JP2004051907A - Halogen-free flame retardant epoxy resin composition, and prepreg, laminated board, copper-clad laminated board and printed circuit board containing the same - Google Patents
Halogen-free flame retardant epoxy resin composition, and prepreg, laminated board, copper-clad laminated board and printed circuit board containing the same Download PDFInfo
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- JP2004051907A JP2004051907A JP2002214643A JP2002214643A JP2004051907A JP 2004051907 A JP2004051907 A JP 2004051907A JP 2002214643 A JP2002214643 A JP 2002214643A JP 2002214643 A JP2002214643 A JP 2002214643A JP 2004051907 A JP2004051907 A JP 2004051907A
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 104
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 22
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract 3
- 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 abstract description 47
- 229920003986 novolac Polymers 0.000 claims abstract description 38
- -1 of resorcinol Chemical class 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 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 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 239000011889 copper foil Substances 0.000 claims description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004745 nonwoven fabric Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002366 halogen compounds Chemical class 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 51
- 239000011347 resin Substances 0.000 abstract description 51
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011342 resin composition Substances 0.000 abstract description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 39
- 239000004593 Epoxy Substances 0.000 description 30
- 239000002966 varnish Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229930003836 cresol Natural products 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 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 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RNNGKNBZYALDNU-UHFFFAOYSA-N phosphoric acid;triphenylene Chemical compound OP(O)(O)=O.C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 RNNGKNBZYALDNU-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、積層品製造用のハロゲンフリーの難燃性エポキシ樹脂組成物と、それを含浸したプリプレグ、積層板、銅張積層板及びプリント配線板に関する。
【０００２】
【従来の技術】
近年、世界的な環境問題、人体に対する安全性についての関心の高まりに伴なって、電気・電子機器については、従来からの難燃性に加えて、より少ない有害性、より高い安全性という要求が増大している。すなわち、電気・電子機器は、単に燃えにくいだけでなく、有害ガスや発煙などの発生が少ないことが要請されている。従来、電気・電子部品を搭載するガラス基材エポキシ樹脂のプリント配線板は、エポキシ樹脂として、難燃剤の臭素を含有する臭素化エポキシ樹脂、特にテトラブロモビスフェノールＡ型エポキシ樹脂が一般に使用されている。
【０００３】
このような臭素化エポキシ樹脂は、良好な難燃性を有するものの、燃焼時に有害なハロゲン化水素（臭化水素）ガスを発生することや、ブロモ化ダイオキシン、フラン類を発生する可能性があるため、その使用が抑制されつつある。
【０００４】
そこで、ハロゲンフリーの各種難燃性エポキシ樹脂組成物が開発されている。その主なものは、リン化合物、窒素化合物、無機化合物等を組み合わせたものである。
【０００５】
この組合せは、主にＵＬ９４Ｖ−０を達成するための難燃システムであり、リン化合物が主難燃剤となる場合が多い。リン化合物を主体とした難燃システムには大きく分けてリン原子をエポキシ樹脂骨格内に組み込んだものとリン化合物を添加剤として使用するものとがある。前者の代表的なものとしては、ＨＣＡ骨格を導入したエポキシ樹脂があり、後者の代表的なものとしては、リン酸エステル類を配合した組成物がある。
【０００６】
この双方とも従来のハロゲン系難燃剤を使用したものと特性的には遜色ないが、コストパフォーマンスにおいては後者が優れる。
【０００７】
しかし、現在プリント配線板では、さらなる高信頼性化が求められている。即ち、高多層板、高アスペクト比基板あるいは過酷な使用条件（例えば−６５℃，１５０℃の冷熱サイクル）でのスルーホール信頼性の向上である。
【０００８】
【発明が解決しようとする課題】
スルーホール信頼性を向上する一つの方法は、スルーホール壁面にかかる応力を緩和低減する必要がある。このためには、絶縁層の膨張係数およびヤング率を低減させることが有効となり、樹脂物性としては、その膨張係数の低減、高Ｔｇ化、ヤング率の低減等が要求される。しかし、樹脂の更なる高Ｔｇ化は、ドリル加工性などの低下を招き、ヤング率の低下は、積層板としての基本物性の低下を招く。膨張係数の低減は、樹脂の低膨張率化や基材の低膨張率化により可能であるが、エポキシ樹脂化合物およびガラス基材での低膨張率化はコストの上昇を招き、無機充填剤の多量の添加による膨張係数の低下は加工性の低下や特性の低下を招く。
【０００９】
また、応力緩和剤として、従来シリコーン化合物、ゴム変性エポキシ化合物などが使用されてきたが、前者については、ハロゲンフリー難燃性エポキシ樹脂との相溶性に劣り、後者については、Ｔｇの低下割合が大きいこと、難燃性を低下させる難点がある。
【００１０】
そこで本発明では、これらの方法に依らず、応力緩和をエポキシ樹脂骨格の変更と適度の応力緩和剤として働く非反応型のリン系難燃剤の併用により樹脂層の応力緩和を行い、スルーホール信頼性を格段に向上させるとともにコストパフォーマンスにも優れるハロゲンフリーの難燃性エポキシ樹脂組成物を提供することを目的とする。
【００１１】
さらに、本発明は、そのようなエポキシ樹脂組成物で含浸されたプリプレグ並びにこれらを用いて製造された積層板、銅張積層板及びプリント配線板を提供することも目的とする。
