JPH01287120A - Resin composition for electrical laminate - Google Patents
Resin composition for electrical laminateInfo
- Publication number
- JPH01287120A JPH01287120A JP11652188A JP11652188A JPH01287120A JP H01287120 A JPH01287120 A JP H01287120A JP 11652188 A JP11652188 A JP 11652188A JP 11652188 A JP11652188 A JP 11652188A JP H01287120 A JPH01287120 A JP H01287120A
- Authority
- JP
- Japan
- Prior art keywords
- styrene monomer
- meth
- weight
- side chain
- resin
- 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 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- -1 methacryloyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- 238000013329 compounding Methods 0.000 abstract 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 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 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 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 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 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
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101000578774 Homo sapiens MAP kinase-activated protein kinase 5 Proteins 0.000 description 1
- 102100028396 MAP kinase-activated protein kinase 5 Human genes 0.000 description 1
- 239000002202 Polyethylene glycol Substances 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
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は電気機器、電子機器、通信器等に使用される電
気用積層板用樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition for electrical laminates used in electrical equipment, electronic equipment, communication devices, and the like.
［従来技術とその問題点］
金属箔張り電気用積層板に代表される電気用積層板に用
いられる樹脂組成物としては従来フェノール樹脂系、エ
ポキシ樹脂系、不飽和ポリエステル樹脂系のものが代表
的なものであり、各種の基材と複合化して用いられてい
る。[Prior art and its problems] Typical resin compositions used in electrical laminates, such as metal foil-clad electrical laminates, are conventionally phenol resin-based, epoxy resin-based, and unsaturated polyester resin-based. It is used in combination with various base materials.
上記樹脂系について例えばフェノール樹脂系は成型に要
する時間が長いこと、成型圧力か高いという問題点を有
している。又、エポキシ樹脂系は成形時に溶剤を除去す
る必要性がある他比較的高価であるという問題点を有し
ている。Regarding the above-mentioned resin systems, for example, phenol resin systems have problems in that molding takes a long time and molding pressure is high. In addition, epoxy resin systems have problems in that they require removal of solvent during molding and are relatively expensive.
不飽和ポリエステル樹脂系は硬化時の発熱が速いため、
硬化収縮による積層板のそりの発生や、積層板表面での
凹凸の発生が起き易いといった問題点がある。Unsaturated polyester resin systems generate heat quickly during curing, so
There are problems such as warping of the laminate due to curing shrinkage and unevenness on the surface of the laminate.
又、難燃性は不充分でこれを与えるための方法には共通
して技術上未解決の点かあり、又、コスト上の問題があ
る。In addition, the flame retardance is insufficient, and the methods for providing it have unresolved technical issues and cost problems.
［発明か解決しようとする課題」
本発明は、電気特性及び機械的諸物性の均衡した電気用
積層板の製造に利用しうる成型操作が容易で、安価な新
規難燃性樹脂組成物の提供を目的とする。[Problem to be solved by the invention] The present invention provides a novel flame-retardant resin composition that can be easily molded and is inexpensive and can be used to manufacture electrical laminates with balanced electrical properties and mechanical properties. With the goal.
［課題を解決するための手段］
本発明者等はこの課題を解決するため鋭意研究をした結
果、主鎖はスチレンモノマー単位と無水マレイン酸残基
を含む共重合体であり、側鎖は、前記無水マレイン酸残
基と１級水酸基を有する（メタ）アクリル酸エステルの
当該水酸基がエステル結合してなる側鎖二重結合型樹脂
のスチレンモノマー溶液が主鎖２０〜６０重量％、側鎖
１０重量％以上、スチレンモノマー２０重量％以上から
構成されてなり、該スチレンモノマー溶液１００重量部
にエポキシ樹脂５〜５０重量部、−数式 〔Ｉ〕〔但し
、Ｒ１は水素、アクリロイル基、又はメタアクリロイル
基、Ｒ２は水素又はメチル基〕にて示される臭素含有（
メタ）アクリレート１０〜５０重量部及びラジカル硬化
触媒を加えてなる電気用積層板用樹脂組成物が課題解決
することを見出した。即ち、本発明の要旨は上記組成物
にある。[Means for Solving the Problem] As a result of intensive research to solve this problem, the present inventors found that the main chain is a copolymer containing a styrene monomer unit and a maleic anhydride residue, and the side chain is The styrene monomer solution of the side chain double bond type resin in which the maleic anhydride residue and the hydroxyl group of the (meth)acrylic ester having a primary hydroxyl group are ester bonded has a main chain of 20 to 60% by weight and a side chain of 10% by weight. 5 to 50 parts by weight of epoxy resin to 100 parts by weight of the styrene monomer solution, formula [I] [where R1 is hydrogen, acryloyl group, or methacryloyl group] group, R2 is hydrogen or methyl group]
It has been found that a resin composition for electrical laminates containing 10 to 50 parts by weight of meth)acrylate and a radical curing catalyst can solve the problem. That is, the gist of the present invention lies in the above composition.
