JPS6368617A - Flame-retarding resin composition and laminate prepared therefrom - Google Patents
Flame-retarding resin composition and laminate prepared therefromInfo
- Publication number
- JPS6368617A JPS6368617A JP21164786A JP21164786A JPS6368617A JP S6368617 A JPS6368617 A JP S6368617A JP 21164786 A JP21164786 A JP 21164786A JP 21164786 A JP21164786 A JP 21164786A JP S6368617 A JPS6368617 A JP S6368617A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- resin composition
- polybutadiene
- laminate
- ethylene oxide
- 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 abstract description 14
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims abstract description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 11
- 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 10
- 239000000463 material Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 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 2
- 239000000126 substance Substances 0.000 claims 2
- 229920003002 synthetic resin Polymers 0.000 claims 2
- 239000000057 synthetic resin Substances 0.000 claims 2
- 239000002648 laminated material Substances 0.000 abstract description 7
- 229920001721 polyimide Polymers 0.000 abstract description 5
- 239000004642 Polyimide Substances 0.000 abstract description 3
- 238000010030 laminating Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- ZSVFYHKZQNDJEV-UHFFFAOYSA-N (2,3,4-tribromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Br)C(Br)=C1Br ZSVFYHKZQNDJEV-UHFFFAOYSA-N 0.000 description 1
- BUPRYTFTHBNSBD-UHFFFAOYSA-N (2,3,4-tribromophenyl) prop-2-enoate Chemical compound BrC1=CC=C(OC(=O)C=C)C(Br)=C1Br BUPRYTFTHBNSBD-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 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
- 238000013007 heat curing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
Landscapes
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、難燃性樹脂組成物および、その用途に係り、
特に、遥燃性、耐熱性および電気特性に優れた多層プリ
ント回路板に好適な積層板に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a flame-retardant resin composition and its use,
In particular, the present invention relates to a laminate suitable for multilayer printed circuit boards that has excellent long-term flammability, heat resistance, and electrical properties.
従来、多層プラント回路板用積層材料として、難燃性を
付与するため、ブロム化変性樹脂や添加型難燃剤を用い
たフェノール樹脂、エポキシ樹脂およびポリイミド樹脂
等の積層板が主に使用されている。特に、大型計算機に
は高密度化が望まれ。Conventionally, laminates made of phenol resins, epoxy resins, polyimide resins, etc. using brominated modified resins or additive flame retardants have been mainly used as laminated materials for multilayer plant circuit boards to impart flame retardancy. . In particular, high density is desired for large computers.
耐熱性２寸法安定性の優れたポリイミド系樹脂が用いら
れている。しかし、近年、大型計算機の高速演算処理化
に伴い、信号伝送速度の向上のため、電気特性の優れた
プリント回路板が要求されている。特に、信号伝送遅延
時間を短かくし、かつ。A polyimide resin with excellent heat resistance and two-dimensional stability is used. However, in recent years, with the increase in high-speed calculation processing of large computers, printed circuit boards with excellent electrical characteristics are required to improve signal transmission speed. In particular, shorten the signal transmission delay time, and.
回路厚を小さくするために低誘電率のプリント回踏板が
必要とされている。このような低誘電率積層材料として
四フッ化エチレン樹脂、ポリブタジェン樹脂積層板等が
開発されている。この種の積層板には、例えば、プロシ
ーデインーグ・エヌ・イー・ビー・シー・オー・エヌ、
（１９８１年）第１６０頁から第１６９頁（Ｐｒｏ
ｃ、 ＮＥＰＣＯＮ（１９８１）ｐｐ１６０−１６９）
および特公昭５ｇ −２１９２６号公報が挙げられる。Low dielectric constant printed circuit boards are needed to reduce circuit thickness. Tetrafluoroethylene resin, polybutadiene resin laminates, and the like have been developed as such low dielectric constant laminate materials. This type of laminate includes, for example, Proceedings N.B.C.O.N.
(1981) pp. 160-169 (Pro
c, NEPCON (1981) pp160-169)
and Japanese Patent Publication No. 5g-21926.