【００１２】
【課題を解決するための手段】
本発明者らは、上記の目的を達成しようと鋭意研究を重ねた結果、エポキシ樹脂構造としては、ビスフェノール系ノボラック型エポキシ樹脂化合物におけるビスフェノール骨格を組み込むことが、Ｔｇ、ヤング率を低下させることなしに内部応力を低減することに有効であることを見いだし、本発明を完成させたものである。また、この方法だけでは十分な効果が期待できず、適当な応力緩和作用を有する縮合型リン酸エステル化合物との併用により、上記目的が達成されることも見いだしされた。
【００１３】
即ち、本発明は、積層品の製造に適用されるエポキシ樹脂組成物であって、
（Ａ）縮合型リン酸エステル化合物および
（Ｂ）ビスフェノール系ノボラック型エポキシ樹脂化合物
を必須成分とすることを特徴とするハロゲンフリーの難燃性エポキシ樹脂組成物である。また、上記難燃性エポキシ樹脂組成物で含浸されたプリプレグ、並びに上記プリプレグを用いて製造された積層板、銅張積層板およびプリント配線板である。
【００１４】
以下、本発明を詳細に説明する。
【００１５】
本発明におけるハロゲンフリーとは、難燃用のハロゲン化合物を含まないともに、特にエポキシ樹脂組成物中の各化合物が、その製造工程その他での反応残渣、反応副成物としてハロゲン化合物の含有量が各化合物の０．１％以下であることが望ましい。
【００１６】
本発明において、適当な応力緩和作用を有する化合物として用いる（Ａ）縮合型リン酸エステル化合物は、レゾルシン等の多価フェノールとフェノール、クレゾール等の１価フェノールとによってリン酸エステル化合成され、多価フェノールの水酸基の全てがエステル化縮合に消費され、１価フェノールがエステル化縮合後の残存するエステル化添加に消費されたものである。また、応力緩和作用をもつための縮合型リン酸エステル化合物としては、融点が８０℃以上のものが好適である。
【００１７】
具体的な縮合型リン酸エステル化合物としては、下記構造式に示されるＰＸ−２００（大八化学社製、商品名）などがある。
【００１８】
【化２】
これらの縮合型リン酸エステル化合物を配合することにより、難燃性を維持するとともに、樹脂組成物の架橋密度を適当に低下させることにより弾性率を適度に低下させることができる。このような作用は、従来使用され特性低下が顕著であったトリフェニルホスフェート（ＴＰＰ）、クレジルジフェニルホスフェート（ＣＤＰ）、キシレニルジフェニルホスフェート（ＸＤＰ）等の非反応型、いわゆる添加型リン酸エステル類にはみられないものである。
【００１９】
（Ａ）縮合型リン酸エステル化合物を配合することによる全エポキシ樹脂組成物のリン含有量は０．２〜５．０％が適当である。
【００２０】
本発明においてＴｇ、ヤング率を低下させないエポキシ樹脂として用いる（Ｂ）ビスフェノール系ノボラック型エポキシ樹脂化合物は、ビスフェノール類のノボラック樹脂をエポキシ化した多官能エポキシ樹脂であって、ビスフェノール類としては、ビスフェノールＡ、ビスフェノールＦ、ジフェノリックペンタン酸（１，１−ビス（４−ヒドロキシフェニル）ペンタン）等が挙げられる。
【００２１】
本発明のエポキシ樹脂組成物における（Ｂ）成分のビスフェノール系ノボラック型エポキシ樹脂の配合割合は、樹脂組成物全体に対して少なくとも５重量％配合することが好ましい。５重量％未満ではスルーホール信頼性の向上に効果がない。
【００２２】
（Ｂ）ビスフェノール系ノボラック型エポキシ樹脂化合物と併用されるエポキシ樹脂としては、グリシジルエーテルタイプのエポキシ樹脂が好適である。具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂等が挙げられ、単独又は２種以上混合して使用することができる。これらのエポキシ樹脂の中ではノボラック型エポキシ樹脂が好適である。また、併用されるエポキシ樹脂には変性エポキシ樹脂も含まれる。例えば難燃性を向上させるリン変性樹脂等を使用することができる。これには、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂をベースとし、下記一般式化３に示されるリン化合物とベンゾキノン、ジフェノキノン、トルキノン、ナフトキノン、アントラキノン等のキノンとを反応させて得られる化合物の骨格を導入したエポキシ樹脂がある。
【００２３】
【化３】
【００２４】
本発明に用いるエポキシ樹脂用硬化剤は、エポキシ樹脂用として通常用いられる硬化剤のうち窒素を含有するもので、ジシアンジアミド（ＤＩＣＹ）とその誘導体、ノボラック型フェノール樹脂、トリアジン変性ノボラック型フェノール樹脂、イミダゾール等のうちの少なくとも一種を用いることができる。これらの化合物のうちでは、トリアジン変性ノボラック型フェノール樹脂が好適であり、変性トリアジン化合物としては、メラミン、ベンゾグアナミン等が特に好適である。このような化合物の具体例としては、大日本インキ化学工業会社製、商品名のＬＡ−７０５１，７０５４等が挙げられる。
【００２５】
本発明には無機充填剤として、水酸化アルミニウム、水酸化マグネシウム、タルク、シリカ等の少なくとも一種を用いることができる。
【００２６】
このうち、水酸化アルミニウム、水酸化マグネシウム等の金属水和物は、分子内に含まれる結晶水や加熱時の転移反応による低温分解化合物の生成により、２８０℃以上での耐熱性が低下する傾向があるため、その添加量に制限がある。その添加量は、金属水和物では高温での半田耐熱性に関係し、タルク、シリカではドリル加工性に関係し、各々５０％を超えるとその関係する特性の低下を招く恐れがある。
【００２７】
本発明のエポキシ樹脂組成物は、上述した成分をプロピレングリコールモノメチルエーテル等の好適な有機溶剤で希釈してワニスとなし、これをガラス不織布、ガラス織布、全芳香族ポリエステル系不織布等の多孔質ガラス基材に塗布、含浸させ、加熱するという通常の方法によりプリプレグを製造することができる。ここで、芳香族ポリエステル系ポリマーとしては、２−ヒドロキシ−６−ナフトエ酸や、Ｐ−ヒドロキシ安息香酸の構造をもつものが挙げられる。
【００２８】
また、このプリプレグを複数枚重ね合わせ、その積層構造の片面又は両面に銅箔を重ね合わせた後、これを通常の条件で加熱・加圧してガラスエポキシ銅張積層板を得ることができる。この時、銅箔を用いなければ積層板が得られる。多層板は、銅張積層板（内層板）に回路を形成し、ついで銅箔をエッチング処理した後、内層板の少なくとも片面にプリプレグおよび銅箔を重ね合わせ、これを例えば、１７０℃，４ＭＰａの圧力で１００分間加熱・加圧するという通常の方法により製造することができる。さらに、プリント配線板は、銅張積層板もしくは多層板にスルーホールを形成し、スルーホールメッキを行った後、所定の回路を形成するという通常の方法により製造することができる。また、ガラス不織布、ポリエステル系液晶ポリマー不織布のプリプレグについては、ビルドアップ多層板のＨＤＩ材料としてレーザービア等の非貫通ビアホールをもつプリント配線板にも使用することができる。
【００２９】
【発明の実施の形態】
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。以下の実施例および比較例において「部」とは「重量部」を意味する。
【００３０】
［リン含有エポキシ樹脂の合成例］
合成例１：化合物Ａ
ビスフェノールＡ型エポキシ樹脂（エポキシ当量１９０）３８０ｇとＨＣＡ−ＨＱ（三光化学社製、商品名）［１０−（２，５−ジヒドロキシフェニル）−１０−ハイドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド］２９２ｇを反応触媒としてＴＰＰ（トリフェニルホイフィン）０．１５ｇを水溶液として用い、１７０℃で５時間反応させ、リン含有率４．１％のエポキシ樹脂を合成した。
【００３１】
合成例２：化合物Ｂ
ビスフェノールＦ型エポキシ樹脂（エポキシ当量１７２）３４４ｇとＨＣＡ−ＨＱ（三光化学社製、商品名）２９２ｇを反応触媒としてＴＰＰ０．１５ｇを水溶液として用い、１７０℃で４時間反応させ、リン含有率４．４％のエポキシ樹脂を合成した。
【００３２】
実施例１
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）１０００部、ビスフェノールＡ型ノボラック型エポキシ樹脂（エポキシ当量２０５、樹脂固形分１００重量％）３００部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）８５０部、縮合型リン酸エステルのＰＸ−２００（大八化学社製、商品名）２８０部、水酸化アルミニウム８００部および２−エチル−４−メチルイミダゾール１．９部の混合物に溶媒としてプロピレングリコールモノメチルエーテル（ＰＧＭ）を加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３３】
