JPH0445530B2 - - Google Patents
Info
- Publication number
- JPH0445530B2 JPH0445530B2 JP60130158A JP13015885A JPH0445530B2 JP H0445530 B2 JPH0445530 B2 JP H0445530B2 JP 60130158 A JP60130158 A JP 60130158A JP 13015885 A JP13015885 A JP 13015885A JP H0445530 B2 JPH0445530 B2 JP H0445530B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin composition
- laminate
- initiator
- 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.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 19
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 8
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010408 film Substances 0.000 description 22
- 239000011888 foil Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 poly(2,6-dimethyl-1,4-phenylene oxide) Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- 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 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
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-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
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- BRHJUILQKFBMTL-UHFFFAOYSA-N [4,4-bis(dimethylamino)cyclohexa-1,5-dien-1-yl]-phenylmethanone Chemical compound C1=CC(N(C)C)(N(C)C)CC=C1C(=O)C1=CC=CC=C1 BRHJUILQKFBMTL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Polymers [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KYZHGEFMXZOSJN-UHFFFAOYSA-N isobutyl benzoate Chemical compound CC(C)COC(=O)C1=CC=CC=C1 KYZHGEFMXZOSJN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002852 poly(2,6-dimethyl-1,4-phenylene oxide) polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
〔技術分野〕
この発明は、ポリフエニレンオキサイド樹脂組
成物を用いる積層板に関する。
〔背景技術〕
衛星通信などに用いられるＸバンド（10GHz）
領域、いわゆる超高周波領域で使用する積層板に
は、優れた高周波特性、殊に誘電特性において優
れていることが要求される。すなわち、広い周波
数範囲、温度範囲および湿度範囲で誘電率および
誘電損失がいずれも一定で、かつ、望ましくは低
いものでなければならない。
従来、このような用途にはポリ４−フツ化エチ
レン、アルミナセラミツク、架橋ポリエチレンな
どが使用されていたが、アルミナセラミツクは加
工性、回路の形成（銅張りの方法）などに難点が
あり、また、ポリ４−フツ化エチレン、架橋ポリ
エチレンは共にガラス転移点が低いため、実用状
態の付近で誘電率、誘電損失が著しく変化すると
いう欠点があり、さらに、その非極性のため、回
路を形成させる金属箔との接着強度が不足すると
いう欠点を有している。
このような事情で、従来、高周波性および耐熱
性が優れた積層板を簡単に得ることができなかつ
た。
〔発明の目的〕
この発明は、このような事情に鑑みてなされた
ものであつて、高周波特性に優れ、かつ、耐熱
性、ピール強度、電気特性が良好な積層板を提供
することを目的としている。
〔発明の開示〕
発明者らは、上記目的を達成するために、種々
工夫した結果、それ自体において高周波特性等の
電気特性に優れるポリフエニレンオキサイドを主
材として用いることとし、その長所を生かした上
で、その耐熱性やピール強度の諸物性を向上させ
るために、ポリフエニレンオキサイドに対しトリ
アリルイソシアヌレートおよび／またはトリアリ
ルシアヌレートを配合することとし、さらに、上
記の物性をより良くし、かつ、成膜性や膜の透明
性等を向上させるために、ブタジエン系の架橋性
ポリマーを配合することとした。
したがつて、この発明は、ポリフエニレンオキ
サイド、トリアリルイソシアヌレートおよび／ま
たはトリアリルシアヌレート、ブタジエン系の架
橋性ポリマー、ならびに、開始剤を含む樹脂組成
物を硬化させて得られる積層板を要旨としてい
る。
以下に、この発明を詳しく説明する。
この発明では、積層板とは、両面または片面に
金属箔が積層、接着されているもの、金属箔が全
くないものを含める。
この発明で用いられるポリフエニレンオキサイ
ド（ポリフエニレンエーテルともいう。以下、
「PPO」と記す）は、たとえば、つぎの一般式、
ここで、Ｒは、水素また炭素数１〜３の炭化水
素基を表し、各Ｒは、同じであつてもよく、異な
つていてもよい。
で表されるものであり、その１例としては、ポリ
（２，６−ジメチル−１，４−フエニレンオキサ
イド）が挙げられる。
PPOは架橋型ではないため、単独では架橋は
起こらない。このため、この発明において、トリ