以下、本発明の内容を詳説する。Hereinafter, the content of the present invention will be explained in detail.
本発明に係る側鎖二重結合型樹脂は、主鎖ポリマーと末
端に炭素−炭素二重結合を有する側鎖とからなるもので
あり、主鎖はスチレンモノマー単位と無水マレイン酸残
基からなる共重合体の形を持ち、無水マレイン酸残基は
該共重合体に側鎖を形成するための官能基を提供するも
のであり、エステル結合で側鎖が形成されている。The side chain double bond type resin according to the present invention consists of a main chain polymer and a side chain having a carbon-carbon double bond at the end, and the main chain consists of a styrene monomer unit and a maleic anhydride residue. It has the form of a copolymer, and the maleic anhydride residue provides a functional group for forming a side chain in the copolymer, and the side chain is formed by an ester bond.
次に本発明にいう側鎖二重結合型樹脂の製造法の−例に
ついて説明する。Next, an example of the method for producing the side chain double bond type resin according to the present invention will be explained.
スチレンと無水マレイン酸との共重合ポリマーとしては
、−数式［ＩＩ）に示す共重合組成及び分子の大きさが
好ましい。As the copolymer of styrene and maleic anhydride, the copolymer composition and molecular size shown in formula [II] are preferred.
無水マレイン酸とスチレンの共重合ポリマーは重合条件
下にあるスチレンに対し無水マレイン酸を加えつつ共重
合を進める方法で作ることが最も容易であり、無水マレ
イン酸の添加を止め共重合液中から無水マレイン酸が殆
ど検出されなくなった時点で重合を停止すると容易にス
チレンモノマー溶液として得ることができる。メルカプ
タン類あるいはその他の連鎖移動剤の共存下に共重合を
行なえば分子量を調節することができる。The easiest way to make a copolymer of maleic anhydride and styrene is to proceed with copolymerization while adding maleic anhydride to styrene under polymerization conditions. If the polymerization is stopped when almost no maleic anhydride is detected, a styrene monomer solution can be easily obtained. The molecular weight can be controlled by copolymerizing in the presence of mercaptans or other chain transfer agents.
側鎖を形成するものの一例としては一般式 ＣＩ［）Ｃ
Ｈ２＝Ｃ−Ｗｍ〇−Ｘ−ＣＨ２０Ｈ（ＩＩＤで示す１級
水酸基を有する（メタ）アクリル酸のエステル化物を挙
げることができる。この分子量は大きくても１０００を
越えないことか好ましい。An example of what forms a side chain is the general formula CI[)C
Examples include esterified products of (meth)acrylic acid having a primary hydroxyl group represented by H2=C-Wm〇-X-CH20H (IID).It is preferable that the molecular weight thereof does not exceed 1000 at most.
−数式〔■〕で示される（メタ）アクリル酸エステルの
水酸基は分子中に１個存在すべきで、−数式ＣＩＩ）で
示す共重合体中の無水マレイン酸残基とエステル化反応
せしめる際にゲル化させないための条件である。又エス
テル化反応のし易さから１級水酸基であることが必要で
ある。- There should be one hydroxyl group in the (meth)acrylic acid ester represented by the formula [■] in the molecule, and - when carrying out an esterification reaction with the maleic anhydride residue in the copolymer represented by the formula CII), This is a condition to prevent gelation. In addition, it is necessary that it be a primary hydroxyl group in order to facilitate the esterification reaction.