実施例２
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）１０００部、ビスフェノールＡ型ノボラック型エポキシ樹脂（エポキシ当量２０５、樹脂固形分１００重量％）３００部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）８５０部、縮合型リン酸エステルのＰＸ−２００（大八化学社製、商品名）２８０部、シリカ８００部および２−エチル−４−メチルイミダゾール１．９部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３４】
実施例３
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）１０００部、ビスフェノールＡ型ノボラック型エポキシ樹脂（エポキシ当量２０５、樹脂固形分１００重量％）３００部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）８５０部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）３２０部および２−エチル−４−メチルイミダゾール２．０部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３５】
実施例４
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）１０００部、ビスフェノールＡ型ノボラック型エポキシ樹脂（エポキシ当量２０５、樹脂固形分１００重量％）３００部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）８５０部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）２００部、ビスフェノールＡ型ベンゾオキサジン樹脂（樹脂固形分７５重量％）３００部、水酸化アルミニウム５００部および２−エチル−４−メチルイミダゾール１．９部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３６】
実施例５
合成例１で合成したリン含有エポキシ樹脂６００部（エポキシ当量１９０）、ビスフェノールＡ型ノボラック型エポキシ樹脂（エポキシ当量２０５、樹脂固形分１００重量％）４００部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）９００部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）１００部、水酸化アルミニウム７５０部および２−エチル−４−メチルイミダゾール１．８２部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３７】
実施例６
合成例２で合成したリン含有エポキシ樹脂６００部、ビスフェノールＡ型ノボラック型エポキシ樹脂（エポキシ当量２０５、樹脂固形分１００重量％）４００部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）９６０部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）９５部、水酸化アルミニウム７４０部および２−エチル−４−メチルイミダゾール１．８２部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３８】
比較例１
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）１４５０部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）８６０部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）２８０部、水酸化アルミニウム８００部および２−エチル−４−メチルイミダゾール１．９部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００３９】
比較例２
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）１０００部、ビスフェノールＡ型エポキシ樹脂のエピコート１００１（油化シェル社製商品名、エポキシ当量４５６、樹脂固形分７０重量％）４３０部、トリアジン変性ノボラック型フェノール樹脂のＬＡ−７０５１（大日本インキ化学社製商品名、水酸基価１２４、樹脂固形分７０重量％）７１０部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）２８０部、水酸化アルミニウム８００部および２−エチル−４−メチルイミダゾール１．９部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００４０】
比較例３
臭素化エポキシ樹脂のエピコート５０４５（油化シェル社製商品名、エポキシ当量４８０、樹脂固形分８０重量％）６００部、ビスフェノールＡ型ノボラック樹脂（大日本インキ化学社製、水酸基価１１８、樹脂固形分７０重量％）１６９部および２−エチル−４−メチルイミダゾール０．６部の混合物に溶媒としてＰＧＭを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００４１】
比較例４
ビスフェノールＡ型エポキシ樹脂のエピコート１００１（油化シェル社製商品名、エポキシ当量４５６、樹脂固形分７０重量％）６５１部、クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）３００部、ビスフェノールＡ型ノボラック樹脂（大日本インキ化学社製、水酸基価１１８、樹脂固形分７０重量％）３３７部、トリフェニレンフォスフェート５４１部、水酸化アルミニウム３６１部および２−エチル−４−メチルイミダゾール０．９部の混合物に溶媒としてＰＧＭとジメチルホルムアミドを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００４２】
比較例５
臭素化エポキシ樹脂のエピコート５０４５（油化シェル社製商品名、エポキシ当量４８０、樹脂固形分８０重量％）６００部、ジシアンジアミド１３部および２−エチル−４−メチルイミダゾール０．５部の混合物に溶媒としてＰＧＭとジメチルホルムアミドを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００４３】
比較例６
ビスフェノールＡ型エポキシ樹脂のエピコート１００１（油化シェル社製商品名、エポキシ当量４５６、樹脂固形分７０重量％）６５１部、クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７０４Ｐ（東都化成社製商品名、エポキシ当量２１０、樹脂固形分７０重量％）３００部、ジシアンジアミド２５部、縮合型リン酸エステルＰＸ−２００（大八化学社製、商品名）２３０部、水酸化アルミニウム２３０部および２−エチル−４−メチルイミダゾール０．７部の混合物に溶媒としてＰＧＭとジメチルホルムアミドを加えて樹脂固形分６５重量％のエポキシ樹脂ワニスを調製した。
【００４４】
実施例１〜６および比較例１〜６で得たエポキシ樹脂ワニスの各々を、１８０μｍガラス織布、１００μｍガラス織布又は５０μｍ全芳香族ポリエステル系不織布に連続的に塗布・含浸させ、１６０℃の温度で乾燥してプリプレグを製造した。
【００４５】
こうして得られた１８０μｍガラス織布プリプレグの８枚を重ね合わせたものと１００μｍガラス織布プリプレグの１枚のものを準備し、この積層体の両面に厚さ１８μｍの銅箔を重ねて１７０℃の温度、４Ｍｐａの圧力で１００分間加熱・加圧し、厚さ１．６ｍｍガラスエポキシ両面銅張積層板と厚さ０．１ｍｍガラスエポキシ両面銅張積層板を得た。
【００４６】
次に、同じプリプレグを重ね合わせ、その両面に厚さ３５μｍの銅箔を重ね合わせて同様に加熱・加圧し、１８０μｍガラス織布を用いたプリプレグから板厚０．８ｍｍ内層板と、１００μｍガラス織布を用いたプリプレグから板厚０．１ｍｍ内層板を製造した。
【００４７】
この板厚０．８ｍｍ内層板に０．５φのクリアランスホールを含む回路を形成し、銅箔表面を酸化処理した後、その両面に上記１８０μｍガラス織布プリプレグを重ね合わせ、その上にそれぞれ厚さ１２μｍ銅箔を重ね合わせて同様に加熱・加圧して板厚１．２ｍｍ４層シールド板を製造した。
