JPS62172025A - Production of addition type imide resin prepolymer - Google Patents
Production of addition type imide resin prepolymerInfo
- Publication number
- JPS62172025A JPS62172025A JP1502086A JP1502086A JPS62172025A JP S62172025 A JPS62172025 A JP S62172025A JP 1502086 A JP1502086 A JP 1502086A JP 1502086 A JP1502086 A JP 1502086A JP S62172025 A JPS62172025 A JP S62172025A
- Authority
- JP
- Japan
- Prior art keywords
- imide
- bis
- prepolymer
- formula
- diamine
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 150000003949 imides Chemical class 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 10
- 239000011976 maleic acid Substances 0.000 abstract description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 8
- 239000002966 varnish Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 2,6-diaminobilinone Chemical compound 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 238000005059 solid analysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- IJHNSHDBIRRJRN-UHFFFAOYSA-N N,N-dimethyl-3-phenyl-3-(2-pyridinyl)-1-propanamine Chemical compound C=1C=CC=NC=1C(CCN(C)C)C1=CC=CC=C1 IJHNSHDBIRRJRN-UHFFFAOYSA-N 0.000 description 1
- 206010041235 Snoring Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960001190 pheniramine Drugs 0.000 description 1
- SFLGSKRGOWRGBR-UHFFFAOYSA-N phthalane Chemical compound C1=CC=C2COCC2=C1 SFLGSKRGOWRGBR-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 235000020083 shōchū Nutrition 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
[技術分野]
本発明は、プリント配線板の基材に含浸する七(脂など
として用いられる付加型イEr?jtlJltプレポリ
マーの製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing an addition-type Er?jtlJlt prepolymer, which is used as a fat to be impregnated into a substrate of a printed wiring board.
[背景技術]
プリント配縁板の高密度実装化、高多層化等に伴ってプ
リント配線板の積層板におけるマトリ7クス樹脂と基材
との高密着性や樹脂の低熱膨張性が必要とされる。この
ことは高耐熱性用脂として開発されプリント配線板のマ
トリ7クス樹脂として用いることが実用化され′ζいる
ポリイミドにおいてら同様に要求される。[Background technology] As printed wiring boards become more densely packaged and multi-layered, high adhesion between the matrix resin and the base material and low thermal expansion of the resin in printed wiring board laminates are required. Ru. This is similarly required for polyimide, which was developed as a highly heat-resistant resin and has been put into practical use as a matrix resin for printed wiring boards.
そしてプリント配線板のマトリ7クス樹脂とし′〔ポリ
イミドを用いる場合、<N+加型イミド的(脂プレポリ
マーを基材に含浸して使用するのが・般的であるが、が
かる付加型イミド樹脂プレポリマーを用いた場合におい
て基材との密着性が不十分になり、また熱]膨張率が大
きくなる/jス囚について木登[)11若シモ6Cシh
木ト1す・鼾−ノーー会伊のイ、t1111へリイ≧V
…脂プレポリマーは高分子量成分を多く含むことが大き
な原因であるという知見が得られた。Then, as a matrix resin for printed wiring boards, [when polyimide is used, <N+additional imide type (generally, the base material is impregnated with a fat prepolymer; When a prepolymer is used, the adhesion with the base material becomes insufficient and the coefficient of thermal expansion becomes large.
Wood 1 Snoring - No meeting Italian I, t1111 ≧V
...We found that a major cause of this is that the fat prepolymer contains a large amount of high molecular weight components.
[発明の目的j
本発明は、上記の点に鑑みて為されたものであり、高分
子量成分を多く含まず基材との密着性に優れると共に熱
膨張率の低いポリイミドを与えることのできる付加型イ
ミド樹脂プレポリマーの製造法を提供することを目的と
するものである。[Purpose of the Invention j The present invention has been made in view of the above points, and is an additive that can provide a polyimide that does not contain a large amount of high molecular weight components, has excellent adhesion to a base material, and has a low coefficient of thermal expansion. The object of the present invention is to provide a method for producing a type imide resin prepolymer.
