JPH01125224A - Electrically insulating laminate and sealing material for electronic parts - Google Patents
Electrically insulating laminate and sealing material for electronic partsInfo
- Publication number
- JPH01125224A JPH01125224A JP63128660A JP12866088A JPH01125224A JP H01125224 A JPH01125224 A JP H01125224A JP 63128660 A JP63128660 A JP 63128660A JP 12866088 A JP12866088 A JP 12866088A JP H01125224 A JPH01125224 A JP H01125224A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- resin
- epoxy resin
- modified polyimide
- polyimide 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.)
- Granted
Links
- 239000003566 sealing material Substances 0.000 title claims description 6
- 239000002648 laminated material Substances 0.000 title 1
- 229920001721 polyimide Polymers 0.000 claims abstract description 30
- 239000009719 polyimide resin Substances 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 13
- 125000005462 imide group Chemical group 0.000 claims abstract description 13
- -1 imide compound Chemical class 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 239000002966 varnish Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000010292 electrical insulation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 239000011888 foil Substances 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011889 copper foil Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract description 2
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000012777 electrically insulating material Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance 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
- H05K1/0346—Organic insulating material consisting of one material containing N
Landscapes
- Organic Insulating Materials (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【産業上の利用分野１
本発明はエポキシ変性ポリイミド樹脂を用いた電気絶縁
材料に関する。
【従来技術】
従来上りポリイミド樹脂は、耐熱性ポリマーとして汎用
されているが、溶媒可溶性及び溶融成形性を向上させる
ために耐熱性が犠牲にされている。
又、ポリイミド樹脂は吸水率が高いという欠点もある。
このためポリイミド樹脂にエポキシ樹脂を配合させて耐
熱性を向上させると共に吸水率の低下も図られているが
、耐熱性が向上し、吸水率も低下するものの、密着力及
び難燃性が低下してしまい、多層積／ｌｉＦ板とか電子
部品封止ｍ材料としては採用できないものであった。
そこで、本発明者等はエポキシ樹脂の配合量を増す代わ
りに、エポキシ樹脂とポリイミド樹脂をつなぐ憎さをす
る成分を配合すれば樹脂間の密着力が高まることを見出
だした。即ち、分子内にイミド基とアミノ基を各々複数
個有する芳香族系化合物にエポキシ樹脂を反応させた得
られるエポキシ変性ポリイミド樹脂を開発しており、こ
の樹脂によれば眉間密着力及び耐湿性の向上がもたらさ
れる。[Industrial Application Field 1] The present invention relates to an electrical insulating material using an epoxy-modified polyimide resin. BACKGROUND OF THE INVENTION Conventional polyimide resins have been widely used as heat-resistant polymers, but heat resistance has been sacrificed in order to improve solvent solubility and melt moldability. Additionally, polyimide resin has a drawback of high water absorption. For this reason, attempts have been made to improve heat resistance and reduce water absorption by blending epoxy resin with polyimide resin, but although heat resistance is improved and water absorption is reduced, adhesion and flame retardancy are reduced. Therefore, it could not be used as a material for multilayer lamination/LIF boards or electronic component sealing materials. Therefore, the present inventors have discovered that instead of increasing the amount of epoxy resin blended, if a component that binds the epoxy resin and polyimide resin is blended, the adhesion between the resins can be increased. Specifically, we have developed an epoxy-modified polyimide resin obtained by reacting an epoxy resin with an aromatic compound having multiple imide groups and amino groups in the molecule, and this resin has excellent glabella adhesion and moisture resistance. Improvements are brought about.
