JPS63120742A - Resin composition for electrical laminate - Google Patents
Resin composition for electrical laminateInfo
- Publication number
- JPS63120742A JPS63120742A JP26612586A JP26612586A JPS63120742A JP S63120742 A JPS63120742 A JP S63120742A JP 26612586 A JP26612586 A JP 26612586A JP 26612586 A JP26612586 A JP 26612586A JP S63120742 A JPS63120742 A JP S63120742A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- flame
- meth
- retardant
- vinyl monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 7
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 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 abstract description 12
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical class C* 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- -1 methacryloyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 238000004080 punching Methods 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000123 paper Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QWVCIORZLNBIIC-UHFFFAOYSA-N 2,3-dibromopropan-1-ol Chemical compound OCC(Br)CBr QWVCIORZLNBIIC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000005267 main chain polymer Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Graft Or Block Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Insulating Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は電気機器、電子機器、通信器等に用いられる金
属箔張り積層板用樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a resin composition for metal foil-clad laminates used in electrical equipment, electronic equipment, communication devices, and the like.
［従来の技術］
金属箔張り電気用積層板に用いられる樹脂としては、フ
ェノール樹脂、エポキシ樹脂、不飽和ボリエステル樹脂
が代表的なものであり、各種の含浸用基材と組合わせて
利用されている。上記積層板には多くの場合、難燃性能
が要求されているが、ラジカル硬化性樹脂の代表である
不飽和ポリエステル樹脂やビニルエステル樹脂の難燃化
の方法は現在でも大きな課題となっている。[Prior art] Typical resins used in metal foil-clad electrical laminates include phenolic resins, epoxy resins, and unsaturated polyester resins, which are used in combination with various impregnating base materials. There is. Flame-retardant performance is often required for the above-mentioned laminates, but the method of making unsaturated polyester resins and vinyl ester resins, which are typical radical-curable resins, flame-retardant is still a major issue. .
［発明が解決しようとする問題点］
これらの樹脂と同様に本発明の構成成分である一般式（
Ｉ）で示されるラジカル硬化性プレポリマーはそれ自体
あるいは他のごニルモノマーと混合して金属箔張り電気
用積層板製造に供しうるものであるが、該積層板の難燃
化がさらに要望されているのが現状である。[Problems to be solved by the invention] Similar to these resins, the general formula (
The radical curable prepolymer shown in I) can be used by itself or mixed with other monomers to produce metal foil-clad electrical laminates, but there is a further demand for flame retardancy of the laminates. The current situation is that
本発明は、一般式ＣＩ）で示されるラジカル硬化性プレ
ポリマーを主成分とする硬化性樹脂液を効果的にｆｉ燃
化して成る電気用ｌ１１１層板用樹脂組成物の提供を目
的とする。The object of the present invention is to provide a resin composition for an electrical 1111 laminate, which is obtained by effectively burning a curable resin liquid containing a radically curable prepolymer represented by the general formula CI) as a main component.
［問題点を解決するための手段］
本発明の前記目的は、一般式
％式％
〔式中、Ａはビニルモノマーとアクリロイルモノマーも
しくはメタクリロイルモノマーとのランダム共重合体主
鎖部分を示し、Ｒは水素またはメチル基を示す〕
にて示される、側鎖末端にアクリロイル基もしくはメタ
クリロイル基ｒ以下、両者を（メタ）アクリロイル基と
呼称」を含有するラジカル硬化性プレポリマー１０〜６
０重量％に対して、一般式
％式％
［）
〔式中、Ｒは炭素数１〜１２の脂肪族もしくは脂環式臭
素置換炭化水素基であって、酸素原子と結合している炭
素は１級もしくは２級である〕にて示される臭素含有難
燃性モノマーが５〜３０ｍ世％の範囲で添加されて成り
、残部が架橋性上ツマ−から成るＢＹ１＆性樹脂配合液
を主成分とする本発明の電気用積層用樹脂組成物によっ
て達成される。[Means for Solving the Problems] The object of the present invention is to satisfy the general formula % [wherein A represents a main chain portion of a random copolymer of a vinyl monomer and an acryloyl monomer or a methacryloyl monomer, and R Radically curable prepolymers 10 to 6 containing an acryloyl group or methacryloyl group (r) at the end of the side chain, both of which are referred to as (meth)acryloyl groups, represented by [representing hydrogen or methyl group]
0% by weight, the general formula % formula % [) [wherein R is an aliphatic or alicyclic bromine-substituted hydrocarbon group having 1 to 12 carbon atoms, and the carbon bonded to the oxygen atom is The main component is a BY1 resin compounded liquid containing a bromine-containing flame retardant monomer (1st class or 2nd class) added in the range of 5 to 30%, and the remainder consisting of a crosslinkable upper layer. This is achieved by the electrical lamination resin composition of the present invention.