アリルイソシアヌレート（以下「TAIC」と略
す）および／またはトリアリルシアヌレート（以
下、「TAC」と略す）が、架橋性モノマーとして
用いられている。TAIC，TACはPPOと相容性
が良く、成膜性、架橋性、耐熱性および誘電特性
の面でよいので用いられる。TAICとTACとは
化学構造的には異性体の関係にあり、ほぼ同様の
性質を有するので、同様に、いずれか一方だけ、
または両方ともに使うことができる。
また、積層板の物性をより良くしたり、樹脂組
成物の成膜性などをより良くするなどの目的で、
架橋性ポリマーが用いられる。
樹脂組成物中の各成分の配合割合は、PPO、
TAICおよび／またはTAC、ならびに、架橋性
ポリマーの合計100重量部に対する割合で、PPO
を50重量部以上95重量部未満、TAICおよび／ま
たはTACを５重量部以上50重量部未満、架橋性
ポリマーを残部とするように含んでいるのが好ま
しい。
ここで、用いられる架橋性ポリマーは、ブタジ
エン系のものであつて、ポリブタジエン（たとえ
ば、１，２−ポリブタジエン、１，４−ポリブタ
ジエン、マレイン変性１，２−ポリブタジエン、
アクリル変性１，２−ポリブタジエン、エポキシ
変性１，２−ポリブタジエンなど）、スチレン・
ブタジエンブロツクポリマーなどがあり、それぞ
れ単独でまたは２つ以上混合して用いられるが、
これらに限定されない。
このほか、樹脂組成物には、必要に応じて開始
剤が用いられる。開始剤としては、有効官能基数
が２のジアルキル系過酸化物、たとえば、２，５
−ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキシン−３、２，５−ジメチル−２，５−
ジ（ｔ−ブチルパーオキシ）ヘキサン、α，α′−
ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピ
ル）ベンゼン｛１，４（または１，３）−ビス（ｔ
−ブチルパーオキシイソプロピル）ベンゼンとも
いう｝などや、そのほか、ベンゾイン、ベンジ
ル、アリルジアゾニウムフロロほう酸塩、ベンジ
ルメチルケタール、２，２−ジエトキシアセトフ
エノン、ベンゾイルイソブチルエーテル、ｐ−
tert−ブチルトリクロロアセトフエノン、ベンジ
ル（ｏ−エトキシカルボニル）−α−モノオキシ
ム、ビアセチル、アセトフエノン、ベンゾフエノ
ン、テトラメチルチウラムスルフイド、アゾビス
イソブチロニトリル、ベンゾイルパーオキサイ
ド、１−ヒドロキシシクロヘキシルフエニルエド
ン、２−ヒドロキシ−２−メチル−１−フエニル
−プロパン−１−オン、１−（４−イソプロピル
フエニル）−２−ヒドロキシ−２−メチルプロパ
ン−１−オン、２−クロロチオキサントン、メチ
ルブンゾイルフオーメート、４，４−ビスジメチ
ルアミノベンゾフエノン（ミヒラーケトン）、ベ
ンゾインメチルエーテル、メチル−０−ベンゾイ
ルベンゾエート、α−アシロキシムエステルなど
や、次式、
であらわされる日本油脂(株)製「ビスクミル」など
が用いられる。
開始剤の配合割合は、特に限定されないが、
PPO、ならびに、TAICおよび／またはTACの
合計100重量部に対する割合で、開始剤を0.1〜
5.0重量部含むようにするのが好ましく、架橋性
ポリマーを用いる場合には、PPO、TAICおよ
び／またはTAC、ならびに、架橋性ポリマーの
合計100重量部に対する割合で、開始剤を0.1〜
5.0重量部含むようにするのが好ましい。
以上の原材料より樹脂組成物を得る方法は、通
常、ブレンドまたは溶液混合の方法による。
たとえば、上記原材料を溶媒（溶剤ともいう）
に、樹脂組成物が５〜50重量％の割合となるよう
完全に溶解させ混合させる。
溶媒としては、トリクロロエチレン、トリクロ
ロエタン、クロロホルム、塩化メチレン、四塩化
炭素などのハロゲン化炭化水素、クロロベンゼ
ン、トルエン、キシレンなどの芳香族炭化水素な
どのうちから選んだ単独または混合溶媒があげら
れる。
前記のような樹脂組成物の溶液より、キヤステ
イング法で樹脂組成物のフイルムをつくったり、
樹脂組成物が含浸された樹脂含浸基材をつくった
りする。
キヤステイング法について詳しく述べれば、前
記樹脂組成物の溶液を、鏡面処理した鉄板または
キヤステイング用キヤリアーフイルムなどの上
に、たとえば、５〜700μmの厚みに流延（たま
は、塗布）し、乾燥させて溶媒を除去することに
よりフイルムを得るというものである。乾燥時の
設定温度は、その上限が溶媒の沸点よりも低い
か、または、キヤステイング用キヤリアーフイル
ムの耐熱温度よりも低いこと（キヤステイング用
キヤリアーフイルム上で乾燥を行う場合）が好ま
しく、その下限が乾燥時間や処理性などによつて
決められる。
樹脂含浸基材は、たとえば、前記樹脂組成物の
溶液を、基材に含浸させ乾燥させることにより得
られる。基材としては、ガラスクロス、ガラスマ
ツト、ポリエステルクロス、ポリエステルマツ
ト、アラミド繊維クロス、紙、不織布等が用いら
れる。
前記のフイルムおよび樹脂含浸基材をそれぞれ
単独でまたは両者組み合わせて、所定の設定厚み
となるように所定枚積層成形して積層板が得られ
る。あるいは、フイルム、樹脂含浸基材と金属箔
とを積層成形して両面または片面金属箔張りの積
層板としたり、あらかじめフイルムおよび／また
は樹脂含浸基材を所定枚積層成形しておき、これ
の片面または両面に金属箔を重ね合わせて積層成
形して金属箔張りの積層板とすることができる。
金属箔としては、銅箔、アルミニウム箔等が用
いられる。
このようにして得る積層板の全体厚みは特に限
定されてないが、0.2〜２mm位が良く、0.6〜0.8mm
位が回路設計上より望ましい。
樹脂組成物が開始剤を含んでいて、熱硬化させ
る場合には、積層成形の際の加熱温度、加熱時間
は、使用する開始剤の反応温度等に依存するの
で、開始剤の種類等に応じて選ぶとよい。たとえ
ば、温度150〜300℃、圧力10〜150Kg／cm2、時間
10〜90分間程度である。
積層成形の際の加熱により樹脂が溶融して、フ
イルム同士、樹脂含浸基材同士、フイルムと樹脂
含浸基材、フイルムと金属箔、樹脂含浸基材と金
属箔を互いに接着させ積層板が得られる。この融
着により、強固な接着が得られる。PPOは接着
性に優れるので、金属箔を積層、接着する場合で
も接着剤がなくてもよい。樹脂組成物に開始剤を
配合していれば、加熱および／または紫外線照射
により、ラジカル架橋が生じ、樹脂が硬化する。
この硬化により、より強固な接着が得られ、強固