[発明の開示1
しかして本発明に係る付加型イミド樹脂プレポリマーは
、一般式が
(式中りは炭素−炭素間の二重結合を有する2価の有敗
基を表し、R1上少なくとも2個の炭素原子を含む2価
の基を表す。)の不飽和ビス−イミドと、一般式が
82N R2−NH2
(式中R2は少なくとも2個の炭素原子を含む2価の基
を表す。)のジアミンとを、非プロトン性極性溶媒中で
50°C以上100°C未満の温度で、残存する未反応
原料が35〜50%になるまで反応させることを特徴と
するものであて)、かがる不飽和ビス−イミドとジアミ
ンとを非プロトン性極性溶媒中で低温反応をおこない、
さらに反応プレポリマー中の未反応原料の残存量を制御
することによって、高分子量成分を多く含まない付加型
イミド樹脂プレポリマーを得ることができるということ
を見出だして本発明を完成しだらのであって、以下本発
明の詳細な説明する。[Disclosure of the Invention 1] The addition type imide resin prepolymer according to the present invention has a general formula (wherein represents a divalent group having a carbon-carbon double bond, and at least 2 on R1). represents a divalent group containing at least 2 carbon atoms) and an unsaturated bis-imide with the general formula 82N R2-NH2 (wherein R2 represents a divalent group containing at least 2 carbon atoms). diamine in an aprotic polar solvent at a temperature of 50°C or more and less than 100°C until the remaining unreacted raw material becomes 35 to 50%), A low-temperature reaction is carried out between an unsaturated bis-imide and a diamine in an aprotic polar solvent,
Furthermore, by controlling the residual amount of unreacted raw materials in the reacted prepolymer, it was possible to obtain an addition-type imide resin prepolymer that does not contain a large amount of high molecular weight components, which led to the completion of the present invention. The present invention will now be described in detail.
本発明の出発原料の一つである不飽和ビス−イミドは一
般式が(I)
で表される。また出発原料の池の一つであるジアミンは
一般式が(If)
、H,N−R2−NH2<n)
で表される。The unsaturated bis-imide, which is one of the starting materials of the present invention, has the general formula (I). Further, diamine, which is one of the starting materials, has the general formula (If): H,NR2-NH2<n).
ユニでN)式中D1.を炭素−炭素間の二重結合をで置
換された誘導体である。またR9は少なくとも2個の炭
素原子を含む2価の基を表す。さらに(ロ)式中R2は
30個以下で且つ少なくとも2個の炭素原子を含む2価
の基を表す。Uni and N) in the formula D1. is a derivative in which the carbon-carbon double bond is substituted with. Moreover, R9 represents a divalent group containing at least 2 carbon atoms. Furthermore, in the formula (b), R2 represents a divalent group containing 30 or less carbon atoms and at least 2 carbon atoms.
また(1)([[)におけるR、、R,は、同一かまt
こは異なるものいずれでもよく、また13個よりも少な
い炭素原子を持っている直鎖のもしくは分枝したアルキ
レン基か、環の中に5個もしくは6個の炭素原子を持っ
ている環状アルキレン基か、O9N及びS原子の少なく
とも1個を含む異種環状基か、またはフェニレンもしく
は多環状芳香族基とすることもできる。これらの種々の
基は反応条件のらとで不必要な1.flJ反応を与えな
い置換=基を持っていてもよい。また上記R,,R2は
、たくさんの7二二レン基か、または脂環状の基とする
こともできる。この場合において、隣合うフェニレン基
または脂環状基は直接に結合される他、酸素もしくは硫
黄などの2価の原子を介して結合されるが、または炭素
原子1個から3個のフルキレン群もしくけ以下の群の内
の1つの群を介して結合されることがある。これらの原
子または群が複数存在する場合には、それぞれが同じで
あってもよく、異なっていてもよい。Also, in (1) ([[), R, ,R, are the same
This may be any different and may be a straight-chain or branched alkylene group having fewer than 13 carbon atoms or a cyclic alkylene group having 5 or 6 carbon atoms in the ring. or a heterocyclic group containing at least one O9N and S atom, or a phenylene or polycyclic aromatic group. These various groups may be unnecessary depending on the reaction conditions. It may have a substituent = group that does not give flJ reaction. Moreover, the above R,, R2 can also be a large number of 72-dylenes groups or an alicyclic group. In this case, adjacent phenylene groups or alicyclic groups may be bonded directly, or may be bonded via a divalent atom such as oxygen or sulfur, or a fullylene group of 1 to 3 carbon atoms may also be bonded. May be coupled through one of the following groups: When a plurality of these atoms or groups exist, each of them may be the same or different.
−NR4−1−P(0)R,−1−N=N−1−N=N
−1−CO−O−1−SO2−1↓
−S i R) R<−1CON H−1−NY−Co
−X−CO−NY−1
−o−co−x−co−o−1
R3
上記式中R5、R4及びYは各々炭素原子1個から・1
個のアルキル基、環中(こ5個もしくは6個の炭素原子
を持つ環状アルキル基、らしくはフェニルまたは多環状
芳香族基を表し、Xは13個より少ない炭素原子を持っ
ている直鎖らしくは分枝したアルキレン基、環中に5個
もしくは6個の炭素原子を持っている環状アルキレン基
、または単環もしくは多環状アリレン基を表す。-NR4-1-P(0)R, -1-N=N-1-N=N
-1-CO-O-1-SO2-1↓ -S i R) R<-1CON H-1-NY-Co
-X-CO-NY-1 -o-co-x-co-o-1 R3 In the above formula, R5, R4 and Y each have from 1 to 1 carbon atom
an alkyl group in the ring (this represents a cyclic alkyl group with 5 or 6 carbon atoms, likely phenyl or a polycyclic aromatic group, and X is a linear chain with fewer than 13 carbon atoms) represents a branched alkylene group, a cyclic alkylene group having 5 or 6 carbon atoms in the ring, or a monocyclic or polycyclic arylene group.