上記に該当する（メタ）アクリル酸エステルとしては、
エチレングリコールモノ （メタ）アクリレート、ジエ
チレングリコール七ノ（メタ）アクリレートのようなポ
リエチレングリコールモノ（メタ）アクリレート、■、
４ブタンジオールモノ（メタ）アクリレート、■、６ヘ
キサンジオールモノ（メタ）アクリレート、ネオペンチ
ルグリコールモノ （メタ）アクリレート、トリメチロ
ールプロパンジ（メタ）アクリレートのような多価アル
レート
コールのモノヒドロキシ（メタ）アクリル、及びモノヒ
ドロキシ（メタ）アクリル酸エステルとε−カプロラク
トンの附加生成物等が挙げられる。The (meth)acrylic esters applicable to the above are:
Polyethylene glycol mono(meth)acrylate, such as ethylene glycol mono(meth)acrylate, diethylene glycol 7-(meth)acrylate,
Monohydroxy (meth)acrylate of polyhydric alcohols such as 4-butanediol mono(meth)acrylate, ) acrylic, and addition products of monohydroxy (meth)acrylic acid ester and ε-caprolactone.
−数式（ＩＩ）で示されるスチレンと無水マレ″Ｘ４−
レン
イン酸共重合体の薫水土七元±穏溶液に対して、−数式
［ＩＩＩ）で示される１級水酸基を有する（メタ）アク
リル酸エステルを加えると、−数式［ＩＶ）で示すよう
なエステル結合を生成させることができる。-Styrene and anhydrous male represented by formula (II)"X4-
When a (meth)acrylic acid ester having a primary hydroxyl group represented by formula [III] is added to a moderate solution of a renic acid copolymer, an ester as represented by formula [IV] is added. A bond can be created.
０〔■〕
［ＩＩ〕に示すスチレンと無水マレイン酸の共重合体の
スチレン溶液に対して、（ｍ）に示す１級水酸基を有す
る（メタ）アクリル酸エステルを加えた混合液に更にエ
ステル化反応を促進するための触媒として、３級アミン
、ピリジン、有機スズ化合物（例えばジブチルスズオキ
サイド）、有機チタン化合物（例えばチタン酸エステル
）、トリフェニルフォスフイン、第４級アンモニウム塩
等を上記混合液の１／１０００〜ｌ／ １００重量の範
囲で加えることか好ましく、温度は通常室温から１００
℃の範囲である。0 [■] To the styrene solution of the copolymer of styrene and maleic anhydride shown in [II], a (meth)acrylic acid ester having a primary hydroxyl group shown in (m) is added, and the mixture is further esterified. As a catalyst for promoting the reaction, a tertiary amine, pyridine, an organic tin compound (e.g. dibutyltin oxide), an organic titanium compound (e.g. titanate ester), triphenylphosphine, a quaternary ammonium salt, etc. are added to the above mixture. It is preferable to add in the range of 1/1000 to 1/100 liters, and the temperature is usually room temperature to 100 liters.
℃ range.
また１級水酸基を有する（メタ）アクリル酸エステルは
スチレンと無水マレイン酸の共重合体に含まれる無水マ
レイン酸残基１当量に対し１〜３当量とすることが好ま
しい。The (meth)acrylic acid ester having a primary hydroxyl group is preferably used in an amount of 1 to 3 equivalents per equivalent of maleic anhydride residue contained in the copolymer of styrene and maleic anhydride.
本発明における側鎖二重結合型樹脂のスチレンモノマー
溶液においては主鎖が２０〜６０重量％、側鎖が１０重
量％以上、スチレンモノマーが２０重量％以上である必
要かある。In the styrene monomer solution of the side chain double bond type resin in the present invention, the main chain must be 20 to 60% by weight, the side chain must be 10% by weight or more, and the styrene monomer must be 20% by weight or more.