な積層板が得られる。この後、放射線照射を行え
ば、開始剤を配合していなくても架橋反応が生じ
て樹脂が硬化し、一層強固な接着が得られ、より
強固な積層板が得られる。金属箔が積層されてい
ても放射線照射にはほとんど影響がない。
PPOの優れた熱融着性を生かすために、予め
金属箔をフイルム、樹脂含浸基材に熱融着した
後、このように放射線を照射すれば接着界面も架
橋させることができる。したがつて、フイルムま
たは樹脂含浸基材と金属箔との間で耐熱性の優れ
た接着が実現できるのである。
このようにして得られた積層板は、PPOの特
性が損なわれず、誘電特性が優れ、かつ、耐熱
性、ピール強度、電気特性も良好である。上記の
ような製造操作によれば容易に得ることができ
る。
つぎに、実施例および比較例について説明す
る。
（実施例 １，３）
第１表に示されている配合材料をトリクレン
（東亜合成化学工業(株)製トリクロロエチレン）中
で溶解混合して、樹脂組成物の20重量％溶液とし
た。この溶液を離型フイルム上に厚み500μmに塗
布した後、乾燥して厚み約100μmのキヤステイン
グフイルムを得た。このフイルムを６枚（実施例
５では15枚）重ねて、温度220℃、圧力50Kg／cm2
（実施例５では100Kg／cm2で30分間積層成形し、厚
み0.8mmの積層板を得た。
（実施例 ２）
第１表に示されている配合原材料をトリクレン
（東亜合成化学工業(株)製トリクロロエチレン）中
で溶解混合して、樹脂組成物の15重量％溶液とし
た。この溶液を第１表に示されている基材に含浸
させ、樹脂含浸基材を作製した。銅箔、樹脂含浸
基材数枚、銅箔の順で、これらを重ね、温度220
℃（実施例６は200℃）、圧力50Kg／cm2で30分間
（実施例６は60分間）積層成形し、厚み0.8mmの積
層板を得た。
（比較例１）
第１表に示されている配合で、実施例１と同様
にしてキヤステイングフイルムを得ようとした
が、この樹脂組成物ではイヤステイングフイルム
が得られなかつた。
（比較例 ２，３）
第１表に示されている配合で実施例２と同様に
して厚み0.8mmの積層板を得た。なお、比較例３
は開始剤が配合されてなく、積層成形の加熱のみ
なので硬化はほとんど生じていない。
第１表中、Ａは２，５−ジメチル−２，５（ｔ
−ブチルパーオキシ）ヘキシン−３、Ｂは２，５
−ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキサン、Ｃはα−α′−ビス（ｔ−ブチルパ
ーオキシ−ｍ−イソプロピル）ベンゼン、１，２
−PBは１，２−ポリブタジエンをそれぞれあら
わす。
[Technical Field] This invention relates to a laminate using a polyphenylene oxide resin composition. [Background technology] X band (10GHz) used for satellite communications, etc.
Laminated plates used in the so-called ultra-high frequency range are required to have excellent high frequency properties, particularly excellent dielectric properties. That is, the dielectric constant and dielectric loss must both be constant and preferably low over a wide frequency range, temperature range, and humidity range. Conventionally, poly(4-fluoroethylene), alumina ceramic, cross-linked polyethylene, etc. have been used for such applications, but alumina ceramic has difficulties in processability, circuit formation (copper cladding method), etc. , poly(4-fluorinated ethylene), and cross-linked polyethylene all have low glass transition points, so they have the disadvantage that the dielectric constant and dielectric loss change significantly near practical conditions.Furthermore, their nonpolar nature makes it difficult to form circuits. It has the disadvantage of insufficient adhesive strength with metal foil. Under these circumstances, conventionally it has not been possible to easily obtain a laminate with excellent high frequency properties and heat resistance. [Purpose of the Invention] The present invention was made in view of the above circumstances, and an object of the present invention is to provide a laminate having excellent high frequency characteristics, as well as good heat resistance, peel strength, and electrical properties. There is. [Disclosure of the Invention] In order to achieve the above object, the inventors have made various efforts and decided to use