基りは(III)式のエチレン系j1に水物から誘導さ
れるもので、例えばマレイン酸無水物、シトラコン陵無
水物、テトラヒドロフタル酸無水物、イタコン酸無水物
、及びシクロジエンとこれ等の無水物の1つの間に起こ
るディールス−アルグー反応の生成物を挙げることがで
きる。The bases are those derived from hydrates in the ethylene system j1 of formula (III), such as maleic anhydride, citracone anhydride, tetrahydrophthalic anhydride, itaconic anhydride, and cyclodiene and these anhydrides. Mention may be made of the products of the Diels-Argout reaction occurring between one of the substances.
O
/′ \
C○
使用することので゛きる式(1)の好ましい不飽和ビス
−イミドとしては次のものを挙げることができる。マレ
イン酸N−N’−エチレン−ビス−イミド、マレイン酸
N−N′−ヘキサメチレン−ビス−イミド、マレインf
iN−N’−メタフェニレン−ビス−イミド、マレイン
酸N−N ′−バラフェニレンービスーイミド、マレイ
ン酸N−N’−・t・4 ′−ノフェニルメタン〜ビス
ーイミI’、[N・N′−メチレンビス(N−フェニル
マンイミド)とも言う]、マレイン酸N−N ′−4・
4 ′−ノフェニルエーテルービスーイミド、マレ4冫
1′−4・4′−ジフェニルスルホン−ビス−イミド、
マレイン酸N−N ’ー4ー4 ’ーノシクロヘキシル
メタンービスーイミド、マレイン酸N−N′−α・α゛
−4・4 ′ーノメチレンシクIフヘキサンービスーイ
ミr1マレイン酸N−N ′ーメタキシリレンービスー
イミド、マレイン酸N−N ′ーンフェニルシクロヘキ
サンービスーイミドなどである。O/'\C○ Preferred unsaturated bis-imides of formula (1) that can be used include the following. Maleic acid N-N'-ethylene-bis-imide, maleic acid N-N'-hexamethylene-bis-imide, maleic f
iN-N'-metaphenylene-bis-imide, maleic acid N-N'-paraphenylene-bis-imide, maleic acid N-N'-・t・4′-nophenylmethane~bis-imide I′, [N・N '-methylenebis(N-phenylmanimide)], maleic acid N-N'-4.
4′-nophenyl ether bis-imide, male 4′-1′-4,4′-diphenyl sulfone-bis-imide,
Maleic acid N-N'-4-4'-cyclohexylmethane-bis-imide, maleic acid N-N'-α・α゛-4,4'-methylenecyclyl fuhexane-bis-imide r1 Maleic acid N-N'-meta These include xylylene-bis-imide, maleic acid N-N'-phenylcyclohexane-bis-imide, and the like.
また使用することのできる式(II)の好ましいシ゛ア
ミンとしては次のものを挙げることができる。Preferred cyamines of formula (II) that can be used include the following.
4−4′−ノアミ7ノシクロヘキシルメタン、1・4′
−ノアミノシクロヘキサン、2・6−ジアミノビリノン
、メタフェニレンノアミン、バラフェニレンノアミン.
414 ’ーノアミ/ーノフェニルメタン、2・2−ビ
ス−(4−アミ7フエニル)フ゛ロバン、ベンジノン、
・t・4’−ジアミ7シ7工二ル才キサイド、・t・4
′−ノアミ/ノフェニルサル7アイド、4・4 ゛−ノ
アミ7ノフェニルスル7オン、ビス−(4−アミ/フェ
ニル)ンフェニルシラン、ビス−(4−アミ/フェニル
)メチル7オスフインオキサイド、ビス−(3−アミノ
フェニル)メチル7すスフィンオキサイド、ビス−(=
iミーアミ/フェニルフェニル7オスフインオキサイド
、ビス−(4−アミ/フェニル)フェニラミン、1・5
−ノアミ/す7りl/ン、メタキシリレンノアミン、パ
ラキシリレンノアミン、1・1−ビス−(バラアミ/フ
ェニル)フタラン、ヘキサメチレンジアミンなどである
。4-4'-Noami7nocyclohexylmethane, 1,4'
-Noaminocyclohexane, 2,6-diaminobilinone, metaphenylenenoamine, paraphenylenenoamine.