［作 用］
一般式（Ｉ）においてＡはビニルモノマーと（メタ）ア
クリロイル基との共重合体主鎖骨格部分を示すものであ
り、Ａを含む主鎖ポリマーは、ｆｆ［平均分子ｍとして
１〜２０万、好適には２〜１０程度である。[Function] In the general formula (I), A represents the main chain skeleton of a copolymer of a vinyl monomer and a (meth)acryloyl group, and the main chain polymer containing A has an average molecular weight of 1 ~200,000, preferably about 2 to 10.
また主鎖ポリマー中に含まれるビニル側鎖の密度は自由
に変えることができるが、積層板用樹脂組成物に用いる
場合には０．１〜２モル／〔工〕１０００９の範囲が好
ましい。Further, the density of the vinyl side chains contained in the main chain polymer can be freely changed, but when used in a resin composition for a laminate, it is preferably in the range of 0.1 to 2 mol/[module] 10,009.
またＡを含む主鎖部分を形成するために用いられるビニ
ルモノマーとしては、（メタ）アクリロイル基と共重合
可能な種類であれば、いずれのものでも使用できる。Furthermore, as the vinyl monomer used to form the main chain portion containing A, any vinyl monomer can be used as long as it is copolymerizable with a (meth)acryloyl group.
これらの代表例には、スチレン、α−メチルスチレン、
ビニルトルエン、クロロスチレン、アクリル酸メチル、
アクリル酸エチル、アクリル酸イソブチル、アクリル酸
イソブチル、アクリル酸−ｔｅｒｔ−ブチル、アクリル
酎−２−エチルヘキシル、メタクリル酸メチル、メタク
リル酸エチル、メタクリル酸イソブチル、メタクリル酸
イソブチル、メタクリル酸−ｔｅｒｔ−ブチル、メタク
リル酸−２−エチルヘキシル、メタクリル酸ラウリル、
メタクリル酸シクロヘキシル、メタクリル酸ベンジル、
メタクリル酸テトラヒドロフルフリル、アクリロニトリ
ル、酢酸ビニル、プロピオン酸ビニル、塩化ビニリデン
および塩化ビニル等が包含される。Typical examples of these include styrene, α-methylstyrene,
vinyltoluene, chlorostyrene, methyl acrylate,
Ethyl acrylate, isobutyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methacrylate 2-ethylhexyl acid, lauryl methacrylate,
cyclohexyl methacrylate, benzyl methacrylate,
Included are tetrahydrofurfuryl methacrylate, acrylonitrile, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl chloride, and the like.
主鎖骨格を形成するために用いるビニルモノマーの組合
わせにより（Ｉ）にて示されるラジカル硬化性プレポリ
マーの性質を変えることができる。The properties of the radically curable prepolymer shown in (I) can be changed depending on the combination of vinyl monomers used to form the main chain skeleton.
本発明の一般式（Ｉ）で表わされるラジカル硬化性プレ
ポリマーの製造方法としては、ビニルモノマーと（メタ
）アクリル酸とを共重合させて側鎖にカルボキシル基を
有する共重合体を製造し、次いでグリシジル（メタ）ア
クリレートを加えて側鎖のカルボキシル基とエステル化
を行なって側鎖末端に（メタ）アクリロイル基を有する
本発明のラジカル硬化性プレポリマーを得る方法が挙げ
られる。同様に、先ず、ビニルモノマーとグリシジル（
メタ）アクリレートとを共重合させて側鎖にグリシジル
基を有する共重合体を得、次いで（メタ）アクリル酸を
添加して側鎖末端に（メタ）アクリロイル基を導入して
製造することも可能である。As a method for producing the radically curable prepolymer represented by the general formula (I) of the present invention, a vinyl monomer and (meth)acrylic acid are copolymerized to produce a copolymer having a carboxyl group in the side chain, Next, glycidyl (meth)acrylate is added to perform esterification with the carboxyl group in the side chain to obtain the radical curable prepolymer of the present invention having a (meth)acryloyl group at the end of the side chain. Similarly, first, vinyl monomer and glycidyl (
It can also be produced by copolymerizing with meth)acrylate to obtain a copolymer having a glycidyl group in the side chain, and then adding (meth)acrylic acid to introduce a (meth)acryloyl group at the end of the side chain. It is.