polyphenylene oxide, which itself has excellent electrical properties such as high frequency properties, as the main material, and take advantage of its advantages. In addition, in order to improve various physical properties such as heat resistance and peel strength, we decided to blend triallyl isocyanurate and/or triallyl cyanurate to polyphenylene oxide, and further improved the above physical properties. However, in order to improve film formability, film transparency, etc., we decided to blend a butadiene-based crosslinkable polymer. Therefore, the present invention provides a laminate obtained by curing a resin composition containing polyphenylene oxide, triallyl isocyanurate and/or triallyl cyanurate, a butadiene-based crosslinkable polymer, and an initiator. This is the summary. This invention will be explained in detail below. In this invention, the term laminate includes one in which metal foil is laminated and bonded on both or one side, and one in which there is no metal foil at all. Polyphenylene oxide (also referred to as polyphenylene ether) used in this invention.Hereinafter,
(denoted as "PPO") is, for example, the following general formula, Here, R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and each R may be the same or different. An example thereof is poly(2,6-dimethyl-1,4-phenylene oxide). Since PPO is not a crosslinking type, crosslinking does not occur alone. Therefore, in this invention, triallyl isocyanurate (hereinafter abbreviated as "TAIC") and/or triallyl cyanurate (hereinafter abbreviated as "TAC") is used as a crosslinking monomer. TAIC and TAC are used because they are compatible with PPO and have good film forming properties, crosslinking properties, heat resistance, and dielectric properties. TAIC and TAC are chemically structurally isomers and have almost the same properties, so similarly, only one of them,
Or you can use both. In addition, for the purpose of improving the physical properties of the laminate and the film forming properties of the resin composition,
A crosslinkable polymer is used. The blending ratio of each component in the resin composition is PPO,
TAIC and/or TAC and PPO in proportion to 100 parts by weight of crosslinkable polymer
It is preferable that the composition contains 50 parts by weight or more and less than 95 parts by weight of TAIC and/or TAC, 5 parts by weight or more and less than 50 parts by weight of TAIC and/or TAC, and the balance being a crosslinkable polymer. The crosslinkable polymer used here is a butadiene-based polymer, such as polybutadiene (for example, 1,2-polybutadiene, 1,4-polybutadiene, malein-modified 1,2-polybutadiene,
(acrylic modified 1,2-polybutadiene, epoxy modified 1,2-polybutadiene, etc.), styrene,
There are butadiene block polymers, etc., which can be used alone or in combination of two or more.