【００４８】
また、この板厚０．８ｍｍ内層板の両側に０．５φのクリアランスホールと０．２φのランドを含む回路を形成し、銅箔表面を酸化処理した後、その両面に上記５０μｍ全芳香族ポリエステル系不織布プリプレグを重ね合わせ、その上にそれぞれ厚さ１２μｍ銅箔を重ね合わせて同様に加熱・加圧して板厚１．０ｍｍ４層シールド板を製造した。
【００４９】
また、この板厚０．１ｍｍ内層板の２ボードに０．５φのクリアランスホールを含む回路を形成し、銅箔表面を酸化処理した後、その間に１００μｍガラス織布プリプレグを１枚入れ、その両面に上記１００μｍガラス織布プリプレグを重ね合わせ、そのプリプレグ上にそれぞれ厚さ１８μｍ銅箔を重ね合わせて同様に加熱・加圧して板厚０．５ｍｍ６層シールド板を製造した。
【００５０】
また、この板厚０．１ｍｍ内層板の２ボードに０．５φのクリアランスホールと片側に０．２φのランドを含む回路を形成し、銅箔表面を酸化処理した後、その間に１００μｍガラス織布プリプレグを１枚入れ、その両面に５０μｍ全芳香族ポリエステル系不織布プリプレグを重ね合わせ、そのプリプレグ上にそれぞれ厚さ１２μｍ銅箔を重ね合わせて同様に加熱・加圧して板厚０．４ｍｍ６層シールド板を製造した。
【００５１】
これらのうち、ガラス織布のみで作成した両面板及びシールド板には０．５φのランドを含む回路を形成し、０．２φのドリルでスルーホール穴を形成し、通常メッキ工程でメッキ厚さ１５〜２０μｍの貫通スルーホール基板を作成する。また、全芳香族ポリエステル系不織布プリプレグを含む多層板では、両側に０．１φのレーザービア（０．１５φランド）をコンフォーマル法で作成する。更に０．５φのランドを含む回路を形成し、０．２φのドリルでスルーホール穴を形成し、通常メッキ工程でメッキ厚さ１５〜２０μｍのレーザービアと貫通スルーホールを含む基板を作成する。
【００５２】
以上のテスト基板のスルーホール信頼性をホットオイルと冷熱サイクル試験で行った。結果を表１〜表６に示す。試験条件は以下のとおりである。
【００５３】
なお、表１〜表６において、各々の実施例および比較例のサブナンバーにおける試料は次のとおりである。
【００５５】
サブナンバー１…厚さ０．１ｍｍガラスエポキシ両面銅張積層板、
サブナンバー２…厚さ１．６ｍｍガラスエポキシ両面銅張積層板、
サブナンバー３…板厚１．２ｍｍ４層シールド板、
サブナンバー４…板厚１．０ｍｍ４層シールド板（ＬＶＨ）、
サブナンバー５…板厚０．５ｍｍ６層シールド板、
サブナンバー６…板厚０．４ｍｍ６層シールド板（ＬＶＨ）。
【００５６】
【表１】
＊２：○印…合格、
＊３：表中の処理条件で処理後、フクレの有無を観察した。
【００５７】
【表２】
＊２：○印…合格、
＊３：表中の処理条件で処理後、フクレの有無を観察した。
【００５８】
【表３】
＊２：○印…合格、
＊３：表中の処理条件で処理後、フクレの有無を観察した。
【００５９】
【表４】
＊２：○印…合格、
＊３：表中の処理条件で処理後、フクレの有無を観察した。
【００６０】
【表５】
＊２：○印…合格、
＊３：表中の処理条件で処理後、フクレの有無を観察した。
【００６１】
【表６】
＊２：○印…合格、
＊３：表中の処理条件で処理後、フクレの有無を観察した。
【００６２】
【発明の効果】
以上の説明および表１乃至表６の結果から明らかなように、本発明によれば、ハロゲンを含有しないで優れた難燃性を示し、高多層板、高アスペクト比基板あるいは過酷な使用条件（例えば−６５℃，１５０℃の冷熱サイクル）でのスルーホール信頼性を格段に向上させたたガラスエポキシ銅張積層板を与えるエポキシ樹脂組成物が提供される。このようなガラスエポキシ銅張積層板を用いれば、良好な環境特性を付与し、かつ種々の特性に優れたプリント配線板を製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a halogen-free flame-retardant epoxy resin composition for producing a laminated product, and a prepreg, a laminate, a copper-clad laminate and a printed wiring board impregnated with the composition.
[0002]
[Prior art]
In recent years, with the growing concern about global environmental issues and the safety of the human body, the demand for less hazardous and higher safety has been required for electric and electronic devices in addition to the conventional flame retardancy. Is increasing. That is, it is demanded that electric and electronic devices not only hardly burn, but also generate less harmful gas and smoke. 2. Description of the Related Art Conventionally, a printed wiring board made of a glass-based epoxy resin on which electric / electronic components are mounted has generally been used as an epoxy resin, a brominated epoxy resin containing bromine as a flame retardant, particularly a tetrabromobisphenol A type epoxy resin. .
[0003]
Such a brominated epoxy resin has good flame retardancy, but may generate harmful hydrogen halide (hydrogen bromide) gas during combustion, and may generate brominated dioxins and furans. Therefore, its use is being suppressed.
[0004]
Therefore, various halogen-free flame-retardant epoxy resin compositions have been developed. The main one is a combination of a phosphorus compound, a nitrogen compound, an inorganic compound and the like.
[0005]
This combination is a flame retardant system mainly for achieving UL94V-0, and a phosphorus compound is often the main flame retardant. Flame-retardant systems mainly based on phosphorus compounds are roughly classified into those in which phosphorus atoms are incorporated in an epoxy resin skeleton and those in which phosphorus compounds are used as additives. A typical example of the former is an epoxy resin having an HCA skeleton introduced therein, and a typical example of the latter is a composition containing a phosphate ester.
[0006]
Both of these are comparable in characteristics to those using a conventional halogen-based flame retardant, but the latter are superior in cost performance.