一般式（ＩＩ）にて示される臭素含有難燃性モノマーは
組成物の難燃化の要請にしたがって種類および添加割合
が選ばれる。The type and addition ratio of the bromine-containing flame-retardant monomer represented by general formula (II) are selected according to the requirements for flame-retardant composition.
例えば紙を基材として積層板を作成する場合、５ｂ２０
３を併用するとき、臭素分が樹脂配合液中に約１０％以
上の場合にＵＬ−９４−Ｖ −０の試験に合格する。For example, when creating a laminate using paper as the base material, 5b20
When 3 is used in combination, the UL-94-V-0 test is passed when the bromine content in the resin mixture is about 10% or more.
臭素含有難燃性モノマーは臭素化１級もしくは２級アル
コールと無水マレイン酸の付加反応により合成すること
ができる。臭素化アルコールとしては、脂肪族もしくは
脂環式の炭素数１〜１２のアルコールが好ましく、市場
から入手が容易な種類としては２．３ジブロムプロパノ
ール、トリブロムネオペンチルアルコール等を挙げるこ
とができるが、これらに限定されるものではない。The bromine-containing flame-retardant monomer can be synthesized by an addition reaction between a brominated primary or secondary alcohol and maleic anhydride. The brominated alcohol is preferably an aliphatic or alicyclic alcohol having 1 to 12 carbon atoms, and examples of types that are easily available on the market include 2.3 dibromopropanol and tribromeneopentyl alcohol. However, it is not limited to these.
臭素含有難燃性モノマーを用いる利点は、添加型とは異
なり硬化樹脂から移行しないことおよび樹脂配合液の粘
度調節が容易になることであり、一般式（Ｉ）で示され
るラジカル硬化性プレポリマーの分子量設定および主鎖
に使用するごニルモノマーの種類と選択が容易になるこ
とである。The advantage of using a bromine-containing flame-retardant monomer is that, unlike additive-type monomers, it does not migrate from the cured resin, and it becomes easy to adjust the viscosity of the resin mixture. This makes it easier to set the molecular weight of the polymer and to select the type and type of monomer used in the main chain.
本発明において用いられる架橋用ビニルモノマーとして
は公知のいずれのものも使用可能であるが、これらの中
にはスチレン、α−メチルスチレン、ｐ−メチルスチレ
ン、ｐ−りＯルスチレン、ｐ−ビニルスチレンのような
置換スチレン類；アクリル酸およびメタアクリル酸エス
テル類；エチレングリコールジアクリレート、エチレン
グリコールジメタアクリレート、１．４−ブタンジオー
ルジアクリレート、１．４−ブタンジオールジメタアク
リレート、トリメヂロールブロバントリアクリレート、
トリメチロールブＯパントリメタアクリレート等のビニ
ル多官能アクリル酸もしくはメタアクリル酸エステル類
：ポリウレタンアクリレート、ポリウレタンメタアクリ
レート、ポリエーテルアクリレート、ポリエーテルメタ
アクリレート等のビニル多官能オリゴエステル類が包含
される。Any known crosslinking vinyl monomer can be used in the present invention, but these include styrene, α-methylstyrene, p-methylstyrene, p-polystyrene, and p-vinylstyrene. Substituted styrenes such as; acrylic and methacrylic esters; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, trimedylolbroban triacrylate,
Vinyl polyfunctional acrylic acid or methacrylic acid esters such as trimethylolbu-O-pantrimethacrylate; vinyl polyfunctional oligoesters such as polyurethane acrylate, polyurethane methacrylate, polyether acrylate, and polyether methacrylate.
［実 施 例］
以下、本発明を実施例によって詳述するが、本発明の要
旨を逸脱しない限り、これらの実施例のみに限定される
ものではない。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples unless it departs from the gist of the present invention.
また、この明細書を通して、温度は全て℃であり、部お
よび％は特記しない限り重量基準である。Also, throughout this specification, all temperatures are in degrees Centigrade and parts and percentages are by weight unless otherwise specified.