Not limited to these. In addition, an initiator may be used in the resin composition as necessary. As an initiator, a dialkyl peroxide having an effective functional group number of 2, for example, 2,5
-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-
Di(t-butylperoxy)hexane, α, α′-
Bis(t-butylperoxy-m-isopropyl)benzene {1,4(or 1,3)-bis(t
-butylperoxyisopropyl)benzene}, and in addition, benzoin, benzyl, allyldiazonium fluoroborate, benzyl methyl ketal, 2,2-diethoxyacetophenone, benzoyl isobutyl ether, p-
tert-butyltrichloroacetophenone, benzyl (o-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, benzophenone, tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, 1-hydroxycyclohexyl phenyl Edon, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, methylbun Zoylformate, 4,4-bisdimethylaminobenzophenone (Michler's ketone), benzoin methyl ether, methyl-0-benzoylbenzoate, α-acyloxime ester, etc., and the following formula, ``Biscumil'' manufactured by Nippon Oil & Fats Co., Ltd., which is expressed as ``Biscumyl'', is used. The blending ratio of the initiator is not particularly limited, but
The initiator is added in a proportion of 0.1 to 100 parts by weight of PPO and TAIC and/or TAC.
It is preferable to contain 5.0 parts by weight of the initiator, and when using a crosslinkable polymer, the initiator is contained in an amount of 0.1 to 100 parts by weight based on the total of 100 parts by weight of PPO, TAIC and/or TAC, and the crosslinkable polymer.
It is preferable to contain 5.0 parts by weight. A method for obtaining a resin composition from the above raw materials is usually a blending or solution mixing method. For example, the above raw materials are called solvents (also called solvents).
Then, the resin composition is completely dissolved and mixed in a proportion of 5 to 50% by weight. Examples of the solvent include single or mixed solvents selected from halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, methylene chloride, and carbon tetrachloride, and aromatic hydrocarbons such as chlorobenzene, toluene, and xylene. From a solution of the resin composition as described above, a film of the resin composition is made by a casting method,
A resin-impregnated base material impregnated with a resin composition is prepared. To describe the casting method in detail, a solution of the resin composition is cast (sometimes coated) onto a mirror-treated iron plate or a carrier film for casting to a thickness of, for example, 5 to 700 μm, and A film is obtained by drying to remove the solvent. The upper limit of the set temperature during drying is preferably lower than the boiling point of the solvent or lower than the heat-resistant temperature of the carrier film for casting (when drying is performed on the carrier film for casting); The lower limit is determined by drying time, processability, etc. The resin-impregnated base material can be obtained, for example, by impregnating a base material with a solution of the resin composition and drying it. As the base material, glass cloth, glass mat, polyester cloth, polyester mat, aramid fiber cloth, paper, nonwoven fabric, etc. are used. A laminate is obtained by laminating and molding a predetermined number of the above-mentioned film and resin-impregnated base material, either alone or in combination, to a predetermined thickness. Alternatively, a film or resin-impregnated base material and metal foil may be laminated to form a laminate plate with metal foil on both sides or one side, or a predetermined number of films and/or resin-impregnated base materials may be laminated in advance and one side of this laminated plate may be formed. Alternatively, a metal foil-covered laminate can be obtained by overlapping metal foils on both sides and laminating them. As the metal foil, copper foil, aluminum foil, etc. are used. The overall thickness of the laminate obtained in this way is not particularly limited, but it is preferably about 0.2 to 2 mm, and 0.6 to 0.8 mm.
