Examples 1 to 3, which are appropriate numerical limit ranges according to the present invention, are more excellent in viscosity, surface tacky, film releasability, and heat resistance than the epoxy resin compositions of Examples 4 and 5 and Comparative Examples 1 and 2, Glass transition temperature and tensile strength. Especially, it showed not only short combustion time but also excellent flame retardancy.
본 발명의 실시예는 본 발명에 포함되는 기술적 사상의 일부를 명확하게 나타내고 있는 것에 불과하며, 본 발명의 명세서에 포함된 기술적 사상의 범위 내에서 당업자가 용이하게 유추할 수 있는 변형 예와 구체적인 실시예는 모두 본 발명의 기술적인 사상의 범위에 포함되는 것은 자명하다.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are not to be construed as limiting in connection with the spirit of the invention. It is obvious that all of the examples are included in the technical idea of the present invention.
Claims (4)
상기 주제는 a) 에폭시 당량이 170~190인 페놀 노볼락형 에폭시수지 10~20중량부;
b) 2개 이상의 에폭시기를 가지는 비스페놀 A형 에폭시수지 15~20중량부;
c) 에폭시 당량이 320~400인 포스파젠계 에폭시수지 20~35중량부;
d) 에폭시 당량이 250~270인 디사이클로펜타디엔계 에폭시수지 15~20중량부를 포함하여 이루어지고,
상기 경화제는 a) 에폭시 당량이 160~196으로 상온에서 액상인 비스페놀 A형 에폭시수지 15~20중량부;
b) 입경이 1~20㎛인 디시안디아마이드 2~15중량부;
c) 무기난연제 5~10중량부를 포함하여 이루어지되,
상기 주제와 경화제는 65~75중량% : 25~35중량%의 비율로 혼합되는 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물.
An epoxy resin composition for prepreg comprising a base and a curing agent,
A) 10 to 20 parts by weight of a phenol novolak type epoxy resin having an epoxy equivalent of 170 to 190;
b) 15 to 20 parts by weight of a bisphenol A type epoxy resin having two or more epoxy groups;
c) 20 to 35 parts by weight of a phosphazene-based epoxy resin having an epoxy equivalent of 320 to 400;
d) 15 to 20 parts by weight of a dicyclopentadiene epoxy resin having an epoxy equivalent of 250 to 270,
A) 15 to 20 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of 160 to 196 and a liquid at room temperature;
b) 2 to 15 parts by weight of dicyandiamide having a particle diameter of 1 to 20 占 퐉;
c) from 5 to 10 parts by weight of an inorganic flame retardant,
The epoxy resin composition for a halogen-free flame-retardant prepreg according to any one of claims 1 to 5, wherein the main component and the curing agent are mixed in a ratio of 65 to 75% by weight: 25 to 35% by weight.
상기 2개 이상의 에폭시기를 가지는 비스페놀 A형 에폭시수지는 상온에서 액상 또는 고상 중 1종 이상인 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물.
The method according to claim 1,
Wherein the bisphenol A epoxy resin having two or more epoxy groups is at least one of a liquid phase and a solid phase at room temperature.
상기 에폭시 당량이 320~400인 포스파젠계 에폭시수지는 인 함량 2~4중량%, 용융온도 80℃, 점도 1000-2000CPS인 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물.
The method of claim 2,
Wherein the phosphazene-based epoxy resin having an epoxy equivalent of 320 to 400 has a phosphorus content of 2 to 4 wt%, a melting temperature of 80 DEG C, and a viscosity of 1000 to 2000 CPS.
상기 무기난연제는 인(P) 함량 11.1중량%, 질소(N) 함량 6.5중량%, 비중 1.8, 물에 대한 용해도 0.4g/100㎖, 분해온도 220℃ 이상의 흰색 파우더인 것을 특징으로 하는 무할로겐 난연성 프리프레그용 에폭시수지 조성물.
The method of claim 3,
Wherein the inorganic flame retardant is a white powder having a phosphorus (P) content of 11.1 wt%, a nitrogen (N) content of 6.5 wt%, a specific gravity of 1.8, a solubility in water of 0.4 g / 100 mL, Epoxy resin composition for prepreg.
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| KR20100077468A (en) * | 2008-12-29 | 2010-07-08 | 주식회사 두산 | Resine composition and prepreg and printed wiring board using the same |
| KR20100116885A (en) * | 2009-04-23 | 2010-11-02 | 삼성전기주식회사 | Resin composition for printed circuit board and printed circuit board using the same |
| KR20100134313A (en) * | 2009-06-15 | 2010-12-23 | 삼성전기주식회사 | Resin composition for printed circuit board and printed circuit board using the same |
| KR20140037646A (en) * | 2012-09-19 | 2014-03-27 | 삼성전기주식회사 | Epoxy resin composition for insulation, insulating film, prepreg, and printed circuit board |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100077468A (en) * | 2008-12-29 | 2010-07-08 | 주식회사 두산 | Resine composition and prepreg and printed wiring board using the same |
| KR20100116885A (en) * | 2009-04-23 | 2010-11-02 | 삼성전기주식회사 | Resin composition for printed circuit board and printed circuit board using the same |
| KR20100134313A (en) * | 2009-06-15 | 2010-12-23 | 삼성전기주식회사 | Resin composition for printed circuit board and printed circuit board using the same |
| KR20140037646A (en) * | 2012-09-19 | 2014-03-27 | 삼성전기주식회사 | Epoxy resin composition for insulation, insulating film, prepreg, and printed circuit board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160736A (en) * | 2022-08-19 | 2022-10-11 | 贵州至当科技有限公司 | High-temperature-resistant colored epoxy resin and preparation method thereof |
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| KR101663942B1 (en) | 2016-10-07 |
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