[0007]
However, printed wiring boards are currently required to have even higher reliability. That is, the improvement of the reliability of the through hole under a high multilayer board, a high aspect ratio substrate, or a severe use condition (for example, a cooling / heating cycle of −65 ° C. and 150 ° C.).
[0008]
[Problems to be solved by the invention]
One way to improve through-hole reliability is to relax and reduce the stress on the wall of the through-hole. For this purpose, it is effective to reduce the expansion coefficient and the Young's modulus of the insulating layer, and as the physical properties of the resin, it is required to reduce the expansion coefficient, increase the Tg, and reduce the Young's modulus. However, a further increase in Tg of the resin causes a decrease in drill workability and the like, and a decrease in the Young's modulus causes a decrease in basic physical properties as a laminate. The expansion coefficient can be reduced by lowering the expansion coefficient of the resin or the base material, but lowering the expansion coefficient of the epoxy resin compound and the glass base material causes an increase in cost, and the use of inorganic fillers is reduced. A decrease in the expansion coefficient due to a large amount of addition causes a decrease in workability and a decrease in properties.
[0009]
Conventionally, silicone compounds, rubber-modified epoxy compounds, and the like have been used as stress relaxation agents, but the former has poor compatibility with halogen-free flame-retardant epoxy resins, and the latter has a lower Tg reduction ratio. There are disadvantages of being large and reducing flame retardancy.
[0010]
Therefore, in the present invention, regardless of these methods, the stress relaxation of the resin layer is performed by changing the epoxy resin skeleton and using a non-reactive phosphorus-based flame retardant acting as an appropriate stress relaxation agent in combination with the stress relaxation. It is an object of the present invention to provide a halogen-free flame-retardant epoxy resin composition having a remarkably improved property and excellent cost performance.
[0011]
Still another object of the present invention is to provide a prepreg impregnated with such an epoxy resin composition, and a laminate, a copper-clad laminate, and a printed wiring board manufactured using the prepreg.
[0012]
[Means for Solving the Problems]
The present inventors have made intensive studies to achieve the above object, and as a result, incorporating a bisphenol skeleton in a bisphenol-based novolak-type epoxy resin compound as an epoxy resin structure does not reduce Tg and Young's modulus. The present inventors have found that the present invention is effective in reducing internal stress, and have completed the present invention. Further, it has been found that a sufficient effect cannot be expected by this method alone, and that the above-mentioned object can be achieved by the combined use with a condensed phosphate compound having an appropriate stress relaxing action.
[0013]
That is, the present invention is an epoxy resin composition applied to the production of a laminate,
A halogen-free flame-retardant epoxy resin composition comprising (A) a condensed phosphate compound and (B) a bisphenol-based novolak epoxy resin compound as essential components. Also, a prepreg impregnated with the flame-retardant epoxy resin composition, and a laminate, a copper-clad laminate and a printed wiring board manufactured using the prepreg.
[0014]
Hereinafter, the present invention will be described in detail.
[0015]
Halogen-free in the present invention does not include a flame-retardant halogen compound, and in particular, each compound in the epoxy resin composition has a content of the halogen compound as a reaction residue or a reaction by-product in the production process or the like. It is desirable that the content be 0.1% or less of each compound.
[0016]
In the present invention, the condensed phosphate ester compound (A) used as a compound having an appropriate stress relaxation action is synthesized by phosphoric esterification with a polyhydric phenol such as resorcinol and a monohydric phenol such as phenol and cresol. All of the hydroxyl groups of the dihydric phenol were consumed in the esterification condensation, and the monohydric phenol was consumed in the remaining esterification addition after the esterification condensation. Further, as the condensed phosphate ester compound having a stress relaxing action, a compound having a melting point of 80 ° C. or more is preferable.
[0017]
Specific examples of the condensed phosphate compound include PX-200 (trade name, manufactured by Daihachi Chemical Co., Ltd.) represented by the following structural formula.
[0018]
Embedded image
By blending these condensed phosphate ester compounds, flame retardancy can be maintained, and the elastic modulus can be appropriately reduced by appropriately reducing the crosslink density of the resin composition. Such action is caused by non-reactive, so-called added phosphoric acid such as triphenyl phosphate (TPP), cresyl diphenyl phosphate (CDP), xylenyl diphenyl phosphate (XDP) and the like, which have been conventionally used and whose characteristics are remarkably deteriorated. It is not found in esters.
[0019]
(A) The appropriate phosphorus content of the entire epoxy resin composition by blending the condensed phosphate compound is 0.2 to 5.0%.
[0020]
The bisphenol novolak type epoxy resin compound (B) used as the epoxy resin which does not lower the Tg and Young's modulus in the present invention is a polyfunctional epoxy resin obtained by epoxidizing a bisphenol novolak resin, and the bisphenols include bisphenol A , Bisphenol F, diphenolic pentanoic acid (1,1-bis (4-hydroxyphenyl) pentane) and the like.
[0021]
The bisphenol novolak type epoxy resin (B) in the epoxy resin composition of the present invention is preferably blended in an amount of at least 5% by weight based on the entire resin composition. If it is less than 5% by weight, there is no effect in improving the reliability of the through hole.
[0022]
As the epoxy resin used in combination with the (B) bisphenol-based novolak epoxy resin compound, a glycidyl ether type epoxy resin is preferable. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin and the like can be mentioned, and these can be used alone or in combination of two or more. Among these epoxy resins, a novolak type epoxy resin is preferable. The epoxy resin used in combination also includes a modified epoxy resin. For example, a phosphorus-modified resin or the like that improves flame retardancy can be used. This is a compound obtained by reacting a phosphorus compound represented by the following general formula 3 with a quinone such as benzoquinone, diphenoquinone, tolquinone, naphthoquinone or anthraquinone based on a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. There is an epoxy resin having a skeleton introduced therein.
[0023]
Embedded image
[0024]
The curing agent for epoxy resin used in the present invention is a curing agent containing nitrogen among curing agents usually used for epoxy resin. Dicyandiamide (DICY) and its derivatives, novolak-type phenol resin, triazine-modified novolak-type phenol resin, imidazole At least one of them can be used. Among these compounds, a triazine-modified novolak-type phenol resin is preferable, and as the modified triazine compound, melamine, benzoguanamine and the like are particularly preferable. Specific examples of such a compound include LA-7051, 7054 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.).
[0025]
In the present invention, at least one of aluminum hydroxide, magnesium hydroxide, talc, silica and the like can be used as the inorganic filler.