しかしながら、分子内にイミド基とアミノ基を各々複数
個有する芳香族系化合物とエポキシ樹脂の二種の物質を
反応させるだけでは、未反応のイミド基が残留して、高
温に長期間さらされると、ミクロなりラックが生じ、耐
電圧特性が劣化するなど耐熱性に悪影響を与えてしまっ
ている。
本発明は上記事情に鑑みて為されたものであり、その目
的とするところは耐熱性に優れ、密着力が強く、しかも
吸水率が低（、難燃性に優れた電気絶縁用積層板及び電
子部品封止用材料を提供することにある。
【課題を解決するための手段］
本発明の電気絶縁用積層板は、分子内にイミド基とアミ
ノ基を各々複数個有する芳香族系化合物にブロム化エポ
キシ樹脂を含むエポキシ樹脂を不飽和イミド化合物の存
在下で反応させてエポキシ変性ポリイミド樹脂を調製し
、このエポキシ変性ポリイミド樹脂のワニスを基材を含
浸させ、乾燥させてプリプレグを形成し、このプリプレ
グを複数枚積層成形して成るものであり、本発明の電子
部品封止用材料は、分子内にイミド基とアミノ基を各々
複数個有する芳香族系化合物にブロム化エポキシ樹脂を
含むエポキシ樹脂を不飽和イミド化合物の存在下で反応
させて調製したエポキシ変性ポリイミド樹脂に硬化剤、
充填剤、離型剤等を配合させて成るものであり、この構
成により上記目的が達成されたものである。
本発明における分子内にイミド基とアミノ基を各々複数
個有する芳香族系化合物としては、例えば、特開昭６２
−２９５８４号公報に開示されでいるように
に′
（式中、Ｘは末端官能基を表し、＾ｒ１１＾ｒ２は２価
の芳香族基、Ｒ１は水素原子、炭素数１〜１０のアルキ
ル基、Ｒ２は水素原子、炭素数１〜２０のアルキル基、
アルコキシ基あるいは水酸基を表し、鋤は０又は正の整
数を示す）
で表される末端官能型イミド樹脂とか一般式（式中、＾
ｒ１は２価の芳香族基、＾ｒ２は４価の芳香族基、＾ｒ
３は３価の芳香族基を示し、ｎ、 ｍは０又は正の整数
（但し、ｎ＋ｐ＞０）である、）で表される芳香族化合
物や、一般式
ＲＩ Ｒ２
（式中、＾「４は４価の芳香族基を示し、Ｒ１，Ｒ２は
水素原子、ハロゲン原子又はフル斗ル基を示し Ｒ１゜
Ｒ２のうちの少なくとも一方は常にアルキル基である。
ｑは正の整数である。）
で表される芳香族化合物を挙げることができ、これらの
化合物は単独で、又は２種以上混合して使用される。
又、本発明においてエポキシ樹脂に含有させるブロム化
エポキシ樹脂としては一般式
（式中、ｒは正の整数）
で表されるブロム化／ボラックエポキシ樹脂や、式
で表わされるテトラブロムビスフェノールＡのジグリシ
ジルエーテル化合物などが使用される。
このブロム化エポキシ樹脂に含まれる臭素は全樹脂分に
対して６〜２０重量％の範囲にあるのが好ましい、６重
量％未満であると、充分な難燃性を確保できず、一方２
０重１％を超えると耐熱性が低下する傾向にある６
エポキシ樹脂成分は芳香族化合物に対して好ましくは重
量比で３：１〜６の範囲で使用される。この範囲を逸脱
してエポキシリッチの場合は、吸水率が低下し、密着性
は向上するが耐熱性が低下しでしまうものである。
本発明において硬化剤としで作用する不飽和イミド化合
物としては式、
■
で表されるマレインイミドや式、
で表されるビスマレイミドが好適に使用される。
この不飽和イミド化合物は芳香族化合物に対して好まし
くは重量比で１〜４：１０の範囲で使用される。不飽和
イミド化合物の量がこの範囲よりも多くなると、耐熱性
が低下し吸水率が高くなる傾向にある。
これら芳香族化合物、エポキシ樹脂成分及び不飽和イミ
ド化合物は混合され、例えば９０〜１００℃で１０〜８
０分間加熱され、次いで常温にまで冷却され約３０分間
攪拌下反応させてエポキシ変性ポリイミド樹脂が製造さ
れる。この場合、不飽和イミド化合物の存在下で反応さ
せることによりアミ７基と反応させてイミノ基を生成さ
せ、このようにして得られた分子内にアミノ基、イミノ
基及びイミド基を含有するポリイミド樹脂プレポリマー
にエポキシ樹脂を反応させることによりアミ７基の残留
を抑制して耐熱性及Ｖ密着性に優れたエポキシ変性ポリ
イミド樹脂が得られるのである。
このエポキシ変性ポリイミド樹脂ワニスがガラス布、不
織布、紙などの基材に含浸され、乾燥されてプリプレグ
が製造される。このプリプレグが複数枚積層成形され、
その片面又は両面に銅箔、アルミニウム箔などの金属箔
が貼着されて金属箔張り積層板が製造される。
又、このエポキシ変性ポリイミド樹脂に硬化剤、シリカ
等の充填剤、プラス繊維、カップリング剤、着色剤、ス
テアリン酸カルシウム等の離型剤、希釈剤などが添加さ
れて電子部品封止用材料が製造される。巳の封止用材料
の配合割合は、例えば、エポキシ変性ポリイミド樹脂３
０重量部、シリカ７０重量部、離型剤０．０５部である
。
次に本発明の実施例を具体的に説明する。以下において
部とあるのは重量部を示す。
（実施例）
イミド樹脂成分として末端官能型イミド樹脂（商品名［
ＴＭＳ−２０Ｊ、住人化学（株）製）２３６部、エポキ
シ樹脂成分として液状エポキシ樹脂（商品名［Ｒ−１４
０ＱＪ、三井石油化学（株）製）１５６部とブロム化ノ
ボラック樹脂（臭素含有１１３６重量％、商品名ｒＢＲ
ＥＮ（Ｍ−８０）」、日本化薬（株）製）１８３部、硬
化剤として不飽和ビスマレイミド８３．５部を混合し、
９０℃で５０分間加熱し、次いで常温にまで冷却して３
０分間攪拌下反応させてエポキシ変性ポリイミド樹脂を
製造した。このもののＴｇは２７０℃であった。未反応
のイミド基は殆ど存在しなかった。
このエポキシ変性ポリイミド樹脂単体スをγラス布に含
浸させ、乾燥させてプリプレグを製造した。
このプリプレグを複数枚積層成形して厚み０．４部論の
積層板を製造した。
この積層板の眉間密着力、吸水率（５ｃｍＸ５ｃｍで厚
み０．４ｍｍの試料片を２３℃の水中に２４時間浸漬）
、長期耐熱性（２００℃、２４ｈｒ）、難燃性（ＵＬ
９４ Ｖ−０）音測定した。結果を第１表に示す。