414 'Noami/nophenylmethane, 2,2-bis-(4-ami7phenyl)ferobane, benzinone,
・t・4'-jiami7shi7engineniruzaikiside,・t・4
'-Noami/nophenylsul7ide, 4,4'-noami7nophenylsul7one, bis-(4-amino/phenyl)nphenylsilane, bis-(4-ami/phenyl)methyl7osphinoxide, bis-( 3-aminophenyl)methyl 7-suphine oxide, bis-(=
i-amiami/phenylphenyl 7-osphine oxide, bis-(4-ami/phenyl)pheniramine, 1.5
-norami/su7rin/in, metaxylylenenoamine, paraxylylenenoamine, 1,1-bis-(barami/phenyl)phthalane, hexamethylenediamine, and the like.
上記不飽和ビス−イミドとノアランとを非プロトン性極
性溶剤中で反応させて付加型イミトリ(脂プレポリマー
を調製するものであるが、非プロトン性極性溶剤として
は、N−メチル−2−ピロリドン、N−N−ノメチルホ
ルムア′8:1″、N−N−ジメチルアセトアミド、1
.3−ツメチル−2−イミグゾリノ/ン、ツメチルスル
ホオキシドなどを用いろ、:とができる。これらは1種
または2種以上を混合して用いることができる。The above-mentioned unsaturated bis-imide and Noalane are reacted in an aprotic polar solvent to prepare an addition-type imitri (lipid prepolymer). As the aprotic polar solvent, N-methyl-2-pyrrolidone , N-N-nomethylforma '8:1'', N-N-dimethylacetamide, 1
.. Using 3-methyl-2-imigzolinone, trimethyl sulfoxide, etc., can be obtained. These can be used alone or in combination of two or more.
ここで、付加型イミトリ(脂プレポリマーはこの反応に
用いる?′8削1こ′18解させた状態でワニスとして
用い、基材への含浸に供されるものであり、このとき塗
工機等て゛塾材にワニスを含浸さ1士る1ごあtこって
一度の含浸工程で基材のレノンフンテントが47〜50
%になるよう]こ、ワニス)負度を155〜65%の^
6ン農度に設定することがお1:なわれる。Here, the addition-type polymer (fatty prepolymer used in this reaction) is used as a varnish in a decomposed state and used for impregnation into the base material, and at this time, the coating machine For example, impregnating the material with varnish will result in a coating of 47 to 50% of the base material in one impregnation process.
%] This varnish) Negativity should be 155-65% ^
It is recommended to set the agricultural rate to 6.
そしてこのような高濃度のワニスを得ようとした場合に
おいて、非プロトン性礪性I8媒のかわりにプロトン性
極性溶媒を用いると、付加型イミド8(脂プレポリマー
はプロトン性極性溶媒への溶解性が良好でなく、ワニス
中に固形物が沈澱したりにごりとして析出したりする不
都合を生じることになる。従って本発明においては不飽
和ビス−イミドとジアミンとを非プロトン性極性溶剤中
で反応させて付加型イミド8(脂プレポリマーを調製す
るものである。When trying to obtain a varnish with such a high concentration, if a protic polar solvent is used instead of the aprotic abrasive I8 medium, addition type imide 8 (fatty prepolymer is dissolved in the protic polar solvent). Therefore, in the present invention, unsaturated bis-imide and diamine are reacted in an aprotic polar solvent. Addition type imide 8 (fat prepolymer is prepared).
またこの反応において、その反応温度は50℃以上、1
00°C未満に設定される。反応温度が50°C未満で
あると、反応がほとんど進行せず、また反応温度が10
0“C以上であると、基材との反応活性に乏しい高分子
量物が付加型イミドO(脂プレポリマーに多量に生成さ
れるという不都合を生じるものである。さらにこの反応
は付加型イミドυ(脂プレポリマー中の残存未反応原料
が35〜50重量%となる時点て・終了されるように調
整される。付加型イミドυ5脂プレポリマー中の残存未
反応原料が35重量%未満であると、基材との反応活性
に乏しい高分子量物が多く生成されることになり、また
50重量%を超えるとプレポリマー溶液(ワニス)中に
未反応原料が析出するという不都合を生じることになる
。In addition, in this reaction, the reaction temperature is 50°C or higher, 1
Set below 00°C. If the reaction temperature is less than 50°C, the reaction will hardly proceed;
If it is 0"C or more, a large amount of high molecular weight substances with poor reaction activity with the base material will be produced in the addition type imide O (fat prepolymer). Furthermore, this reaction will cause the disadvantage that the addition type imide υ (It is adjusted so that the remaining unreacted raw material in the fat prepolymer reaches 35 to 50% by weight. The remaining unreacted raw material in the addition type imide υ5 fat prepolymer is less than 35% by weight. If the amount exceeds 50% by weight, unreacted raw materials will precipitate in the prepolymer solution (varnish). .