[0026]
Among these, metal hydrates such as aluminum hydroxide and magnesium hydroxide tend to have reduced heat resistance at 280 ° C. or higher due to the formation of water of crystallization contained in the molecule and a low-temperature decomposition compound due to a transition reaction upon heating. Therefore, the amount added is limited. The amount of addition relates to solder heat resistance at a high temperature in the case of metal hydrate, and relates to drilling workability in the case of talc and silica. If each exceeds 50%, there is a possibility that the related properties may be deteriorated.
[0027]
The epoxy resin composition of the present invention is prepared by diluting the above-mentioned components with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, and forming the varnish from a glass nonwoven fabric, a glass woven fabric, a porous aromatic polyester nonwoven fabric, or the like. A prepreg can be manufactured by a usual method of coating, impregnating, and heating a glass substrate. Here, examples of the aromatic polyester-based polymer include those having a structure of 2-hydroxy-6-naphthoic acid or P-hydroxybenzoic acid.
[0028]
Also, a plurality of the prepregs may be laminated, and a copper foil may be laminated on one or both sides of the laminated structure, and then heated and pressed under ordinary conditions to obtain a glass epoxy copper clad laminate. At this time, a laminate can be obtained without using a copper foil. In the multilayer board, a circuit is formed on a copper-clad laminate (inner board), and then, after the copper foil is subjected to an etching treatment, a prepreg and a copper foil are laminated on at least one surface of the inner board, and this is, for example, 170 ° C., 4 MPa. It can be manufactured by a usual method of heating and pressurizing under pressure for 100 minutes. Further, the printed wiring board can be manufactured by a usual method of forming a predetermined circuit after forming a through hole in a copper-clad laminate or a multilayer board, performing through-hole plating. In addition, a prepreg made of a glass nonwoven fabric or a polyester-based liquid crystal polymer nonwoven fabric can be used as an HDI material of a build-up multilayer board for a printed wiring board having a non-through via hole such as a laser via.
[0029]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.
[0030]
[Synthesis example of phosphorus-containing epoxy resin]
Synthesis Example 1: Compound A
380 g of bisphenol A type epoxy resin (epoxy equivalent 190) and HCA-HQ (trade name, manufactured by Sanko Chemical Co., Ltd.) [10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene- Using 292 g of [10-oxide] as a reaction catalyst and 0.15 g of TPP (triphenylhufin) as an aqueous solution, the mixture was reacted at 170 ° C. for 5 hours to synthesize an epoxy resin having a phosphorus content of 4.1%.
[0031]
Synthesis Example 2: Compound B
Using 344 g of bisphenol F type epoxy resin (epoxy equivalent 172) and 292 g of HCA-HQ (trade name, manufactured by Sanko Chemical Co., Ltd.) as a reaction catalyst, 0.15 g of TPP was used as an aqueous solution and reacted at 170 ° C. for 4 hours to obtain a phosphorus content of 4. A 4% epoxy resin was synthesized.
[0032]
Example 1
1000 parts of cresol novolak type epoxy resin YDCN-704P (trade name, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, resin solid content 70% by weight), bisphenol A type novolak type epoxy resin (epoxy equivalent 205, resin solid content 100% by weight) 300 parts, 850 parts of a triazine-modified novolak type phenol resin LA-7051 (trade name, manufactured by Dainippon Ink and Chemicals, Inc., hydroxyl value 124, resin solid content 70% by weight), PX-200 of condensed phosphate ester (Daichi Chemical Propylene glycol monomethyl ether (PGM) as a solvent was added to a mixture of 280 parts of aluminum hydroxide, 800 parts of aluminum hydroxide and 1.9 parts of 2-ethyl-4-methylimidazole as a solvent. A resin varnish was prepared.
[0033]
Example 2
1000 parts of cresol novolak type epoxy resin YDCN-704P (trade name, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, resin solid content 70% by weight), bisphenol A type novolak type epoxy resin (epoxy equivalent 205, resin solid content 100% by weight) 300 parts, 850 parts of a triazine-modified novolak type phenol resin LA-7051 (trade name, manufactured by Dainippon Ink and Chemicals, Inc., hydroxyl value 124, resin solid content 70% by weight), PX-200 of condensed phosphate ester (Daichi Chemical PGM as a solvent was added to a mixture of 280 parts of trade name (trade name, manufactured by Co., Ltd.), 800 parts of silica and 1.9 parts of 2-ethyl-4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0034]
Example 3
1000 parts of cresol novolak type epoxy resin YDCN-704P (trade name, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, resin solid content 70% by weight), bisphenol A type novolak type epoxy resin (epoxy equivalent 205, resin solid content 100% by weight) 300 parts, 850 parts of triazine-modified novolak type phenolic resin LA-7051 (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 124, resin solid content 70% by weight), condensed phosphate ester PX-200 (Daihachi Chemical Co., Ltd.) PGM as a solvent was added to a mixture of 320 parts (manufactured and trade name) and 2.0 parts of 2-ethyl-4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0035]
Example 4
1000 parts of cresol novolak type epoxy resin YDCN-704P (trade name, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, resin solid content 70% by weight), bisphenol A type novolak type epoxy resin (epoxy equivalent 205, resin solid content 100% by weight) 300 parts, 850 parts of triazine-modified novolak type phenolic resin LA-7051 (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 124, resin solid content 70% by weight), condensed phosphate ester PX-200 (Daihachi Chemical Co., Ltd.) PGM as a solvent in a mixture of 200 parts of bisphenol A type benzoxazine resin (resin solid content 75% by weight), 300 parts of aluminum hydroxide and 1.9 parts of 2-ethyl-4-methylimidazole. In addition, an epoxy resin varnish having a resin solid content of 65% by weight was prepared.