（比較例１）
イミド樹脂成分として実施例と同一の末端官能型イミド
樹脂４２６部、エポキシ樹脂成分として実施例と同一の
液状エポキシ樹脂２３１部と実施例と同一のブロム化ノ
ボラフク樹脂２５９部を混合し、常温下、３０分かけて
反応させてエポキシ樹脂変性ポリイミド樹脂を製造した
。このもののＴｇは２３０℃であった。 次いで、実施
例と同様にして積層板を製造し、同様の測定を打った。
結果を第１表に示す。
（比較例２）
Ｔｇが２５０℃のポリイミド樹脂ワニスを使用した以外
は実施例と同様にして積層板を製造し、同様の測定を行
った。結果を第１表に示す。
（比較例３）
Ｔｇが１５０℃のエポキシ樹脂ワニスを使用した以外は
実施例と同様にして積層板を製造し、同様の測定を行っ
た。結果を第１表に示す。
実施例 比較例
層間密着力
（ｋｇ／ａｍ） １，２０ １，４
０ ０，９０ １．７０吸水率
（％） ０，６５ ０，５３ １，００
０．４３長期耐熱性 ○ ｘ ＯＸ×
第１表の結果より、実施例にあっては、密着力は比較例
１及び３のものよりは劣るものの、実用上問題となる程
の差ではなく、ポリイミド樹脂単体の比較例２から着し
く向上していることが判る。
又、吸水率も低（、長期耐熱性、難燃性にも優れて、全
体的にバランスの採れた性能を有し、マルチ材として好
適に採用できることが理解でさる。
【発明の効果］
本発明の電気絶縁用積層板は、分子内にイミド基とアミ
７基を各々複数個有する芳香族系化合物にブロム化エポ
キシ樹脂を含むエポキシ樹脂を不飽和イミド化合物の存
在下で反応させてエポキシ変性ポリイミド樹脂を調製し
、このエポキシ変性ポリイミド樹脂のワニスを基材を含
浸させ、乾燥させてプリプレグを形成し、このプリプレ
グを複数枚積層成形して成るものであり、本発明の電子
部品封止用材料は、上記エポキシ変性ポリイミド樹脂を
配合させて成るものであり、いずれも未反応のイミド基
の残留率の小さい特定のエポキシ変性ポリイミド樹脂を
用いることにより、耐熱性に優れ、Ｗ着力が強く、しか
む吸水率の低く、難燃性に優れ、電気絶縁材料として好
適に採用でさるものである。
代理人 弁理士 石 １）艮 七However, if only two substances, an aromatic compound and an epoxy resin, each having a plurality of imide groups and amino groups in the molecule, are reacted, unreacted imide groups will remain, and if exposed to high temperatures for a long period of time, , microscopic racks are generated, which has an adverse effect on heat resistance, such as deterioration of withstand voltage characteristics. The present invention was made in view of the above circumstances, and its purpose is to provide a laminate for electrical insulation that has excellent heat resistance, strong adhesion, and low water absorption (and has excellent flame retardancy). An object of the present invention is to provide a material for encapsulating electronic components. [Means for Solving the Problems] The electrically insulating laminate of the present invention is made of an aromatic compound having a plurality of imide groups and a plurality of amino groups in the molecule. An epoxy resin including a brominated epoxy resin is reacted in the presence of an unsaturated imide compound to prepare an epoxy-modified polyimide resin, and a base material is impregnated with a varnish of the epoxy-modified polyimide resin and dried to form a prepreg, The electronic component sealing material of the present invention is made by laminating and molding a plurality of sheets of this prepreg, and the electronic component sealing material of the present invention is an epoxy resin containing an aromatic compound having a plurality of imide groups and a plurality of amino groups in the molecule, and a brominated epoxy resin. A curing agent is added to an epoxy-modified polyimide resin prepared by reacting a resin in the presence of an unsaturated imide compound.