It is more desirable in terms of circuit design. If the resin composition contains an initiator and is thermally cured, the heating temperature and heating time during laminated molding will depend on the reaction temperature of the initiator used, etc. It is good to choose. For example, temperature 150~300℃, pressure 10~150Kg/ cm2 , time
It takes about 10 to 90 minutes. The resin is melted by heating during lamination molding, and films are adhered to each other, resin-impregnated base materials to each other, films and resin-impregnated base materials, films and metal foils, and resin-impregnated base materials to metal foils to each other to obtain a laminate. . This fusion bond provides strong adhesion. PPO has excellent adhesive properties, so it does not require an adhesive when laminating and bonding metal foils. If an initiator is blended into the resin composition, radical crosslinking will occur by heating and/or ultraviolet irradiation, and the resin will be cured.
This curing provides stronger adhesion and a stronger laminate. If radiation is then applied, a crosslinking reaction will occur and the resin will harden even if no initiator is added, resulting in even stronger adhesion and a stronger laminate. Even if metal foil is laminated, it has almost no effect on radiation irradiation. In order to take advantage of PPO's excellent heat-adhesive properties, if the metal foil is heat-sealed to the film or resin-impregnated base material in advance and then irradiated with radiation, the adhesive interface can also be crosslinked. Therefore, adhesion with excellent heat resistance can be realized between the film or resin-impregnated base material and the metal foil. The thus obtained laminate does not impair the properties of PPO, has excellent dielectric properties, and also has good heat resistance, peel strength, and electrical properties. It can be easily obtained by the manufacturing operation described above. Next, Examples and Comparative Examples will be described. (Examples 1 and 3) The compounded materials shown in Table 1 were dissolved and mixed in Trichloroethylene (trichloroethylene manufactured by Toagosei Chemical Industry Co., Ltd.) to form a 20% by weight solution of a resin composition. This solution was applied onto a release film to a thickness of 500 μm and dried to obtain a casting film about 100 μm thick. Six sheets of this film (15 sheets in Example 5) were stacked at a temperature of 220°C and a pressure of 50 kg/ cm2.
(In Example 5, lamination molding was carried out at 100 kg/cm 2 for 30 minutes to obtain a laminate with a thickness of 0.8 mm. ) to prepare a 15% by weight solution of the resin composition.The base materials shown in Table 1 were impregnated with this solution to produce resin-impregnated base materials.Copper foil, Layer several sheets of resin-impregnated base material and copper foil in that order, and heat to 220℃.
℃ (200° C. in Example 6) and a pressure of 50 kg/cm 2 for 30 minutes (60 minutes in Example 6) to obtain a 0.8 mm thick laminate. (Comparative Example 1) An attempt was made to obtain a casting film using the formulation shown in Table 1 in the same manner as in Example 1, but an ear-staining film could not be obtained with this resin composition. (Comparative Examples 2 and 3) A laminate with a thickness of 0.8 mm was obtained in the same manner as in Example 2 using the formulations shown in Table 1. In addition, comparative example 3
Since no initiator is added and only heating is performed during lamination molding, there is almost no curing. In Table 1, A is 2,5-dimethyl-2,5(t
-butylperoxy)hexyne-3, B is 2,5
-dimethyl-2,5-di(t-butylperoxy)hexane, C is α-α'-bis(t-butylperoxy-m-isopropyl)benzene, 1,2
-PB each represents 1,2-polybutadiene.
【表】【table】
この発明にかかる積層板は、PPO、ならびに、
TAICおよび／またはTACを含む樹脂組成物を
硬化して得られるので、高周波特性に優れ、か
つ、耐熱性、ピール強度、電気特性が良好なもの
である。
The laminate according to the present invention includes PPO and
Since it is obtained by curing a resin composition containing TAIC and/or TAC, it has excellent high frequency properties, and has good heat resistance, peel strength, and electrical properties.