上記従来技術でＰＴＦＥ積層板は、樹脂が熱可塑性であ
り、ガラス転移温度が低いため、高温における熱膨張率
が大きく寸法安定性が十分でないなどの問題があり、特
に、多層化接着した際のスルホール信頼性等に不安があ
って、多層プリント回路板に適用する場合、エポキシ樹
脂と同程度の配線密度をとっており、低誘電率材料とし
てのメリットがあまりない、また、ＰＴＦＥには適当な
溶媒がないので、一般に、加熱溶融圧着による接着法が
とられているが、溶融温度が非常に高いという欠点があ
る。ポリブタジェン樹脂は分子構造上、易燃性であると
いう欠点があり、難燃性を付与するためにデカブロモジ
フェニルエーテル、トリフェニルホスフェート等の添加
型難燃剤やトリブロモフェニルメタクリレート、トリブ
ロモフェニルアクリレート等の反応型薙燃剤を添加する
必要があるが、これらの添加によりポリブタジェン樹脂
本来の電気特性、耐熱性２寸法安定性を損うという問題
がある。In the conventional technology described above, PTFE laminates have problems such as a high coefficient of thermal expansion at high temperatures and insufficient dimensional stability because the resin is thermoplastic and the glass transition temperature is low. There are concerns about through-hole reliability, etc., and when applied to multilayer printed circuit boards, it has a wiring density similar to that of epoxy resin, so it does not have much merit as a low dielectric constant material, and it is not suitable for PTFE. Since there is no solvent, bonding methods using heat melting and pressure bonding are generally used, but this method has the disadvantage that the melting temperature is extremely high. Polybutadiene resin has the disadvantage of being easily flammable due to its molecular structure, so additives such as decabromodiphenyl ether and triphenyl phosphate, as well as tribromophenyl methacrylate and tribromophenyl acrylate, are used to impart flame retardancy. Although it is necessary to add a reactive flame retardant, there is a problem in that the addition of these impairs the electrical properties, heat resistance, and two-dimensional stability inherent to the polybutadiene resin.
本発明の目的は、大型計算機に使用されているポリイミ
ド系多層プリント配線板に代る材料として、ポリイミド
積層材料と同程度の高密度配線が可能で難燃性の低誘電
率積層材料の樹脂組成物。The purpose of the present invention is to create a resin composition of a flame-retardant, low-permittivity laminate material that enables high-density wiring comparable to that of polyimide laminate materials, as a material that can replace polyimide-based multilayer printed wiring boards used in large-scale computers. thing.
積層板を提供することにある。Our objective is to provide laminates.
本発明の第一は難燃性樹脂組成物に関し、その特徴は（
ａ）テトラブロモビスフェノールＡ／エチレンオキサイ
ド反応物のジメタクリレートと（ｂ）１．２−ポリブタ
ジェンおよびその誘導体を必須成分としてなる離燃性樹
脂組成物である。The first aspect of the present invention relates to a flame-retardant resin composition, the characteristics of which are (
This is a flame retardant resin composition comprising a) dimethacrylate, a tetrabromobisphenol A/ethylene oxide reactant, and (b) 1,2-polybutadiene and its derivatives as essential components.
第二は、難燃性樹脂組成物を基材に含浸、乾燥して得ら
れたプリプレグを積層成形してなる積層板に関する。The second relates to a laminate formed by laminating and molding prepregs obtained by impregnating and drying a base material with a flame-retardant resin composition.
本発明の樹脂組成物における１、２−ポリブタジェン成
分としては、１，２−ポリブタジェン単独重合をはじメ
、環化１，２−ポリブタジェン、末端エポキシ化工、２
−ポリブタジェン、１，２−ポリブタジェングリコール
、１，２−ポリブタジェンジカルボン酸、ウレタン変性
１，２−ポリブタジェン、マレイン化１，２−ポリブタ
ジェン、末端アクリル変性１，２−ポリブタジェン、末
端エステル変性１，２−ポリブタジェン等ビニル側鎖基
をもつ１，２−ポリブタジェンを基本成分として含む種
々の重合体及び共重合体等の誘導体を用いることができ
る。The 1,2-polybutadiene component in the resin composition of the present invention includes 1,2-polybutadiene homopolymerization, cyclized 1,2-polybutadiene, terminal epoxy-modified,
-Polybutadiene, 1,2-polybutadiene glycol, 1,2-polybutadiene dicarboxylic acid, urethane-modified 1,2-polybutadiene, maleated 1,2-polybutadiene, terminal acrylic-modified 1,2-polybutadiene, terminal ester-modified Various polymers and derivatives such as copolymers containing 1,2-polybutadiene having a vinyl side group such as 1,2-polybutadiene as a basic component can be used.