[0036]
Example 5
600 parts of the phosphorus-containing epoxy resin synthesized in Synthesis Example 1 (epoxy equivalent 190), 400 parts of a bisphenol A type novolak type epoxy resin (epoxy equivalent 205, resin solid content 100% by weight), LA-7051 of a triazine modified novolak type phenol resin. 900 parts (product name, hydroxyl value 124, resin solid content 70% by weight, manufactured by Dainippon Ink and Chemicals), 100 parts of condensed phosphate ester PX-200 (product name, manufactured by Daihachi Chemical Co., Ltd.), 750 parts of aluminum hydroxide PGM as a solvent was added to a mixture of 1.82 parts of 2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0037]
Example 6
600 parts of the phosphorus-containing epoxy resin synthesized in Synthesis Example 2, 400 parts of a bisphenol A type novolak type epoxy resin (epoxy equivalent: 205, resin solid content: 100% by weight), LA-7051 of a triazine modified novolak type phenol resin (Dainippon Ink Chemicals) 960 parts of condensed phosphoric acid ester PX-200 (trade name, manufactured by Daihachi Chemical Co., Ltd.), 740 parts of aluminum hydroxide and 2-ethyl- PGM as a solvent was added to a mixture of 1.82 parts of 4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0038]
Comparative Example 1
1450 parts of cresol novolak type epoxy resin YDCN-704P (trade name, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, resin solid content 70% by weight), LA-7051 of triazine-modified novolak type phenol resin (trade name of Dainippon Ink and Chemicals, Inc.) 860 parts, condensed phosphate ester PX-200 (trade name, manufactured by Daihachi Chemical Co., Ltd.), 280 parts, aluminum hydroxide 800 parts and 2-ethyl-4-methylimidazole PGM was added as a solvent to 1.9 parts of the mixture to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0039]
Comparative Example 2
1000 parts of cresol novolak type epoxy resin YDCN-704P (trade name, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210, resin solid content 70% by weight), Epicoat 1001 of bisphenol A type epoxy resin (trade name, manufactured by Yuka Shell Co., epoxy equivalent) 456 parts, resin solid content 70% by weight) 430 parts, triazine-modified novolak type phenol resin LA-7051 (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 124, resin solids content 70% by weight) 710 parts, condensed phosphoric acid PGM was added as a solvent to a mixture of 280 parts of ester PX-200 (trade name, manufactured by Daihachi Chemical Co., Ltd.), 800 parts of aluminum hydroxide and 1.9 parts of 2-ethyl-4-methylimidazole, and the resin solid content was 65% by weight. Was prepared.
[0040]
Comparative Example 3
600 parts of brominated epoxy resin Epicoat 5045 (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 480, resin solid content: 80% by weight), bisphenol A type novolak resin (manufactured by Dainippon Ink and Chemicals, hydroxyl value: 118, resin solid content) PGM as a solvent was added to a mixture of 169 parts (70% by weight) and 0.6 part of 2-ethyl-4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0041]
Comparative Example 4
651 parts of epicoat 1001 of bisphenol A type epoxy resin (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 456, resin solid content: 70% by weight), YDCN-704P, cresol novolac type epoxy resin (trade name, manufactured by Toto Kasei, epoxy equivalent) 210, resin solids content 70% by weight) 300 parts, bisphenol A type novolak resin (manufactured by Dainippon Ink and Chemicals, hydroxyl value 118, resin solids content 70% by weight) 337 parts, triphenylene phosphate 541 parts, aluminum hydroxide 361 parts PGM and dimethylformamide were added as a solvent to a mixture of 0.9 parts of 2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0042]
Comparative Example 5
A solvent was added to a mixture of 600 parts of brominated epoxy resin Epicoat 5045 (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 480, resin solid content: 80% by weight), 13 parts of dicyandiamide, and 0.5 part of 2-ethyl-4-methylimidazole. Was added to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0043]
Comparative Example 6
651 parts of epicoat 1001 of bisphenol A type epoxy resin (trade name, manufactured by Yuka Shell Co., epoxy equivalent: 456, resin solid content: 70% by weight), YDCN-704P, cresol novolac type epoxy resin (trade name, manufactured by Toto Kasei, epoxy equivalent) 210, resin solid content 70% by weight) 300 parts, dicyandiamide 25 parts, condensed phosphate ester PX-200 (trade name, manufactured by Daihachi Chemical Co., Ltd.) 230 parts, aluminum hydroxide 230 parts and 2-ethyl-4-methyl PGM and dimethylformamide as solvents were added to a mixture of 0.7 parts of imidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.
[0044]
Each of the epoxy resin varnishes obtained in Examples 1 to 6 and Comparative Examples 1 to 6 was continuously applied and impregnated on a 180-μm glass woven fabric, a 100-μm glass woven fabric or a 50-μm wholly aromatic polyester-based nonwoven fabric. The prepreg was dried by drying at a temperature.
[0045]
One obtained by laminating eight 180 μm glass woven prepregs obtained in this way and one of 100 μm glass woven prepregs were prepared, and a copper foil having a thickness of 18 μm was laminated on both sides of this laminated body at 170 ° C. The mixture was heated and pressed at a temperature of 4 MPa for 100 minutes to obtain a 1.6 mm thick glass epoxy double-sided copper-clad laminate and a 0.1 mm thick glass epoxy double-sided copper-clad laminate.
[0046]
Next, the same prepreg was overlapped, copper foil having a thickness of 35 μm was overlapped on both surfaces thereof, and heated and pressed in the same manner. From the prepreg using a 180 μm glass woven fabric, an inner layer plate having a thickness of 0.8 mm and a 100 μm glass An inner layer plate having a thickness of 0.1 mm was manufactured from a prepreg using a cloth.
[0047]
A circuit including a clearance hole of 0.5φ is formed on the inner layer plate having a thickness of 0.8 mm, and after oxidizing the surface of the copper foil, the 180 μm glass woven prepreg is superimposed on both surfaces thereof, and the thickness of each is laid thereon. A 12-μm copper foil was overlaid and heated and pressed in the same manner to produce a 1.2-mm thick 4-layer shield plate.
[0048]
Also, a circuit including a clearance hole of 0.5φ and a land of 0.2φ is formed on both sides of the inner layer plate having a thickness of 0.8mm, and after oxidizing the surface of the copper foil, the above 50 μm wholly aromatic polyester is formed on both surfaces. A nonwoven fabric prepreg was laminated, and a copper foil having a thickness of 12 μm was laminated thereon, and heated and pressed similarly to produce a 4-layer shield plate having a thickness of 1.0 mm.
[0049]
Also, a circuit including a clearance hole of 0.5φ was formed on two boards of the inner layer board having a thickness of 0.1 mm, and after oxidizing the copper foil surface, one 100 μm glass woven prepreg was put between them, and both sides were placed. Then, the above-mentioned 100 μm glass woven prepreg was overlapped, and 18 μm-thick copper foil was overlapped on each of the prepregs, and similarly heated and pressed to produce a 0.5 mm thick 6-layer shield plate.
[0050]
In addition, a circuit including a clearance hole of 0.5φ and a land of 0.2φ on one side is formed on two boards having an inner layer thickness of 0.1mm, and after oxidizing the copper foil surface, a 100μm glass cloth One prepreg is placed, 50 μm wholly aromatic polyester non-woven prepreg is superimposed on both sides, copper foil of 12 μm thickness is superimposed on each prepreg, and heated and pressed in the same manner. Was manufactured.