Claims (1)
シアヌレートおよび／またはトリアリルシアヌレ
ート、ブタジエン系の架橋性ポリマー、ならび
に、開始剤を含む樹脂組成物を硬化させて得られ
る積層板。 ２ 樹脂組成物中の各成分の配合割合が、ポリフ
エニレンオキサイド、トリアリルイソシアヌレー
トおよび／またはトリアリルシアヌレート、なら
びに、架橋性ポリマーの３者間では、３者合計
100重量部に対し、ポリフエニレンオキサイドを
50重量部以上95重量部未満、トリアリルイソシア
ヌレートおよび／またはトリアリルシアヌレート
を５重量部以上50重量部未満、架橋性ポリマーを
残部とし、開始剤と前記３者間では、３者合計
100重量部に対し開始剤を0.1〜5.0重量部とする
ようになつている特許請求の範囲第１項記載の積
層板。 ３ 樹脂組成物がキヤステイングフイルム化さ
れ、このフイルムが積層成形されてなる特許請求
の範囲第１項または第２項記載の積層板。 ４ 樹脂組成物が基材に含浸されて、この基材が
積層成形されてなる特許請求の範囲第１項または
第２項記載の積層板。[Scope of Claims] 1. A laminate obtained by curing a resin composition containing polyphenylene oxide, triallyl isocyanurate and/or triallyl cyanurate, a butadiene-based crosslinkable polymer, and an initiator. 2. If the blending ratio of each component in the resin composition is polyphenylene oxide, triallyl isocyanurate and/or triallyl cyanurate, and crosslinkable polymer, the total of the three components
Polyphenylene oxide per 100 parts by weight
50 parts by weight or more and less than 95 parts by weight, 5 parts by weight or more and less than 50 parts by weight of triallyl isocyanurate and/or triallyl cyanurate, the remainder being a crosslinkable polymer, and between the initiator and the above three, the total of the three.
The laminate according to claim 1, wherein the initiator is contained in an amount of 0.1 to 5.0 parts by weight per 100 parts by weight. 3. The laminate according to claim 1 or 2, wherein the resin composition is formed into a casting film, and this film is laminated and molded. 4. The laminate according to claim 1 or 2, wherein the resin composition is impregnated into a base material, and this base material is laminated and molded.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13015885A JPS61287739A (en) | 1985-06-15 | 1985-06-15 | Laminated board |
| CA000504084A CA1285675C (en) | 1985-03-25 | 1986-03-14 | Method of preparing polyphenylene oxide composition and laminate using the composition |
| GB08606764A GB2172892B (en) | 1985-03-25 | 1986-03-19 | Method of preparing polyphenylene oxide composition and laminate using the composition |
| FR8604025A FR2579213B1 (en) | 1985-03-25 | 1986-03-20 | PROCESS FOR THE PREPARATION OF A POLY (OXYPHENYLENE) COMPOSITION, AND A LAMINATE USING THE SAME |
| DE3644998A DE3644998C2 (en) | 1985-03-25 | 1986-03-21 | Process for the production of a film or sheeting based on polyphenylene oxide, and the use thereof for the production of laminates |
| DE19863609664 DE3609664C2 (en) | 1985-03-25 | 1986-03-21 | Process for producing a film or sheet based on polyphenylene oxide and its use |
| US07/157,936 US4874826A (en) | 1985-03-25 | 1988-02-19 | Method of preparing polyphenylene oxide composition and laminates using such compositions |
| US07/379,281 US5124415A (en) | 1985-03-25 | 1989-07-13 | Method of preparing polyphenylene oxide composition and laminates using such compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13015885A JPS61287739A (en) | 1985-06-15 | 1985-06-15 | Laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61287739A JPS61287739A (en) | 1986-12-18 |
| JPH0445530B2 true JPH0445530B2 (en) | 1992-07-27 |
Family
ID=15027380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13015885A Granted JPS61287739A (en) | 1985-03-25 | 1985-06-15 | Laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61287739A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6429799U (en) * | 1987-08-17 | 1989-02-22 | ||
| US5218030A (en) * | 1989-02-08 | 1993-06-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Curable polyphenylene ether resin composition and a cured resin composition obtainable therefrom |
| DE69204689T2 (en) * | 1991-01-11 | 1996-05-09 | Asahi Chemical Ind | A curable polyphenylene ether resin composition and a cured resin composition producible therefrom. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637578A (en) * | 1968-01-23 | 1972-01-25 | Fmc Corp | Polyester-polyphenylene ether mixed resins |
-
1985
- 1985-06-15 JP JP13015885A patent/JPS61287739A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637578A (en) * | 1968-01-23 | 1972-01-25 | Fmc Corp | Polyester-polyphenylene ether mixed resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61287739A (en) | 1986-12-18 |
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