ここで、この反応調整のために付加型イミド樹脂プレポ
リマーの分子量分布を測定する必要があるが、この分子
量分布はDMF溶媒を使用し、分離カラムとして昭和電
工(株)製AD−803/S(8,OX250mm、理
論段数6000段)を2本装着したデル浸透クロマトグ
ラフ(東洋ソーブ(株)製HLC−803D)によって
測定することかて゛きる。分子量の計算は、5種類の単
分散ポリエチレングリコールおよびエチレングリコール
モア7−のリテンシジンタイムと分子量の常用対数から
、3次式の回帰曲線を求め、これを試料に適用し、試料
のりテンションタイムから逆に分子量を求めるという方
法でおこなうことができる。また各成分の割合(%)は
、示差屈折計(128X11−8RI単位)を用い、試
料濃度を0.5±0.2%、試料注入量を100μlと
して測定し、屈折計出力0〜1■、チャート速度5 +
1161/分として得られたクロマトグラフを、必要な
分子量区分に分け、切り抜き重量法により、それぞれの
比率を求めることによって算出することができる。Here, it is necessary to measure the molecular weight distribution of the addition-type imide resin prepolymer in order to adjust this reaction. It is possible to measure using a Dell permeation chromatograph (HLC-803D manufactured by Toyo Sorb Co., Ltd.) equipped with two (8, OX 250 mm, theoretical plates 6000 plates). To calculate the molecular weight, a cubic regression curve is obtained from the retention time and the common logarithm of the molecular weight of five types of monodispersed polyethylene glycols and ethylene glycol moa7-, and this is applied to the sample, and the regression curve is calculated from the sample glue tension time. Conversely, this can be done by determining the molecular weight. In addition, the proportion (%) of each component was measured using a differential refractometer (128 x 11-8 RI units) with a sample concentration of 0.5 ± 0.2% and a sample injection amount of 100 μl, and the refractometer output was 0 to 1 μl. , chart speed 5 +
It can be calculated by dividing the chromatograph obtained as 1161/min into necessary molecular weight categories and determining the respective ratios using the cutout weight method.
さらに、不飽和ビス−イミドとジアミンとを反応させる
にあたっての不飽和ビス−イミドとジアミンとの配合割
合は、モル比て1,0/1.0〜10/1が一般的で、
特に1.0/1.0〜3/1が好ましい。不飽和ビス−
イミドの配合量が多すぎると未反応原料が多く残存し易
くなってプレポリマー溶f1.(ワニス)に析出物が発
生し易くなり、逆にジアミンの配合量が多すぎると付加
型イミド444脂プレポリマーに高分子量物の生成が多
くなるものである。Furthermore, when reacting unsaturated bis-imide and diamine, the molar ratio of unsaturated bis-imide and diamine is generally 1.0/1.0 to 10/1.
Particularly preferred is 1.0/1.0 to 3/1. unsaturated bis-
If the amount of imide blended is too large, a large amount of unreacted raw material tends to remain, causing the prepolymer to dissolve f1. Precipitates are likely to form in the (varnish), and conversely, if the amount of diamine blended is too large, a large amount of high molecular weight substances will be produced in the addition type imide 444 resin prepolymer.
上記のようにして得られる付加型イミド樹脂プレポリマ
ーのプレポリマー溶液(ワニス)は、プリント配線板に
おける積層板のtJl造にあたって基材に含浸されるが
、基材の種類は特に限定されない。The prepolymer solution (varnish) of the addition-type imide resin prepolymer obtained as described above is impregnated into a base material when manufacturing a laminate for a printed wiring board, but the type of the base material is not particularly limited.
通常はプラスクロスが用いられることになるが、その他
石英lyL維布などの無機繊維布、ケブラー繊41k
Ie f、−1/ 、f−1j:I: b土19.I
/I−Lm ii# 、酎:4 t−1711、入
ν シ t f” &る。そして基材に常法に従
ってプレポリマー溶液を含浸したのち、加熱乾燥してプ
リプレグを作成し、このようにして得たプリプレグI数
枚を、銅、ニッケル等の金属箔あるいは回路形成された
内層材とともに積層すると共に、常法に従って加熱加圧
して積層成形することによって、プリント配線板を得る
ものである。Normally, plus cloth is used, but other inorganic fiber cloth such as quartz lyL fiber cloth, Kevlar fiber 41k
Ie f, -1/, f-1j: I: b Sat 19. I
/I-Lm ii#, Shochu: 4 t-1711, Enter ν S t f” &ru.Then, the base material was impregnated with the prepolymer solution according to a conventional method, and then heated and dried to create a prepreg. A printed wiring board is obtained by laminating several sheets of the prepreg I obtained by laminating them together with a metal foil such as copper or nickel or an inner layer material on which a circuit is formed, and then heating and pressing them to form a laminated layer according to a conventional method.
次に本発明を実施例によって説明する。Next, the present invention will be explained by examples.