It is made by blending a filler, a mold release agent, etc., and with this structure, the above object is achieved. Examples of aromatic compounds having a plurality of imide groups and a plurality of amino groups in the molecule in the present invention include, for example, JP-A-62
As disclosed in Japanese Patent No. 29584, , R2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
It represents an alkoxy group or a hydroxyl group, and 0 or a positive integer).
r1 is a divalent aromatic group, ^r2 is a tetravalent aromatic group, ^r
3 represents a trivalent aromatic group, n and m are 0 or a positive integer (however, n+p>0)), and aromatic compounds represented by the general formula RI R2 (wherein ^" 4 represents a tetravalent aromatic group, R1 and R2 represent a hydrogen atom, a halogen atom or a fluorocarbon group, and at least one of R1 and R2 is always an alkyl group. q is a positive integer. ) These compounds can be used alone or in a mixture of two or more. In addition, in the present invention, the brominated epoxy resin to be contained in the epoxy resin has the general formula (In the formula, r is a positive integer) A brominated/borac epoxy resin represented by the following formula, a diglycidyl ether compound of tetrabromobisphenol A represented by the formula, etc. are used. Contained in this brominated epoxy resin Bromine is preferably in the range of 6 to 20% by weight based on the total resin content; if it is less than 6% by weight, sufficient flame retardance cannot be ensured;
If it exceeds 0% by weight and 1%, heat resistance tends to decrease.6 The epoxy resin component is preferably used in a weight ratio of 3:1 to 6 to the aromatic compound. If the epoxy richness deviates from this range, the water absorption rate will decrease and the adhesion will improve, but the heat resistance will decrease. In the present invention, maleimide represented by the formula (2) and bismaleimide represented by the formula (2) are preferably used as the unsaturated imide compound that acts as a curing agent. The unsaturated imide compound is preferably used in a weight ratio of 1 to 4:10 to the aromatic compound. When the amount of the unsaturated imide compound exceeds this range, the heat resistance tends to decrease and the water absorption rate tends to increase. These aromatic compounds, epoxy resin components, and unsaturated imide compounds are mixed, for example, at a temperature of 90 to 100° C.
The mixture is heated for 0 minutes, then cooled to room temperature, and reacted with stirring for about 30 minutes to produce an epoxy-modified polyimide resin. In this case, the polyimide containing an amino group, an imino group, and an imide group in the molecule obtained by reacting with an amine 7 group to generate an imino group by reacting in the presence of an unsaturated imide compound. By reacting the resin prepolymer with the epoxy resin, it is possible to suppress the residual of amide 7 groups and obtain an epoxy-modified polyimide resin with excellent heat resistance and V adhesion. This epoxy-modified polyimide resin varnish is impregnated into a base material such as glass cloth, nonwoven fabric, paper, etc., and dried to produce a prepreg. Multiple sheets of this prepreg are laminated and molded,
A metal foil-clad laminate is manufactured by pasting metal foil such as copper foil or aluminum foil on one or both sides of the laminate. In addition, hardening agents, fillers such as silica, plus fibers, coupling agents, colorants, release agents such as calcium stearate, diluents, etc. are added to this epoxy-modified polyimide resin to produce materials for encapsulating electronic components. be done. The blending ratio of the sealing material for the snake is, for example, epoxy modified polyimide resin 3 parts
0 parts by weight, 70 parts by weight of silica, and 0.05 parts of mold release agent. Next, embodiments of the present invention will be specifically described. In the following, parts indicate parts by weight. (Example) Terminal functional imide resin (product name [
TMS-20J, manufactured by Sumima Kagaku Co., Ltd.) 236 parts, liquid epoxy resin (trade name [R-14
0QJ, manufactured by Mitsui Petrochemical Co., Ltd.) and 156 parts of brominated novolac resin (bromine content: 1136% by weight, trade name rBR)
EN (M-80), manufactured by Nippon Kayaku Co., Ltd., 183 parts and 83.5 parts of unsaturated bismaleimide as a curing agent were mixed,
Heat at 90°C for 50 minutes, then cool to room temperature for 3
The mixture was reacted with stirring for 0 minutes to produce an epoxy-modified polyimide resin. The Tg of this product was 270°C. Almost no unreacted imide groups were present. This epoxy-modified polyimide resin alone was impregnated into a gamma lath cloth and dried to produce a prepreg. A plurality of sheets of this prepreg were laminated and molded to produce a laminate having a thickness of 0.4 parts. Glabella adhesion and water absorption rate of this laminate (sample piece of 5cm x 5cm and 0.4mm thick immersed in water at 23℃ for 24 hours)
, long-term heat resistance (200℃, 24hr), flame retardant (UL
94 V-0) Sound was measured. The results are shown in Table 1. (Comparative Example 1) 426 parts of the same terminal functional imide resin as in the example as the imide resin component, 231 parts of the same liquid epoxy resin as in the example as the epoxy resin component, and 259 parts of the same brominated novolafuku resin as in the example were mixed. The mixture was reacted at room temperature for 30 minutes to produce an epoxy resin-modified polyimide resin. The Tg of this product was 230°C. Next, a laminate was manufactured in the same manner as in the example, and the same measurements were performed. The results are shown in Table 1. (Comparative Example 2) A laminate was manufactured in the same manner as in the example except that a polyimide resin varnish having a Tg of 250° C. was used, and the same measurements were performed. The results are shown in Table 1. (Comparative Example 3) A laminate was manufactured in the same manner as in the example except that an epoxy resin varnish having a Tg of 150° C. was used, and the same measurements were performed. The results are shown in Table 1. Example Comparative example Interlayer adhesion (kg/am) 1,20 1,4
0 0,90 1.70 Water absorption rate (%) 0,65 0,53 1,00
0.43 Long term heat resistance ○ x OX It can be seen that there is a significant improvement from Comparative Example 2 of polyimide resin alone. It also has a low water absorption rate (with excellent long-term heat resistance and flame retardancy), and has an overall well-balanced performance, so it is understood that it can be suitably used as a mulch material. [Effects of the Invention] This book The electrically insulating laminate of the invention is produced by epoxy-modifying an aromatic compound having a plurality of imide groups and a plurality of amino-7 groups in the molecule with an epoxy resin containing a brominated epoxy resin in the presence of an unsaturated imide compound. A polyimide resin is prepared, a base material is impregnated with a varnish of this epoxy-modified polyimide resin, and a prepreg is formed by drying, and a plurality of sheets of this prepreg are laminated and molded. The material is made by blending the above-mentioned epoxy-modified polyimide resin, and by using a specific epoxy-modified polyimide resin with a small residual rate of unreacted imide groups, it has excellent heat resistance, strong W adhesion, It has a low water absorption rate, excellent flame retardancy, and is suitable for use as an electrical insulating material. Agent: Patent Attorney Ishi 1) Ai Shichi
Claims (4)
芳香族系化合物にブロム化エポキシ樹脂を含むエポキシ
樹脂を不飽和イミド化合物の存在下で反応させてエポキ
シ変性ポリイミド樹脂を調製し、このエポキシ変性ポリ
イミド樹脂のワニスを基材に含浸させ、乾燥させてプリ
プレグを形成し、このプリプレグを複数枚積層成形して
成ることを特徴とする電気絶縁用積層板。(1) An epoxy resin containing a brominated epoxy resin is reacted with an aromatic compound having a plurality of imide groups and a plurality of amino groups in the molecule in the presence of an unsaturated imide compound to prepare an epoxy-modified polyimide resin. A laminate for electrical insulation, characterized in that a base material is impregnated with a varnish of epoxy-modified polyimide resin, dried to form a prepreg, and a plurality of prepregs are laminated and molded.
に対して６〜２０重量％であることを特徴とする請求項
１記載の電気絶縁用積層板。(2) The electrically insulating laminate according to claim 1, wherein bromine contained in the brominated epoxy resin is 6 to 20% by weight based on the total resin content.
芳香族系化合物にブロム化エポキシ樹脂を含むエポキシ
樹脂を不飽和イミド化合物の存在下で反応させて調製し
たエポキシ変性ポリイミド樹脂を配合させて成ることを
特徴とする電子部品封止用材料。(3) An epoxy-modified polyimide resin prepared by reacting an epoxy resin including a brominated epoxy resin in the presence of an unsaturated imide compound is blended with an aromatic compound having a plurality of imide groups and a plurality of amino groups in the molecule. A material for encapsulating electronic components, characterized by comprising:
に対して６〜２０重量％であることを特徴とする請求項
３記載の電子部品封止用材料。(4) The electronic component sealing material according to claim 3, wherein the bromine contained in the brominated epoxy resin is 6 to 20% by weight based on the total resin content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128660A JPH01125224A (en) | 1987-07-06 | 1988-05-26 | Electrically insulating laminate and sealing material for electronic parts |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16822087 | 1987-07-06 | ||
| JP62-168220 | 1987-07-06 | ||
| JP63128660A JPH01125224A (en) | 1987-07-06 | 1988-05-26 | Electrically insulating laminate and sealing material for electronic parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01125224A true JPH01125224A (en) | 1989-05-17 |
| JPH0562591B2 JPH0562591B2 (en) | 1993-09-08 |
Family
ID=15864014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63128660A Granted JPH01125224A (en) | 1987-07-06 | 1988-05-26 | Electrically insulating laminate and sealing material for electronic parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01125224A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036599A (en) * | 1973-08-03 | 1975-04-05 | ||
| JPS6229584A (en) * | 1985-07-31 | 1987-02-07 | Sumitomo Chem Co Ltd | Thermally curable imide compound |
-
1988
- 1988-05-26 JP JP63128660A patent/JPH01125224A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036599A (en) * | 1973-08-03 | 1975-04-05 | ||
| JPS6229584A (en) * | 1985-07-31 | 1987-02-07 | Sumitomo Chem Co Ltd | Thermally curable imide compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0562591B2 (en) | 1993-09-08 |
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