[0051]
Of these, a circuit including a land of 0.5φ is formed on a double-sided board and a shield plate made only of glass woven cloth, a through-hole is formed by a drill of 0.2φ, and a plating thickness is usually formed in a plating process. A through-hole substrate of 15 to 20 μm is formed. In the case of a multilayer board including a wholly aromatic polyester-based nonwoven fabric prepreg, laser vias (0.15 land) of 0.1 φ are formed on both sides by a conformal method. Further, a circuit including a land of 0.5φ is formed, a through-hole is formed by a drill of 0.2φ, and a substrate including a laser via having a plating thickness of 15 to 20 μm and a through-hole is formed in a normal plating process.
[0052]
The through hole reliability of the test board described above was evaluated by a hot oil and a thermal cycle test. The results are shown in Tables 1 to 6. The test conditions are as follows.
[0053]
In Tables 1 to 6, the samples in the sub-numbers of the respective examples and comparative examples are as follows.
[0055]
Sub number 1: 0.1mm thick glass epoxy double-sided copper-clad laminate,
Sub number 2: 1.6 mm thick glass epoxy double-sided copper-clad laminate,
Sub number 3: 1.2 mm thick 4-layer shield plate,
Sub number 4: 1.0 mm thick 4-layer shield plate (LVH),
Sub number 5: Plate thickness 0.5 mm, 6-layer shield plate,
Sub number 6: 0.4 mm thick, 6 layer shield plate (LVH).
[0056]
[Table 1]
* 2: ○: passed,
* 3: After treatment under the treatment conditions in the table, the presence or absence of blisters was observed.
[0057]
[Table 2]
* 2: ○: passed,
* 3: After treatment under the treatment conditions in the table, the presence or absence of blisters was observed.
[0058]
[Table 3]
* 2: ○: passed,
* 3: After treatment under the treatment conditions in the table, the presence or absence of blisters was observed.
[0059]
[Table 4]
* 2: ○: passed,
* 3: After treatment under the treatment conditions in the table, the presence or absence of blisters was observed.
[0060]
[Table 5]
* 2: ○: passed,
* 3: After treatment under the treatment conditions in the table, the presence or absence of blisters was observed.
[0061]
[Table 6]
* 2: ○: passed,
* 3: After treatment under the treatment conditions in the table, the presence or absence of blisters was observed.
[0062]
【The invention's effect】
As is clear from the above description and the results of Tables 1 to 6, according to the present invention, excellent flame retardancy is exhibited without containing halogen, and a high multilayer board, a high aspect ratio substrate, or severe use conditions ( For example, there is provided an epoxy resin composition which provides a glass epoxy copper-clad laminate having significantly improved through-hole reliability at -65 ° C and 150 ° C cooling / heating cycle. By using such a glass epoxy copper clad laminate, it is possible to provide a printed wiring board having good environmental characteristics and excellent in various characteristics.
Claims (10)
（Ａ）縮合型リン酸エステル化合物および
（Ｂ）ビスフェノール系ノボラック型エポキシ樹脂化合物
を必須成分とすることを特徴とするハロゲンフリーの難燃性エポキシ樹脂組成物。An epoxy resin composition applied to the production of a laminate,
A halogen-free flame-retardant epoxy resin composition comprising (A) a condensed phosphate ester compound and (B) a bisphenol-based novolak epoxy resin compound as essential components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002214643A JP2004051907A (en) | 2002-07-24 | 2002-07-24 | Halogen-free flame retardant epoxy resin composition, and prepreg, laminated board, copper-clad laminated board and printed circuit board containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002214643A JP2004051907A (en) | 2002-07-24 | 2002-07-24 | Halogen-free flame retardant epoxy resin composition, and prepreg, laminated board, copper-clad laminated board and printed circuit board containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004051907A true JP2004051907A (en) | 2004-02-19 |
Family
ID=31936882
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002214643A Pending JP2004051907A (en) | 2002-07-24 | 2002-07-24 | Halogen-free flame retardant epoxy resin composition, and prepreg, laminated board, copper-clad laminated board and printed circuit board containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004051907A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006278647A (en) * | 2005-03-29 | 2006-10-12 | Mitsubishi Paper Mills Ltd | Resin impregnated base material for circuit boards |
| JP2007031461A (en) * | 2005-07-22 | 2007-02-08 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated board |
| JP2010541028A (en) * | 2007-08-10 | 2010-12-24 | ゴア エンタープライズ ホールディングス，インコーポレイティド | Unauthorized opening reaction system |
| WO2020031495A1 (en) | 2018-08-06 | 2020-02-13 | 大八化学工業株式会社 | Flame retardant for thermosetting resin including aromatic phosphoric acid ester, thermosetting resin composition including same, and cured material and application of same |
-
2002
- 2002-07-24 JP JP2002214643A patent/JP2004051907A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006278647A (en) * | 2005-03-29 | 2006-10-12 | Mitsubishi Paper Mills Ltd | Resin impregnated base material for circuit boards |
| JP2007031461A (en) * | 2005-07-22 | 2007-02-08 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated board |
| JP2010541028A (en) * | 2007-08-10 | 2010-12-24 | ゴア エンタープライズ ホールディングス，インコーポレイティド | Unauthorized opening reaction system |
| WO2020031495A1 (en) | 2018-08-06 | 2020-02-13 | 大八化学工業株式会社 | Flame retardant for thermosetting resin including aromatic phosphoric acid ester, thermosetting resin composition including same, and cured material and application of same |
| KR20210040388A (en) | 2018-08-06 | 2021-04-13 | 다이하치 카가쿠 고교 가부시키가이샤 | Flame retardant for thermosetting resin containing aromatic phosphoric acid ester, thermosetting resin composition containing the same, cured product thereof, and use thereof |
| JPWO2020031495A1 (en) * | 2018-08-06 | 2021-09-02 | 大八化学工業株式会社 | Flame retardant for thermosetting resin containing aromatic phosphoric acid ester, thermosetting resin composition containing it, cured product thereof and its use |
| JP7269665B2 (en) | 2018-08-06 | 2023-05-09 | 大八化学工業株式会社 | Thermosetting resin composition containing flame retardant for thermosetting resin containing aromatic phosphate ester, cured product thereof, and use thereof |
| US11965126B2 (en) | 2018-08-06 | 2024-04-23 | Daihachi Chemical Industry Co., Ltd. | Flame retardant for thermosetting resin including aromatic phosphoric acid ester, thermosetting resin composition including same, and cured material and application of same |
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