テトラブロモビスフェノールＡ／エチレンオキサイド反
応物のジメタクリレートと１，２−ポリブタジェン類と
の配合比（重合）は８０ ： ２０〜２０：８０の範囲
で選ばれ、前者の含有率がこれより多いと硬化樹脂の比
誘電率が高くなり、また、それが少なすぎると難燃性効
果が有意でなくなる。The blending ratio (polymerization) of tetrabromobisphenol A/ethylene oxide reactant dimethacrylate and 1,2-polybutadiene is selected in the range of 80:20 to 20:80, and if the content of the former is higher than this, curing occurs. The relative dielectric constant of the resin becomes high, and if it is too low, the flame retardant effect becomes insignificant.
また、１，２−ポリブタジェンの数平均分子量がｓ、ｏ
ｏ ｏ〜ｓｏ、ｏｏｏの範囲で選定され、この分子量
範囲より小さいとブリプレ勢のタックフリー性に問題が
生じ、その範囲より大きいと有機溶媒に対する溶解性が
低下する。In addition, the number average molecular weight of 1,2-polybutadiene is s, o
The molecular weight is selected within the range of o to so, ooo, and if the molecular weight is smaller than this range, a problem will arise in the tack-free property of the bristle, and if it is larger than this range, the solubility in organic solvents will be reduced.
次に１本発明における積層板の一般的な製造方法につい
て説明する。Next, a general method for manufacturing a laminate according to the present invention will be explained.
まず、テトラブロモビスフェノールＡ／エチレンオキサ
イド反応物のジメタクリレートおよび１゜２−ポリブタ
ジェン、または、その誘導体を、有機溶媒に溶解させて
ワニスを調製する。有機溶媒は、例えば、トルエン、キ
シレン、アセトン、メチルエチルケトン、メチルイソブ
チルケトン、Ｎ。First, a varnish is prepared by dissolving the tetrabromobisphenol A/ethylene oxide reactant dimethacrylate and 1°2-polybutadiene or a derivative thereof in an organic solvent. Examples of organic solvents include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and N.
Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン、ジ
メチルスルホキシド、トリクロロエチレン、トリクロロ
エタン、塩化メチレン、ジオキサンなどがあり樹脂組成
物を均一に溶解する溶媒であれば限定することなく使用
できる。調整したワニスにラジカル重合開始剤を添加し
て含浸用ワニスとする。Examples of the solvent include N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, trichloroethane, methylene chloride, and dioxane, and any solvent that can uniformly dissolve the resin composition can be used without limitation. A radical polymerization initiator is added to the prepared varnish to obtain a varnish for impregnation.
ラジカル重合開始剤の典型的な例はベンゾイルパーオキ
サイド、ジクミルパーオキサイド、メチルエチルケトン
パーオキシド、ｔ−プチルパーオキシラウエート、ジ−
ｔ−ブチルパーオキシフタレート、ジベンジルオキシド
、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキサン。Typical examples of radical polymerization initiators are benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylauate, di-
t-Butylperoxyphthalate, dibenzyl oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
ｔ−ブチルクミルパーオキシド、ｔ−ブチルハイドロパ
ーオキシド、ジ−ｔ−ブチルパーオキシド。t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide.
２．５−ジメチル−２，５−ジー（ｔ−ブチルパーオキ
シ）ヘキシン（３）、ジイソプロピルベンゼンハイドロ
パーオキシド、ｐ−メンタンハイドロパーオキシド、ビ
ナンハイドロオキシド、２゜５−ジメチルヘキサン−２
，５−シバイドロバ−オキシド、クメンハイドロパーオ
キシドなどがある。これらは樹脂組成物１００重量部に
対して好ましくは０．１〜１０重量部添加する。2.5-dimethyl-2,5-di(t-butylperoxy)hexyne (3), diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, vinylane hydroxide, 2゜5-dimethylhexane-2
, 5-sibide lobar oxide, cumene hydroperoxide and the like. These are preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the resin composition.
次に得られた含浸用ワニスをシート状基材に含浸塗工し
、室温〜１７０℃で乾燥し、粘着性のないプリプレグを
得る。この時の乾燥温度の設定は用いた溶媒および開始
剤等によって決まる。最後に得られたプリプレグを必要
枚数重ね、１００〜２５０℃で１〜１ｏＯｋｇｆ／ｄの
圧力下で加熱硬化反応を行い、積層板を得る。Next, the obtained impregnating varnish is impregnated and coated on a sheet-like base material and dried at room temperature to 170°C to obtain a non-tacky prepreg. The setting of the drying temperature at this time is determined by the solvent and initiator used. Finally, the required number of prepregs obtained are stacked, and a heat curing reaction is performed at 100 to 250°C under a pressure of 1 to 10 kgf/d to obtain a laminate.
シート状基材は、一般に、積層材料に使用されているも
のはほとんどすべて使用できる。無機繊維は、Ｓ ｉ
Ｏｘ 、 Ａ Ｑ ｚｏａ等を成分とするＥガラス、Ｃ
ガラス、Ａガラス、Ｓガラス、Ｄガラス。As the sheet-like base material, almost all those generally used for laminated materials can be used. The inorganic fiber is Si
E glass, C whose components are Ox, AQ zoa, etc.
Glass, A glass, S glass, D glass.
ＹＭ−３１−Ａガラス、および石英を使用したＱガラス
等の各種ガラス繊維がある。また、有機繊維は、芳香族
ポリアミドイミド骨格をもつ高分子化合物を成分とする
アラミド繊維等がある。There are various glass fibers such as YM-31-A glass and Q glass using quartz. Furthermore, examples of organic fibers include aramid fibers containing a polymer compound having an aromatic polyamide-imide skeleton.
以下、本発明の一実施例を挙げて詳細に説明する。 Hereinafter, one embodiment of the present invention will be described in detail.
〈実施例１〉
テトラブロモビスフェノールＡ／エチレンオキサイド反
応物のジメタクリレート（第−工業製薬製）と１，２−
ポリブタジェン（数平均分子量約１３．０００）をトル
エンに溶解させ、重合体配合比５：５（重量比）、固型
分量４０％のワニスを得た。<Example 1> Tetrabromobisphenol A/ethylene oxide reactant dimethacrylate (manufactured by Dai-Kogyo Seiyaku) and 1,2-
Polybutadiene (number average molecular weight about 13.000) was dissolved in toluene to obtain a varnish with a polymer blending ratio of 5:5 (weight ratio) and a solid content of 40%.
さらにラジカル重合剤として２，５−ジメチル２゜５ジ
（ｔ−ブチルパーオキシ）ヘキシン３を該ワニス１００
重量部に対して２重量部添加したのち、このワニスをガ
ラスクロス布（日東紡製Ｅガラス。Furthermore, 2,5-dimethyl 2.5 di(t-butylperoxy)hexyne 3 was added to the varnish 100 as a radical polymerization agent.
After adding 2 parts by weight to 2 parts by weight, this varnish was applied to a glass cloth cloth (E glass manufactured by Nittobo Co., Ltd.).
厚さ０．１ｍ）に含浸塗工し、１１０℃、十分量恒温空
気中で乾燥してタックフリーのプリプレグを得た。次に
、このプリプレグを十枚重ね、圧力３０ ｋｇ ｆ ／
ｊ、温度１３０℃で三十分間加熱し、さらに、２２０”
Ｃに昇温させて一時間接着硬化反応をプレス中で行い積
層板を得た。The prepreg was impregnated to a thickness of 0.1 m) and dried at 110° C. in a sufficient amount of constant temperature air to obtain a tack-free prepreg. Next, stack ten sheets of this prepreg and apply a pressure of 30 kgf/
j, heated at a temperature of 130℃ for 30 minutes, and further heated to 220"
The adhesive curing reaction was carried out in a press for one hour by raising the temperature to C. to obtain a laminate.
〈実施例２〉
１．２−ポリブタジェン中、環状化１，２−ポリブタジ
ェンを２０重量％用いた他は、実施例１と同様にして積
層板を得たる。<Example 2> A laminate was obtained in the same manner as in Example 1, except that 20% by weight of cyclized 1,2-polybutadiene was used in 1,2-polybutadiene.
く比較例〉
１．２−ポリブタジェンのみを用いて、実施例１と同様
な方法で積層板を得た。Comparative Example> 1. A laminate was obtained in the same manner as in Example 1 using only 2-polybutadiene.
実施例および比較例による積層板の主な特性を表に示す
。The main properties of the laminates according to Examples and Comparative Examples are shown in the table.
本発明によれば、慣用の装置と工程をそのまま適用して
、公知の基材からタックフリーのプリプレグを容易に製
作し、さらに、従来品より難燃性。According to the present invention, a tack-free prepreg can be easily produced from a known base material by applying conventional equipment and processes as is, and is more flame retardant than conventional products.
Claims (1)
、化学式、表等があります▼ ビスフェノールＡ／エチレンオキサイド反応物のジメタ
クリレートと（ｂ）１，２−ポリブタジエンまたはその
誘導体とを必須成分とし、（ａ）と（ｂ）の配合比が８
０：２０〜２０：８０であることを特徴とする難燃性樹
脂組成物。 ２、合成樹脂を基材に含浸、乾燥してなるプリプレグが
積層接着された積層板において、 前記合成樹脂が（ａ）テトラブロモビスフェノールＡ／
エチレンオキサイド反応物のジメタクリレートと（ｂ）
１，２−ポリブタジエンまたはその誘導体とを必須成分
としてなる難燃性樹脂組成物であることを特徴とする積
層板。[Scope of Claims] 1. (a) Tetrabromo represented by the following chemical formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Bisphenol A/ethylene oxide reactant dimethacrylate and (b) 1,2-polybutadiene or its derivative as an essential component, and the blending ratio of (a) and (b) is 8.
A flame retardant resin composition characterized in that the ratio is 0:20 to 20:80. 2. In a laminate in which prepregs formed by impregnating and drying a synthetic resin into a base material are laminated and bonded, the synthetic resin is (a) tetrabromobisphenol A/
ethylene oxide reactant dimethacrylate and (b)
1. A laminate comprising a flame-retardant resin composition containing 1,2-polybutadiene or a derivative thereof as an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21164786A JPS6368617A (en) | 1986-09-10 | 1986-09-10 | Flame-retarding resin composition and laminate prepared therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21164786A JPS6368617A (en) | 1986-09-10 | 1986-09-10 | Flame-retarding resin composition and laminate prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6368617A true JPS6368617A (en) | 1988-03-28 |
Family
ID=16609249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21164786A Pending JPS6368617A (en) | 1986-09-10 | 1986-09-10 | Flame-retarding resin composition and laminate prepared therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6368617A (en) |
-
1986
- 1986-09-10 JP JP21164786A patent/JPS6368617A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0234450B1 (en) | Thermosetting resin and prepreg and laminate using the same | |
| US4784917A (en) | Thermosetting resin composition and laminate and process for the production thereof | |
| CN107227015B (en) | Low dielectric material | |
| JPH01121356A (en) | Thermosetting resin composition and prepreg and laminated board produced by using same | |
| KR0155542B1 (en) | Thermosetting resin composition printed circuit board using the resin composition nd process for producing printed circuit board | |
| JPS58122927A (en) | Production of prepreg | |
| JPH0579686B2 (en) | ||
| JPS62161846A (en) | Thermosetting resin composition, laminate using same and production thereof | |
| JPH04258658A (en) | Flame-retardant thermosetting resin composition | |
| JPS6356548A (en) | Thermosetting resin composition, laminated sheet produced by using same and production thereof | |
| JPS6368617A (en) | Flame-retarding resin composition and laminate prepared therefrom | |
| JPS62192406A (en) | Flame-retarding resin composition and prepreg and laminate using same | |
| JPS63117053A (en) | Thermosetting resin composition and laminated sheet | |
| US5212244A (en) | Thermosetting resin composition, and prepreg and laminated sheet which use the same | |
| JPS6128545A (en) | Resin composition, laminate, and their preparation | |
| JPH0632875A (en) | New curable polyphenylene ether-epoxy resin composition | |
| JP2866661B2 (en) | Thermosetting resin composition, prepreg and laminate using the same | |
| JPH02167329A (en) | Thermosetting resin composition, printed-circuit board using same resin composition and production thereof | |
| JP2533747B2 (en) | Laminated board and manufacturing method thereof | |
| JP2570138B2 (en) | Laminated board using flame-retardant resin composition | |
| JPS6372720A (en) | Flame-retarding resin composition and laminate prepared by using same | |
| JPH01145A (en) | Thermosetting resin compositions, prepregs and laminates | |
| JPH07247416A (en) | Curable polyphenylene ether resin composition having flame retardancy | |
| JPS62161847A (en) | Thermosetting resin composition, laminate using same and production thereof | |
| JPH03166255A (en) | Flame retardant polyphenylene oxide-based resin composition and metal-clad laminated board thereof |