主鎖が２０重量％未満の場合は樹脂組成物の粘度が低く
、良好な成形品が得られない。又６０重量％を越える場
合は樹脂組成物の粘度が高くなり基材への含浸性が悪く
なる。側鎖が１０重量％未満の場合は成形品の機械的強
度が低く耐溶剤性が悪くなる。スチレンモノマーが２０
重置火未満の場合樹脂組成物の粘度が高くなり、基材へ
の含浸性が悪くなるだけでなくコスト高となる欠点があ
る。If the main chain content is less than 20% by weight, the viscosity of the resin composition will be low and a good molded product will not be obtained. If the amount exceeds 60% by weight, the viscosity of the resin composition increases and impregnation into the substrate becomes poor. If the side chain content is less than 10% by weight, the mechanical strength of the molded article will be low and the solvent resistance will be poor. Styrene monomer is 20
If the temperature is less than the superposition temperature, the viscosity of the resin composition becomes high, which not only impairs the impregnation of the base material but also increases the cost.
本発明において用いられるエポキシ樹脂としては、性能
上代表的にはビスフェノールＡ型エポキシ樹脂が用いら
れるがこの他レゾルシン型、ビスフェノールＦ型、テト
ラヒドロキシフェニルエタン型、ノボラック型、グリセ
リントリエーテル型、脂環型等のエポキシ樹脂やエポキ
シ化大豆油が挙げられる。As the epoxy resin used in the present invention, bisphenol A type epoxy resin is typically used in terms of performance, but other types include resorcin type, bisphenol F type, tetrahydroxyphenylethane type, novolac type, glycerin triether type, and alicyclic type. Examples include epoxy resins such as molds and epoxidized soybean oil.
エポキシ樹脂は側鎖二重結合型樹脂に存在するカルボキ
シル基に対し、当量附近とすればよい。The epoxy resin may have an equivalent weight to the carboxyl group present in the side chain double bond type resin.
本発明において用いられる一般式［Ｉ］で示される臭素
含有（メタ）アクリレートは側鎖にラジカル反応で結合
し、難燃化に寄与するものである。The bromine-containing (meth)acrylate represented by the general formula [I] used in the present invention is bonded to the side chain by a radical reaction and contributes to flame retardation.
前記のような側鎖二重結合型樹脂のスチレンモノマー溶
液に対して、エポキシ樹脂とジブロモネ＝ ９−
オペンチルグリコールのモノ又はジ（メタ）アクリレー
トを加えて、ラジカル重合触媒を加えて、硬化を開始す
るとラジカル硬化か起こり、特に加熱硬化においては、
エポキシ樹脂はスチレンと無水マレイン酸共重合体に生
じたカルボキシル基との附加反応による架橋反応がラジ
カル重合と同時併発的に起こる。Epoxy resin and mono- or di(meth)acrylate of dibromone=9-opentyl glycol are added to the styrene monomer solution of the side chain double bond type resin as described above, and a radical polymerization catalyst is added to cure the resin. Once started, radical curing occurs, especially in heat curing.
In epoxy resins, a crosslinking reaction occurs simultaneously with radical polymerization due to an addition reaction between styrene and carboxyl groups generated in a maleic anhydride copolymer.
ラジカル硬化触媒としては、ポリエステル樹脂やビニル
エステル樹脂に用いて有効な有機過酸化物触媒を、必要
なら硬化促進剤と組合せて用いればよい。硬化時の温度
は常温以上２００℃未満がよい。As the radical curing catalyst, an organic peroxide catalyst effective for use with polyester resins and vinyl ester resins may be used in combination with a curing accelerator, if necessary. The temperature during curing is preferably at least room temperature and below 200°C.
ジブロモネオペンチルグリコールのエステルとして、ア
クリル酸又はメタアクリル酸によるモノエステルとジエ
ステルが共に良好であり、これらの混合物も同様に用い
られる。As esters of dibromoneopentyl glycol, monoesters and diesters of acrylic acid or methacrylic acid are both suitable, and mixtures thereof can also be used.
以上のような組成物を用いることにより、更に共重合体
に生成するカルボキシル基にエポキシ樹脂を反応結合せ
しめる反応をジブロモネオペンチルグリコールのモノ又
はジ（メタ）アクリレートを加えたのち、二重結合の重
合による硬化と同時併発的に行ないうる。By using the above-mentioned composition, the reaction of bonding the epoxy resin to the carboxyl groups formed in the copolymer can be carried out by adding mono- or di(meth)acrylate of dibromoneopentyl glycol, and then removing the double bonds. It can be carried out simultaneously with curing by polymerization.