第1表に示す原料を第1表の配合で32の四つロフラス
コに計り込み、撹拌棒、温度計、冷却器をフラスコに取
り付けたのち、側口上り窒素ガスをフラスコに通じた。The raw materials shown in Table 1 were measured in the proportions shown in Table 1 into a 32 four-hole flask, and a stirring rod, a thermometer, and a condenser were attached to the flask, and then nitrogen gas was introduced into the flask from the side port.
このようにしてフラスコ内の空気を窒素置換したのち、
オイルバスによって加熱をおこなった。内容物の溶解に
伴って攪拌を開始し、第1表に示す加熱温度に設定して
反応をおこなわせた。そして第1表に示す時間攪拌を続
けたのち、すばやく反応物を室温まで冷却してプレポリ
マー溶液を得た(実施例1乃至4、比較例1乃至4)。After replacing the air in the flask with nitrogen in this way,
Heating was performed using an oil bath. Stirring was started as the contents were dissolved, and the reaction was carried out by setting the heating temperature shown in Table 1. After continuing stirring for the time shown in Table 1, the reactants were quickly cooled to room temperature to obtain prepolymer solutions (Examples 1 to 4, Comparative Examples 1 to 4).
このようにして得られた実施例1乃至4、比較例1乃至
4の付加型イミド樹脂プレポリマー溶液の分析値及び特
性値を第2表に示す。Table 2 shows the analytical values and characteristic values of the addition type imide resin prepolymer solutions of Examples 1 to 4 and Comparative Examples 1 to 4 thus obtained.
第1表においてXlは構造式が
で示され、*2は構造式が
で示されるものである。また第2表において[樹脂組成
」(玉量%)は、前記のデル浸透クロマトグラフ(GP
C)測定におけるピーク面積から算出したものである。In Table 1, Xl has a structural formula, and *2 has a structural formula. In addition, in Table 2, "resin composition" (ball percentage) is based on the Dell permeation chromatograph (GP) described above.
C) Calculated from the peak area in measurement.
さらに第2表において1安定性」は、それぞれのプレポ
リマー溶液を設定温度(20”(:’、−5°C)で放
置したときの安定性を示すものであり、プレポリマー溶
液がらの固形分の析出の有無によって判定した。「安定
性」の欄において○は7日以上安定、Δは7日未満に固
形分析出、×は1日以内に固形分析出を示す。Furthermore, in Table 2, "1 Stability" indicates the stability when each prepolymer solution is left at the set temperature (20"(:', -5°C), and the solid state of the prepolymer solution Judgment was made based on the presence or absence of precipitation. In the "stability" column, ○ indicates stability for 7 days or more, Δ indicates solid analysis occurs in less than 7 days, and × indicates solid analysis within 1 day.
次に実施例1乃至4、比較例1乃至4の付加型イミド樹
脂プレポリマー溶液を用い、表面処理をおこなった1
05 (3/ tn2の〃ラスクロスに第3表に示す条
件で含浸をおこなった。そして乾燥行中で加熱して2次
反応をおこなわせることにより、レノンコンテントが4
7〜50%のプリプレグを作成した(実施例5乃至8、
比較例5乃至8)。得られたプリプレグの特性を第3表
に示す。Next, surface treatment was performed using the addition type imide resin prepolymer solutions of Examples 1 to 4 and Comparative Examples 1 to 4.
05 (3/tn2) was impregnated under the conditions shown in Table 3. Then, by heating in the drying line to perform a secondary reaction, the renone content was reduced to 4.
7 to 50% prepreg was created (Examples 5 to 8,
Comparative Examples 5 to 8). Table 3 shows the properties of the obtained prepreg.
犬にこのようにして得られたプリプレグを30emX
30 amの大きさにし、これを4枚% h 、この両
数外面に表面処理をおこなった同サイズの0゜5オンス
/ft2の銅箔を置いて、これを1.61厚の金型に挟
み、蒸気プレスを用いて5KH/cm2の加圧をおこな
いつつ直ちに130℃まで加熱し、20分間保持した。The prepreg thus obtained was given to a dog at 30<em>X
30 am in size, 4% h of this, placed a 0°5 oz/ft2 copper foil of the same size with surface treatment on both outer surfaces, and put this into a 1.61 thick mold. It was immediately heated to 130° C. while applying a pressure of 5 KH/cm 2 using a steam press and held for 20 minutes.
さらに圧力を10 K g/ am2に設定すると共に
170°Cに加熱し、90分後に圧力をかけたまま室温
まで冷却することによって、両面銅張り積層板を得た(
*地側9乃至12、比較例9乃至12)。得られた積層
板の性能を第4表に示す。Further, the pressure was set to 10 Kg/am2 and heated to 170°C, and after 90 minutes, the material was cooled to room temperature with the pressure applied to obtain a double-sided copper-clad laminate (
*Base side 9 to 12, Comparative Examples 9 to 12). Table 4 shows the performance of the obtained laminate.