製造例 １
撹拌機、冷却管、滴下ロート、温度計付セパラブルフラ
スコ（５０００Ｉ１１）にアクリル酸（１２ｇ、１モル
）、アクリル酸エチル（８００ｇ、８モル）、アクリロ
ニトリル（５３ｇ、１モル）、メチルエチルケトン（７
００ｇ） 、ドデシルメルカプタン（１０ｇ）を仕込み
、窒素雰囲気下に７５℃に加熱した。Production Example 1 Acrylic acid (12 g, 1 mol), ethyl acrylate (800 g, 8 mol), acrylonitrile (53 g, 1 mol), methyl ethyl ketone in a separable flask (5000I11) equipped with a stirrer, cooling tube, dropping funnel, and thermometer. (7
00g) and dodecyl mercaptan (10g) were charged and heated to 75°C under a nitrogen atmosphere.
アゾビスイソブチロニトリル（５ｇ）をメチルエチルケ
トン＜５０９）に溶解し、この液を約１時間かけて滴下
ロートより滴下し、反応器内温度を７５〜８０℃に保ち
つつ添加した。触媒の添加終了後、同温度で８時間反応
を続けた。Azobisisobutyronitrile (5 g) was dissolved in methyl ethyl ketone (<509), and this solution was added dropwise from the dropping funnel over about 1 hour while maintaining the temperature inside the reactor at 75 to 80°C. After the addition of the catalyst was completed, the reaction was continued at the same temperature for 8 hours.
次いで反応器内を１８０℃迄加熱して、小母の未反応モ
ノマーと共にメチルエチルケトンを留去した。Next, the inside of the reactor was heated to 180° C., and methyl ethyl ketone was distilled off together with the unreacted monomers.
反応器（フラスコ）に得られたポリマーは９２０ｇであ
った。このポリマーのｆｆ１ｆｆｉ平均分子聞は４万で
あった。The amount of polymer obtained in the reactor (flask) was 920 g. The ff1ffi average molecular weight of this polymer was 40,000.
この反応器内にグリシジルメタアクリレート（１４２ｇ
、１モル）、およびスチレン（１０００ｇ＞を仕込み、
バラベンゾキノン（０，２ｇ） 、トリフェニルホスフ
ィン（４ｇ）を添加した後、１１０℃で５時間反応させ
た。グリシジルメタアクリレートは約８８％エステル化
反応した。得られたラジカル硬化性プレポリマーを含む
樹脂液は不揮発分５３％の黄褐色液で粘度７．１ボイズ
（２５℃）であった。Glycidyl methacrylate (142 g
, 1 mol), and styrene (1000 g>),
After adding rosebenzoquinone (0.2 g) and triphenylphosphine (4 g), the mixture was reacted at 110° C. for 5 hours. Approximately 88% of glycidyl methacrylate was esterified. The resulting resin liquid containing the radically curable prepolymer was a yellowish brown liquid with a nonvolatile content of 53% and a viscosity of 7.1 voids (at 25°C).
製造例 ２
セパラブルフラスコ（１０００ｄ ’）に撹拌機を付し
、この中で２．３−ジブロムプロパノール（４３４（Ｊ
、２モル）および無水マレイン酸（１９７ｇ、２モル）
を加熱撹拌した。約５０℃で均一溶液となった。ここで
トリエチルアミン（１ｇ）を添加した。温度を８０℃と
して６時間反応させた。室温に冷却して放置すると白色
結晶となった。Production Example 2 A separable flask (1000 d') was equipped with a stirrer, and 2,3-dibromopropanol (434 (J)
, 2 mol) and maleic anhydride (197 g, 2 mol)
was heated and stirred. A homogeneous solution was obtained at about 50°C. At this point triethylamine (1 g) was added. The temperature was set to 80°C and the reaction was carried out for 6 hours. When cooled to room temperature and left to stand, white crystals formed.
製造Ｍ３
セパラブルフラスコ（１０００Ｉｄ）に撹拌機を付し、
この中でトリブロムネオペンデルアルコール（６８２ｇ
、２モル）および無水マレイン酸（１９７４７，２モル
）を加熱撹拌した。約１０℃で均一溶液となった。ここ
でトリエチルアミン１ｇを添加した。Production M3 Attach a stirrer to a separable flask (1000Id),
Among these, tribrome neopendel alcohol (682g
, 2 mol) and maleic anhydride (19747, 2 mol) were heated and stirred. A homogeneous solution was obtained at about 10°C. At this point, 1 g of triethylamine was added.
温度を８０℃として６時間反応させた。室温に冷却して
放置すると白色結晶となった。The temperature was set to 80°C and the reaction was carried out for 6 hours. When cooled to room temperature and left to stand, white crystals formed.
実 施 例
坪量１３５ｇ／尻のクラフト紙（１０αＸ１０備）を「
ニカレデン３−３０５Ｊ（商品名、日本カーバイド社製
メチロールメラミン）水溶液に浸してローラーで絞り、
１２０℃で３０分乾燥した。Implementation example: Kraft paper (10α x 10 paper) with a basis weight of 135g/
Nikaledene 3-305J (trade name, Nippon Carbide Co., Ltd. methylolmelamine) soaked in an aqueous solution and squeezed with a roller,
It was dried at 120°C for 30 minutes.
得られた紙基材中に１１，４重量％メラミンが展着した
。この紙を平皿に入れた表１に示す組成の含浸用樹脂液
に浮かべて、樹脂液を滲み込ませた。11.4% by weight of melamine was spread in the paper base material obtained. This paper was placed in a flat plate and floated on an impregnating resin solution having the composition shown in Table 1 to allow the resin solution to seep into it.
樹脂液を含んだ紙を６枚と市販接着剤付銅箭「ＨＫ−５
６Ｊ （商品名、三井金属鉱業社製）を−枚重ね合わ
せてセロハンの袋に入れて、これを２枚の鉄板にはさみ
、３０ Ｋｇの重りをのせた。Six sheets of paper containing resin liquid and a commercially available adhesive-coated copper bamboo ``HK-5''
6J (trade name, manufactured by Mitsui Kinzoku Mining Co., Ltd.) were stacked one on top of the other, placed in a cellophane bag, sandwiched between two iron plates, and a 30 kg weight was placed on top.
この状態で１２０℃の空気オーブンに入れ、１２０
℃で１時間、さらに１００℃で１０時間硬化させた。得
られた積層板は、１．５９〜１．６１ ｍ厚であった。In this state, put it in an air oven at 120℃.
It was cured at 100°C for 1 hour and then at 100°C for 10 hours. The resulting laminate was 1.59-1.61 m thick.
積層板の特性値を表２に示ず。Table 2 does not show the characteristic values of the laminate.
表 １ 樹脂配合液組成
表２ 積層板物性
欠陥の生じなくなる温度
［発明の効果］
本発明の電気用積層用樹脂組成物は、優れた難燃性を有
しており、かつ耐熱性、耐水性および打扱き特性も良好
である。Table 1 Resin compound composition Table 2 Temperature at which physical property defects of laminates no longer occur [Effects of the invention] The resin composition for electrical laminates of the present invention has excellent flame retardancy, heat resistance, and water resistance. It also has good handling characteristics.
Claims (1)
しくはメタクリロイルモノマーとのランダム共重合体主
鎖部分を示し、Ｒは水素またはメチル基を示す） にて示される、側鎖末端にアクリロイル基もしくはメタ
クリロイル基を含有するラジカル硬化性プレポリマー１
０〜６０重量％に対して、 一般式 〔II〕 〔式中、Ｒは炭素数１〜１２の脂肪族もしくは脂環式臭
素置換炭化水素基であって、酸素原子と結合している炭
素は１級もしくは２級である〕にて示される臭素含有難
燃性モノマーが５〜３０重量％の範囲で含有されて成り
、残部が架橋用ビニルモノマーから成る難燃性樹脂配合
液を主成分とする電気用積層板用樹脂組成物。(1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. Radically curable prepolymer 1 containing an acryloyl group or a methacryloyl group at the end of the side chain, shown by
0 to 60% by weight, the general formula [II] [wherein R is an aliphatic or alicyclic bromine-substituted hydrocarbon group having 1 to 12 carbon atoms, and the carbon bonded to the oxygen atom is The main component is a flame-retardant resin compounded liquid containing 5 to 30% by weight of a bromine-containing flame-retardant monomer (1st class or 2nd class), with the remainder being a crosslinking vinyl monomer. A resin composition for electrical laminates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26612586A JPS63120742A (en) | 1986-11-07 | 1986-11-07 | Resin composition for electrical laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26612586A JPS63120742A (en) | 1986-11-07 | 1986-11-07 | Resin composition for electrical laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63120742A true JPS63120742A (en) | 1988-05-25 |
Family
ID=17426673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26612586A Pending JPS63120742A (en) | 1986-11-07 | 1986-11-07 | Resin composition for electrical laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63120742A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398259C (en) * | 2003-01-24 | 2008-07-02 | 克斯美库股份有限公司 | Spring lock-type clamp device |
-
1986
- 1986-11-07 JP JP26612586A patent/JPS63120742A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398259C (en) * | 2003-01-24 | 2008-07-02 | 克斯美库股份有限公司 | Spring lock-type clamp device |
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