この反応を前記組成物を電気用積層板の基材に含浸せし
めて後に起こさしめれば、優れた電気用積層板を得る。If this reaction occurs after the composition is impregnated into the substrate of the electrical laminate, a superior electrical laminate is obtained.
即ち本発明によれば、難燃性と同時に成型硬化ひずみの
少い積層板を作りうることがわかる。That is, according to the present invention, it is possible to produce a laminate that is not only flame retardant but also exhibits less molding and curing strain.
以下実施例にて本発明を説明する。The present invention will be explained below with reference to Examples.
実施例
坪量１３５ｇ／ゴのクラフト紙（２５ｃｍ Ｘ ２５ｃ
ｍ ）を「ニカレヂンＳ−３０５Ｊ（商品名９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°Ｃて３０分乾燥した。Example Kraft paper (25cm x 25c) with a basis weight of 135g/g
m) was soaked in an aqueous solution of Nikaledin S-305J (trade name 9 manufactured by Nippon Carbide Co., Ltd., methylolmelamine), squeezed with a roller, and dried at 120°C for 30 minutes.
得られた紙基材中に１１，７重量％−シ占長展着した。11.7% by weight was spread on the obtained paper base material.
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。樹脂液を含ませた紙
を６枚とフェノール系接着剤使用の市販接着剤付銅箔ｒ
ＭＫ−５［ｉＪ （商品名、三井金属鉱業社製）を１
枚重ね合わせて、２枚の鏡面板にはさみ、これを１２０
℃に予熱しであるプレスに入れ、０ 、５ｋｇ ／ ｅ
Ｊの圧力で１０分間保持した。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. 6 sheets of paper soaked in resin liquid and copper foil with commercially available adhesive using phenolic adhesive
MK-5 [iJ (product name, manufactured by Mitsui Kinzoku Mining Co., Ltd.) 1
Layer them together, sandwich them between two mirrored plates, and make a 120mm
Place it in a press that is preheated to 0.5kg/e
The pressure was maintained at J for 10 minutes.
鏡面板と一緒の状態で積層板をプレスから取出し、１２
０°Ｃの空気オーブンに入れ、５時間加熱をつづけた。Take out the laminate together with the mirror plate from the press and press 12.
The mixture was placed in an air oven at 0°C and heating continued for 5 hours.
鏡面板と一緒に積層板をオーブンから取出し、放冷した
のち積層板を取外した。The laminate was taken out of the oven together with the mirrored plate, and after being left to cool, the laminate was removed.
得られた積層板は、１，５７〜１．６３ｍｍ厚であった
。The resulting laminate had a thickness of 1.57 to 1.63 mm.
積層板の特性値を表２に示す。Table 2 shows the characteristic values of the laminate.
比較例
実施例と同じ方法にて表１に示す含浸用樹脂配合液を用
いて積層板を作製した。得られた積層板の性能を表２に
示した。Comparative Example A laminate was produced using the impregnating resin mixture shown in Table 1 in the same manner as in the Example. Table 2 shows the performance of the obtained laminate.
（以下余白）
［効 果コ
以上の説明かられかるごとく本願発明の構成をとること
によりフェノール樹脂等の欠点を有しないばかりか、ラ
ジカル硬化性の難燃性不飽和ポリエステル樹脂に優る電
気用積層板用樹脂組成物の提供に成功したのである。(Left below) [Effects] As can be seen from the above explanation, the structure of the present invention not only does not have the disadvantages of phenolic resins, but also is superior to radical-curable flame-retardant unsaturated polyester resins. They succeeded in providing a resin composition for plates.
特許出願人 昭和高分子株式会社 昭和電工株式会社Patent applicant: Showa Kobunshi Co., Ltd. Showa Denko Co., Ltd.
Claims (1)
む共重合体であり、側鎖は前記無水マレイン酸残基と１
級水酸基を有する（メタ）アクリル酸エステルの当該水
酸基がエステル結合してなる側鎖二重結合型樹脂のスチ
レンモノマー溶液が主鎖２０〜６０重量％、側鎖１０重
量％以上、スチレンモノマー２０重量％以上から構成さ
れてなり、該スチレンモノマー溶液１００重量部にエポ
キシ樹脂５〜５０重量部、 一般式 ▲数式、化学式、表等があります▼ 〔但し、Ｒ＿１は水素、アクリロイル基、又はメタアク
リロイル基、Ｒ＿２は水素又はメチル基〕にて示される
臭素含有（メタ）アクリレート１０〜５０重量部及び、
ラジカル硬化触媒を加えてなる電気用積層板用樹脂組成
物。[Claims] The main chain is a copolymer containing a styrene monomer unit and a maleic anhydride residue, and the side chain is a copolymer containing a styrene monomer unit and a maleic anhydride residue.
A styrene monomer solution of a side chain double bond type resin formed by ester bonding of the hydroxyl group of a (meth)acrylic acid ester having a class hydroxyl group has a main chain of 20 to 60% by weight, a side chain of 10% by weight or more, and a styrene monomer of 20% by weight. % or more, 100 parts by weight of the styrene monomer solution, 5 to 50 parts by weight of epoxy resin, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R_1 is hydrogen, acryloyl group, or methacryloyl group , R_2 is hydrogen or methyl group] 10 to 50 parts by weight of bromine-containing (meth)acrylate; and
A resin composition for electrical laminates containing a radical curing catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11652188A JPH01287120A (en) | 1988-05-13 | 1988-05-13 | Resin composition for electrical laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11652188A JPH01287120A (en) | 1988-05-13 | 1988-05-13 | Resin composition for electrical laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01287120A true JPH01287120A (en) | 1989-11-17 |
Family
ID=14689195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11652188A Pending JPH01287120A (en) | 1988-05-13 | 1988-05-13 | Resin composition for electrical laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01287120A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242506B1 (en) | 1998-07-22 | 2001-06-05 | Mingxin Fan | Flame retardant additive for radiation curable acrylic compositions |
-
1988
- 1988-05-13 JP JP11652188A patent/JPH01287120A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242506B1 (en) | 1998-07-22 | 2001-06-05 | Mingxin Fan | Flame retardant additive for radiation curable acrylic compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4954304A (en) | Process for producing prepreg and laminated sheet | |
| JPS61243844A (en) | Thermosetting resin composition, laminated sheet and production thereof | |
| JPH11343476A (en) | Adhesive composition and copper-clad laminate | |
| JPH01287120A (en) | Resin composition for electrical laminate | |
| JPS6356548A (en) | Thermosetting resin composition, laminated sheet produced by using same and production thereof | |
| JPH01287121A (en) | Resin composition for electrical laminate | |
| JP2625646B2 (en) | Adhesive composition for flexible printed circuit boards | |
| JPH01287118A (en) | Resin composition for electrical laminate | |
| JPS63117053A (en) | Thermosetting resin composition and laminated sheet | |
| JPH0219995B2 (en) | ||
| JPH01215815A (en) | Thermosetting resin composition and metal-clad laminate thereof | |
| JPH0288626A (en) | Epoxy resin composition, and production of prepreg and laminate therefrom | |
| EP0336266B1 (en) | Electrical laminate produced by using special thermosetting resin compostions | |
| JP2621671B2 (en) | Production method of radiation-curable copper foil with paint | |
| JPS6092844A (en) | Laminated board for electricity and metallic foil lined laminated board | |
| JPH02212506A (en) | Impregnating resin composition, production of prepreg and laminate | |
| JPH0534375B2 (en) | ||
| JPH03131616A (en) | Thermosetting resin composition and laminated board for electrical use | |
| JPH1036463A (en) | Resin composition for laminate and production of metal-foil-clad laminate | |
| JPH04197717A (en) | Manufacture of electric laminated sheet | |
| JPH09207282A (en) | Heat-resistant protective film | |
| JPS63218721A (en) | Resin composition for laminated sheet | |
| JPH01286837A (en) | Metallic foil plated electric laminate | |
| JPS6353027A (en) | Copper-lined laminated board | |
| JPH0454701B2 (en) |