第3表において「8(脂組成」はGPC測定におけるピ
ーク面積から算出したものであり、また「プリプレグ外
観」における判定基準は、○;樹脂むら無し、×;樹脂
むら有ワである。さらに第4表の「エツチング後の板外
観」における判定基準は、○;かすれやボイド無し、×
:がすれやボイド有りであり、また「熱膨張率」は40
〜250℃までの間の(以下余、白)1
1 」
第1表、第2表のように溶媒として非プロトン性極性溶
媒を用い、反応温度を150〜100°Cに設定すると
共に残存する未反応原料が35〜50%となるように反
応を調整した実施例1乃至4の付加型イミド樹脂プレポ
リマーは、第2表に見られるように安定性iこ優れ、ま
た第3表に見られるようにプリプレグの外観に優れ、さ
らに第4表に見られるようにプリント配線板において層
間接着力が高いと共に、熱膨張率が小さいことが確認さ
れる。従って本発明において製造される付加型イミド樹
脂プレポリマーは高密着性や低熱膨張率を示すポリイミ
ドを与えることが確認される。In Table 3, "8 (fat composition)" is calculated from the peak area in GPC measurement, and the criteria for "prepreg appearance" are: ○: no resin unevenness, ×: resin unevenness. The criteria for the “board appearance after etching” in Table 4 are: ○; no fading or voids; ×
: There are scratches and voids, and the "thermal expansion coefficient" is 40.
~250°C (remainder, white) 1 1 ” Using an aprotic polar solvent as the solvent as shown in Tables 1 and 2, the reaction temperature is set at 150 to 100°C and the remaining The addition type imide resin prepolymers of Examples 1 to 4, in which the reaction was adjusted so that the unreacted raw material content was 35 to 50%, had excellent stability as shown in Table 2, and as shown in Table 3. As shown in Table 4, the prepreg has an excellent appearance, and as shown in Table 4, it has a high interlayer adhesive strength and a low coefficient of thermal expansion in printed wiring boards. Therefore, it is confirmed that the addition type imide resin prepolymer produced in the present invention provides a polyimide exhibiting high adhesiveness and low coefficient of thermal expansion.
[発明の効果]
上述のように本発明は、一般式が
(式中りは炭素−炭素間の二重結合を有する2価の有機
基を表し、R,は少なくとも2個の炭素原子を含む2価
の基を表す。)の不飽和ビス−イミドと、一般式が
王−(、N−+イ、−N )(。[Effects of the Invention] As described above, the present invention has the following advantages: represents a divalent group) and an unsaturated bis-imide whose general formula is -(, N-+i, -N) (.
(式中[で、は少なくと(,12個の炭素原rを含む2
価の基を表す。)のノアランとを、非プロトン性極性溶
媒中で50 ’C以上100 ’C未満の温度で、残存
rる未反応原!4が35−50%になるまC反応さ瞳る
ようにしたものであり、溶媒として非プロトン性極性溶
媒を用い、反応温度をi30〜10()Cに設定すると
共に残存rる未反応原料が35〜50%となるように反
応を調整rることで、基祠との高い密着性や低熱膨張率
を示す付加型イミド樹脂プレポリマーを得ることができ
るらのである。(In the formula, [ is at least (, 2 containing 12 carbon atoms r
Represents a valence group. ) in an aprotic polar solvent at a temperature of 50'C or more and less than 100'C, the remaining unreacted raw material! The C reaction is allowed to continue until 4 is 35-50%, and an aprotic polar solvent is used as the solvent, the reaction temperature is set at 30 to 10 C, and the remaining unreacted raw material is By adjusting the reaction so that the ratio is 35 to 50%, it is possible to obtain an addition-type imide resin prepolymer that exhibits high adhesion to the substrate and a low coefficient of thermal expansion.
代理人 弁理士 石En艮七
手続有音1正店:(自発)
昭和61年2月28[j
昭和61年特許顧第15020号
2、発明の名称
付加型イミド樹脂ブ1〆ボリマーの製造法3、補正をす
る者
事件との関係 特許出願人
住 所 大阪府門真市大字門真1048番地名称(58
3)松下電工株式会社
代表者 藤 井 1 犬
・t1代理人
郵便番号 530
5、補正命令の日付
自 発
6、補正により増加する発明の数 なし7、補正の対末
明細書 −1〜−1、ツメl
、而へ。Agent: Patent Attorney Seki En 艮 7 Proceedings 1 Profession: (Voluntary) February 28, 1985 [j 1986 Patent Attorney No. 15020 2, Process for producing a named imide resin binder polymer 3. Relationship with the case of the person making the amendment Patent applicant address 1048 Kadoma, Kadoma City, Osaka Prefecture Name (58
3) Matsushita Electric Works Co., Ltd. Representative Fujii 1 Inu/t1 agent postal code 530 5. Date of amendment order 6. Number of inventions increased by amendment None 7. End of amendment Specification -1 to -1 , Tsume l, to.
Claims (1)
基を表し、R_1は少なくとも2個の炭素原子を含む2
価の基を表す。)の不飽和ビス・イミドと、一般式が H_2N−R_2−NH_2 (式中R_2は少なくとも2個の炭素原子を含む2価の
基を表す。)のジアミンとを、非プロトン性極性溶媒中
で50℃以上100℃未満の温度で、残存する未反応原
料が35〜50%になるまで反応させることを特徴とす
る付加型イミド樹脂プレポリマーの製造法。(1) General formulas include ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, D represents a divalent organic group having a carbon-carbon double bond, and R_1 is a
Represents a valence group. ) and a diamine with the general formula H_2N-R_2-NH_2 (wherein R_2 represents a divalent group containing at least two carbon atoms) in an aprotic polar solvent. A method for producing an addition-type imide resin prepolymer, which comprises reacting at a temperature of 50° C. or more and less than 100° C. until the remaining unreacted raw material becomes 35 to 50%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1502086A JPS62172025A (en) | 1986-01-27 | 1986-01-27 | Production of addition type imide resin prepolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1502086A JPS62172025A (en) | 1986-01-27 | 1986-01-27 | Production of addition type imide resin prepolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62172025A true JPS62172025A (en) | 1987-07-29 |
JPH0359090B2 JPH0359090B2 (en) | 1991-09-09 |
Family
ID=11877167
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1502086A Granted JPS62172025A (en) | 1986-01-27 | 1986-01-27 | Production of addition type imide resin prepolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62172025A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0431435A (en) * | 1990-05-28 | 1992-02-03 | Matsushita Electric Works Ltd | Addition type imide resin prepolymer and resin film prepared therefrom |
JPH05148360A (en) * | 1991-11-29 | 1993-06-15 | Matsushita Electric Works Ltd | Production of polyimide resin |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5856383A (en) * | 1981-09-29 | 1983-04-04 | 日立化成工業株式会社 | Method of producing printed circuit board |
-
1986
- 1986-01-27 JP JP1502086A patent/JPS62172025A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5856383A (en) * | 1981-09-29 | 1983-04-04 | 日立化成工業株式会社 | Method of producing printed circuit board |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0431435A (en) * | 1990-05-28 | 1992-02-03 | Matsushita Electric Works Ltd | Addition type imide resin prepolymer and resin film prepared therefrom |
JPH05148360A (en) * | 1991-11-29 | 1993-06-15 | Matsushita Electric Works Ltd | Production of polyimide resin |
Also Published As
Publication number | Publication date |
---|---|
JPH0359090B2 (en) | 1991-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4393188A (en) | Thermosetting prepolymer from polyfunctional maleimide and bis maleimide | |
US4526835A (en) | Multi-layer printed circuit board and process for production thereof | |
JPS61163938A (en) | Addition-type imide resin prepolymer, prepreg and laminated sheet | |
CN101068851B (en) | Polyimide, polyimide film and laminated body | |
US5508357A (en) | Polyimides, thermosetting resin compositions containing the polyimides, formed articles of the resin compositions, and production process of polyimides | |
WO2006118230A1 (en) | Material for plating and use thereof | |
FR2463784A1 (en) | PROCESS FOR PREPARING A THERMOSETTING IMIDE TYPE PREPOLYMER AND IMIDE-TYPE PREPOLYMER OBTAINED BY THIS METHOD | |
US4283522A (en) | Process for preparing thermosetting prepolymer from mixture of polyfunctional maleimide and bis-maleimide | |
JPS62172025A (en) | Production of addition type imide resin prepolymer | |
JPH01129025A (en) | Polyaminobisimide resin | |
JPS60210640A (en) | Production of laminated sheet | |
JPS62235383A (en) | Thermosetting adhesive film | |
JP2606390B2 (en) | Polyimide adhesive sheet and method for producing the same | |
JPH03185066A (en) | Thermosetting resin composition | |
JPS5810419B2 (en) | Solutions with good storage stability and their usage | |
JPS6225126A (en) | Addition-type imide resin prepolymer, prepreg and laminated board | |
JPH04351634A (en) | Adhesive capable of being chemically etched | |
JPS6140322A (en) | Production of curable polyaminobisimide resin | |
JPH01157846A (en) | Manufacture of flexible laminated plate lined with metal on both sides | |
JPS60202130A (en) | Addition-type imide resin prepolymer, prepreg, and laminated sheet | |
JPH01245024A (en) | Addition type imide resin prepolymer, prepreg and laminate | |
JPH01240526A (en) | Addition type imide resin prepolymer, prepreg and laminated board | |
JPH02289620A (en) | Reaction catalyst for addition-type imide resin prepolymer formation | |
JPH0345626A (en) | Addition type imide resin prepolymer and its production, prepreg and laminate | |
JPH01161031A (en) | Fluorinated bismaleimide resin composition for laminated sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |