JPH03252478A - Film adhesive - Google Patents
Film adhesiveInfo
- Publication number
- JPH03252478A JPH03252478A JP5059190A JP5059190A JPH03252478A JP H03252478 A JPH03252478 A JP H03252478A JP 5059190 A JP5059190 A JP 5059190A JP 5059190 A JP5059190 A JP 5059190A JP H03252478 A JPH03252478 A JP H03252478A
- Authority
- JP
- Japan
- Prior art keywords
- film
- anhydride
- diamine
- lower alkyl
- adhesive
- 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
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 239000000853 adhesive Substances 0.000 title claims abstract description 28
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- 229920005575 poly(amic acid) Polymers 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000009719 polyimide resin Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000012644 addition polymerization Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Adhesive Tapes (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、耐熱性、接着性に優れた、回路板等に好適な
ポリイミド樹脂によるフィルム状の接着剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a film-like adhesive made of polyimide resin that has excellent heat resistance and adhesive properties and is suitable for circuit boards and the like.
（従来の技術）
従来、回路板に使用されるフィルム接着剤は、ポリエス
テル系樹脂またはエポキシ系樹脂のものがほとんどであ
った。 ポリエステル系のフィルム接着剤は、耐熱性が
低く、高温で処理される回路板用としては不適であった
。 またエポキシ系のフィルム接着剤は、可撓性や誘電
特性に劣るという欠点があった。 耐熱性フィルム接着
剤のなかで、ポリイミド前駆体であるポリアミド酸樹脂
溶液を塗布してフィルム化し、接着の際に高温でイミド
化するものは、ポリイミド前駆体の組成によっては、生
成ポリイミド展と金属箔又は板との接着力が不十分とな
り、回路パターン形成時にいずれかの接着面で剥離現象
を生じ、不良の原因となる欠点があった。(Prior Art) Conventionally, most film adhesives used for circuit boards have been polyester resins or epoxy resins. Polyester film adhesives have low heat resistance and are unsuitable for circuit boards that are processed at high temperatures. Furthermore, epoxy film adhesives have the disadvantage of poor flexibility and dielectric properties. Among heat-resistant film adhesives, those that apply a polyamic acid resin solution, which is a polyimide precursor, to form a film and imidize it at high temperature during adhesion, depending on the composition of the polyimide precursor, may cause the formation of polyimide expansion and metal The adhesive force with the foil or plate is insufficient, and peeling occurs on either adhesive surface during circuit pattern formation, resulting in defects.
（発明が解決しようとする課題）
本発明は、上記の欠点を解消するためになされたもので
、耐熱性、接着性に優れ、取扱いが容易で回路板の生産
性、経済性に寄与するフィルム接着剤を提供しようとす
るものである。(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned drawbacks, and is a film that has excellent heat resistance and adhesive properties, is easy to handle, and contributes to the productivity and economic efficiency of circuit boards. The aim is to provide adhesives.
［発明の構成］
（課題を解決するための手段）
本発明者らは、上記の目的を達成しようと鋭意研究を重
ねた結果、後述する特定のポリイミド樹脂からなるフィ
ルム接着剤が上記の目的を達成することを見いだし、本
発明を完成したものである。[Structure of the Invention] (Means for Solving the Problem) As a result of intensive research aimed at achieving the above object, the present inventors have found that a film adhesive made of a specific polyimide resin described below achieves the above object. The present invention has been completed by discovering what the invention has achieved.
すなわち、本発明は、
（Ａ） （１） ｓ、ｓ′、 ４．４′−ベンゾフ
ェノンテトラカルボン酸くその無水物及び低級アルキル
エステルを含む）と（２） ４．４′−オキシフタル
酸くその無水物及び低級アルキルエステルを含む）のモ
ル比が９９／１〜１／９９の混合物を９５モル％以上含
む芳香族テトラカルボン酸と、
（Ｂ）一般式（Ｉ）又は（Ｉ）
（但し、式中Ｘは、ＣＨ２，０１Ｓ０２、Ｃ（ＣＨ３）
２ 、Ｃ（ＣＦ３ ）２又はＳを、Ｒ１Ｒ２は、ＣＨ３
、Ｃ２Ｈ５、ＯＣＨ３又はＱＣ２Ｈ，を、Ｒ３，Ｒ’は
Ｃ２Ｈ，を、Ｒ５はフェニル基又はシクロヘキサン基を
表し、Ｒ１−Ｒ４はいずれもＲ５に関してアミノ基のオ
ルソ位に置換されている）で示される芳香族ジアミンを
１０モル％以上含むジアミン
とを反応させてなることを特徴とするフィルム接着剤で
ある。That is, the present invention provides (A) (1) s, s', 4,4'-benzophenonetetracarboxylic acid anhydrides and lower alkyl esters) and (2) 4,4'-oxyphthalic acid. (B) general formula (I) or (I) In the formula, X is CH2,01S02, C(CH3)
2, C(CF3)2 or S, R1R2 is CH3
, C2H5, OCH3 or QC2H, R3, R' represents C2H, R5 represents a phenyl group or a cyclohexane group, and R1-R4 are all substituted at the ortho position of the amino group with respect to R5). This film adhesive is produced by reacting an aromatic diamine with a diamine containing 10 mol% or more.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明に用いる（Ａ＞芳香族テトラカルボン酸としては
、 （１） ３．３’、 ４．４′−ベンゾフェノン
テトラカルボン酸（その無水物及び低級アルキルエステ
ルを含む）と（２）４．４′−オキシフタル酸（その無
水物及び低級アルキルエステルを含む）とのモル比が９
９／１〜１／９９の混合物で、かつ９５モル％以上含む
ものである。 またこの混合物以外の芳香族テトラカル
ボン酸を５モル％未満含んでもよい。The (A> aromatic tetracarboxylic acids used in the present invention) include (1) 3.3', 4.4'-benzophenone tetracarboxylic acid (including its anhydride and lower alkyl ester) and (2) 4.4 '-oxyphthalic acid (including its anhydride and lower alkyl ester) in a molar ratio of 9
It is a mixture of 9/1 to 1/99 and contains 95 mol% or more. The mixture may also contain less than 5 mol% of aromatic tetracarboxylic acids other than this mixture.
なお、（２）４．４’−オキシフタル酸は、次式に示さ
れる化合物である。In addition, (2) 4,4'-oxyphthalic acid is a compound shown by the following formula.
本発明に用いる（Ｂ）ジアミンとしては、一般式＜Ｉ）
又は（ＩＩ）
（但し、式中Ｘは、ＣＨ２，０、ＳＯ２、Ｃ（ＣＨ３）
２、Ｃ（ＣＦ３）２又はＳを、Ｒ１Ｒ２は、ＣＨ，、Ｃ
２Ｈ，，０ＣＲ３又はＱＣ２Ｈ，を、Ｒ３，Ｒ’はＣ，
Ｈ，を、Ｒ５はフェニル基又はシクロヘキサン基を表し
、Ｒ１−Ｒ４はいずれもＲ５に関してアミノ基のオルソ
位に置換されている）で示される芳香族ジアミンを１０
モル％以上含むジアミンである。 芳香族ジアミンとし
ては、３，３′−ジメチル−５，５′−ジエチル−４，
４′−ジアミノジフェニルメタン、３．３”、 ５．５
′−テトラエチル−４，４′−ジアミノジフェニルメタ
ン、３．３′−ジメチル−４，４′−ジアミノジシクロ
ヘキシルメタン、３．３′−ジメトキシ−４，４′−ジ
アミノジフェニルメタン、３，３′−ジェトキシ−４，
４′−ジアミノジフェニルメタン、３．３′−ジエチル
−４，４′−ジアミノジフェニルエーテル、３，３′−
ジメトキシ−４，４′−ジアミノジフェニルエーテル、
３，３′−ジメチル−４，４’−ジアミノジフェニルス
ルホン、３，３′−ジエチル−４４′−ジアミノジフェ
ニルスルホン、３，３′−ジメトキシ−４，４′−ジア
ミノジフェニルスルホン、３．３′−ジェトキシ−４，
４′−ジアミノジフェニルスルホン、３３′−ジメチル
−４，４′−ジアミノジフェニルプロパン、３，３′−
ジエチル−４，４′−ジアミノジフェニルプロパン、３
，３′−ジメトキシ−４，４′−ジアミノジフェニルプ
ロパン、３，３′−ジェトキシ−４，４′−ジアミノジ
フェニルプロパン、３，３′−ジメチル−４，４′−ジ
アミノジフェニルスルファイド、３，３′−ジエチル−
４４′−ジアミノジフェニルスルファイド、３，３′−
ジメトキシ−４，４′−ジアミノジフェニルスルファイ
ド、３．３′−ジェトキシ−４，４′−ジアミノジフェ
ニルスルファイド、４．４′−ジメチル−５，５′−ジ
アミノジフェニルへキサフルオロプロパン等が挙げられ
、これらは単独又は２種以上混合して使用することがで
きる。 また、これらの芳香族ジアミンの他に９０モル
％未満のジアミンを配合することもできる。The diamine (B) used in the present invention has the general formula <I)
or (II) (wherein X is CH2,0, SO2, C(CH3)
2, C(CF3)2 or S, R1R2 is CH,,C
2H,,0CR3 or QC2H, R3, R' is C,
H, R5 represents a phenyl group or a cyclohexane group, and R1-R4 are all substituted at the ortho position of the amino group with respect to R5).
It is a diamine containing mol% or more. As the aromatic diamine, 3,3'-dimethyl-5,5'-diethyl-4,
4'-diaminodiphenylmethane, 3.3", 5.5
'-Tetraethyl-4,4'-diaminodiphenylmethane, 3.3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3.3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-jethoxy- 4,
4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-
dimethoxy-4,4'-diaminodiphenyl ether,
3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diethyl-44'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminodiphenylsulfone, 3.3' -jetoxy-4,
4'-diaminodiphenyl sulfone, 33'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-
Diethyl-4,4'-diaminodiphenylpropane, 3
, 3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-jethoxy-4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3, 3'-diethyl-
44'-diaminodiphenyl sulfide, 3,3'-
Dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-jethoxy-4,4'-diaminodiphenyl sulfide, 4,4'-dimethyl-5,5'-diaminodiphenyl hexafluoropropane, etc. These can be used alone or in a mixture of two or more. Further, in addition to these aromatic diamines, less than 90 mol% of diamines can be blended.
（Ａ）の芳香族テトラカルボン酸と＜８）のジアミンの
反応は、はぼ等モルを有ｍ溶媒中で３０℃以下、好まし
くは０°Ｃ以下の反応温度下に３〜１２時間反応させて
ポリアミド酸溶液が得られる。The reaction between the aromatic tetracarboxylic acid (A) and the diamine <8) is carried out by reacting approximately equimolar amounts in a solvent at a reaction temperature of 30°C or lower, preferably 0°C or lower for 3 to 12 hours. A polyamic acid solution is obtained.
この付加重合反応において用いる有機溶媒としては、例
えばＮ、Ｎ′−ジメチルスルホオキシド、Ｎ。Examples of the organic solvent used in this addition polymerization reaction include N,N'-dimethylsulfoxide and N.
Ｎ′−ジメチルホルムアミド、Ｎ、Ｎ′−ジエチルホル
ムアミド、Ｎ、Ｎ′−ジメチルアセ１〜アミド、ＮＮ′
−メチル−２−ピロリドン、ヘキサメチレンホスホアミ
ド等が挙げられ、これらは単独又は２種以上混合して使
用することができる。 このポリアミド酸溶液を離型紙
またはフィルムにコーティングしてポリイミドフィルム
を作成する場合は、ポリアミド酸樹脂を５〜４０重量％
、好ましくは１０〜３０重量％の濃度とし、かつ対数粘
度が０．５〜６ｄ／ｇ、より好ましくは０，８〜４ ｄ
ｌ／ｇであることが望ましい。 この濃度であるとポリ
イミド樹脂の物性、塗布・乾燥工程の経済性上望ましい
６ボリアミド酸溶液を離型紙又はフィルムにコーティン
グする操作は流延塗布で行われることが好ましく、具体
的には次のようにして行う。 すなわち、離型紙又はフ
ィルムにポリアミド酸溶液を、製膜用スリットから吐出
させて均一な厚さ（一般的に厚さが１０〜３００μ■と
なるように調整する）の塗膜層を形成させる。 その他
コーティング手段としては、ロールコータ−、ナイフコ
ーターコンマコーター、ドクターコーター、フローコー
ター等の公知手段を利用することもできる。 上記のよ
うにして開塾されたポリアミド酸塗布層を、加熱して脱
溶媒および脱水環化し１００〜３５０℃、好ましくは２
００〜３５０℃に加熱してポリイミド樹脂フィルムを形
成し、フィルム接着剤とすることができる。N'-dimethylformamide, N,N'-diethylformamide, N,N'-dimethylace1-amide, NN'
-Methyl-2-pyrrolidone, hexamethylene phosphoamide, etc., and these can be used alone or in combination of two or more. When creating a polyimide film by coating a release paper or film with this polyamic acid solution, add 5 to 40% by weight of polyamic acid resin.
, preferably a concentration of 10 to 30% by weight, and a logarithmic viscosity of 0.5 to 6 d/g, more preferably 0.8 to 4 d/g.
It is desirable that it is 1/g. This concentration is desirable in terms of the physical properties of the polyimide resin and the economics of the coating and drying process. The operation of coating the release paper or film with the 6-bolyamic acid solution is preferably carried out by casting, and specifically, the following method is used: Do it. That is, a polyamic acid solution is discharged onto a release paper or film through a film-forming slit to form a coating layer with a uniform thickness (generally adjusted to a thickness of 10 to 300 .mu.m). Other known coating means such as a roll coater, knife coater, comma coater, doctor coater, flow coater, etc. can also be used. The polyamic acid coating layer opened as described above is heated to remove the solvent and cyclodehydrate to 100 to 350°C, preferably 2
A polyimide resin film can be formed by heating to 00 to 350°C and used as a film adhesive.
こうして得られたフィルム接着剤は、銅箔、アルミニウ
ム箔、ニッケル箔等の金属箔に加熱・加圧して利用する
ことができる。 例えばこのフィルム接着剤を金属箔上
に重ねた後、加熱・加圧してフィルム接着剤を融着させ
る。 この時の温度は２００〜３５０℃、好ましくは３
００〜３５０℃である。The film adhesive thus obtained can be used by heating and pressurizing a metal foil such as copper foil, aluminum foil, or nickel foil. For example, after this film adhesive is layered on a metal foil, heat and pressure are applied to fuse the film adhesive. The temperature at this time is 200-350℃, preferably 3
00-350°C.
ここでは単に一層の接着について説明したか、フィルム
接着剤を介して多層化することも可能である。 また金
属箔への接着について述べたが金属板、合成樹脂板等、
フィルム接着剤が接着できるところであればいずれでも
よく、特に制限はない。Although only one layer of adhesion has been described here, it is also possible to provide multiple layers via a film adhesive. Also, although we mentioned adhesion to metal foil, metal plates, synthetic resin plates, etc.
Any place that can be bonded with a film adhesive may be used, and there is no particular restriction.
本発明のフィルム接着剤は、いわゆる接着剤や溶剤を含
まないため、耐熱性が良好で、またフレキシビリティ−
があるなめ回路板等の接着に好適である。The film adhesive of the present invention does not contain so-called adhesives or solvents, so it has good heat resistance and flexibility.
Suitable for adhering slanted circuit boards, etc.
（実施例）
次に、本発明を実施例により説明するが、本発明はこれ
らの実鉋例に限定されるものではない６実施例 １
三ロフラスコに乾燥窒素を通してフラスコ内を置換した
後、３．３”、 ５．５′−テトラエチル−４，４′−
ジアミノジフェニルメタン１５５ｇおよび４，４′−ジ
アミノジフェニルエーテル１００Ｇを入れ、これにＮ−
メチル−２−ピロリドン２２８０ ｎｌを加えて溶解し
た。 溶解後、０℃に冷却し攪拌しながら３．３′。(Example) Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these examples.Example 1 After replacing the inside of the flask by passing dry nitrogen into a three-hole flask, .3", 5.5'-tetraethyl-4,4'-
Add 155 g of diaminodiphenylmethane and 100 g of 4,4'-diaminodiphenyl ether, and add N-
2280 nl of methyl-2-pyrrolidone was added and dissolved. After dissolving, cool to 0°C and stir for 3.3'.
４．４′−ベンゾフェノンテトラカルボン酸１６１ｇお
よび４．４′−オキシフタル酸無水物１５５ｇを加えた
。161 g of 4.4'-benzophenonetetracarboxylic acid and 155 g of 4.4'-oxyphthalic anhydride were added.
反応による発熱を氷水中で抑えながら撹拌を続け、その
まま６時間撹拌反応させてポリアミド酸溶液を得た。
この溶液の対数粘度は２．５ｄｌ／ｇであった。 得ら
れたポリアミド酸溶液を離型フィルム上に流延塗布によ
り厚さ３５μｍに均一にコーティングし、１００℃、２
００℃、３００℃で各１時間加熱、脱溶媒及び脱水環化
を行ってポリイミド樹脂のフィルム接着剤を製造しな。Stirring was continued while suppressing the heat generated by the reaction in ice water, and the stirring reaction was continued for 6 hours to obtain a polyamic acid solution.
The logarithmic viscosity of this solution was 2.5 dl/g. The obtained polyamic acid solution was uniformly coated on a release film to a thickness of 35 μm by casting, and heated at 100°C for 2 hours.
A polyimide resin film adhesive is produced by heating at 00°C and 300°C for 1 hour each, followed by solvent removal and dehydration and cyclization.
実施例 ２
三ロフラスコに乾燥窒素を通してフラスコ内を置換した
後、３，３′−ジメチル−５，５′−ジエチル−４゜４
′−ジアミノジフェニルメタン１４１ｇおよび４．４′
−ジアミノジフェニルエーテル１００ｇを入れ、これに
Ｎ−メチル−２−ピロリドン２２３０ ｍｌ を加えて
溶解した。 溶解後、０℃に冷却撹拌しながら、３．３
′、 ４．４′−ベンゾフェノンテトラカルボン酸１６
１Ｑおよび４．４′−オキシフタル酸無水％ １５５０
を加えた。 反応による発熱を氷水中で抑えながら攪拌
を続け、そのまま６時間撹拌反応させて、ポリアミド酸
溶液を得た。 このポリアミド酸溶液を離型フィルム上
に流延塗布により厚さ３５μｍに均一にコーティングし
、１００℃、２００℃、３００℃で各１時間加熱、脱溶
媒及び脱水環化を行ってポリイミド樹脂フィルム接着剤
を製造した。Example 2 After purging the inside of the flask with dry nitrogen, 3,3'-dimethyl-5,5'-diethyl-4゜4
141 g of '-diaminodiphenylmethane and 4.4'
100 g of -diaminodiphenyl ether was added, and 2230 ml of N-methyl-2-pyrrolidone was added and dissolved. After dissolving, cool to 0°C while stirring, 3.3
', 4.4'-benzophenonetetracarboxylic acid 16
1Q and 4.4'-oxyphthalic anhydride% 1550
added. Stirring was continued while suppressing the heat generated by the reaction in ice water, and the stirring reaction was continued for 6 hours to obtain a polyamic acid solution. This polyamic acid solution was uniformly coated on a release film to a thickness of 35 μm by casting, and heated at 100°C, 200°C, and 300°C for 1 hour each, followed by solvent removal and dehydration cyclization to bond the polyimide resin film. The drug was manufactured.
実施例 ３
三ロフラスコ乾燥窒素を通してフラスコ内を置換した後
、４．４′−ジメチル−５，５′−ジアミノジフェニル
へキサフルオログロバン１８１Ｑおよび４．４′−ジア
ミノジフェニルエーテル１００ｇを入れ、これにＮ−メ
チル−２−ピロリドン２３９０１を加えて溶解した。
溶解後、０℃に冷却攪拌しながら、３．３’、 ４．４
’−ベンゾフェノンテトラカルボン酸１６１Ｑおよび４
，４′−オキシフタル酸無水物１５５ｇを加えた。 反
応による発熱を氷水中で抑えながら攪拌を続け、そのま
ま６時間撹拌反応させてポリアミド酸溶液を得た。 こ
のポリアミド酸溶液を離型フィルム上に流延塗布により
厚さ３５μｍに均一にコーティングし、１００℃、２０
０℃、３００℃で各１時間加熱、脱溶媒及び脱水環化を
行ってポリイミド樹脂のフィルム接着剤を製造した。Example 3 After purging the inside of the flask with dry nitrogen, 4,4'-dimethyl-5,5'-diaminodiphenyl hexafluorogloban 181Q and 100 g of 4,4'-diaminodiphenyl ether were added, and N -Methyl-2-pyrrolidone 23901 was added and dissolved.
After dissolving, cool to 0°C while stirring, 3.3', 4.4
'-benzophenonetetracarboxylic acid 161Q and 4
, 155 g of 4'-oxyphthalic anhydride were added. Stirring was continued while suppressing the heat generated by the reaction in ice water, and the stirring reaction was continued for 6 hours to obtain a polyamic acid solution. This polyamic acid solution was uniformly coated on a release film to a thickness of 35 μm by casting, and
A polyimide resin film adhesive was produced by heating at 0° C. and 300° C. for 1 hour each, followed by solvent removal and dehydration and cyclization.
比較例
比較例として市販のアクリルゴム系フィルム接着剤を入
手した。Comparative Example As a comparative example, a commercially available acrylic rubber film adhesive was obtained.
実施例１〜３及び比較例で得たフィルム接着剤を使用し
て銀箔と接着させ、耐半田性、接着性を試験し、結果を
得たので第１表に示した。 いずれも本発明のものが優
れており、本発明の効果を確認することができた。The film adhesives obtained in Examples 1 to 3 and Comparative Example were used to adhere to silver foil, and the solder resistance and adhesion were tested. The results are shown in Table 1. The products of the present invention were superior in all cases, and the effects of the present invention could be confirmed.
なお、接着条件は、実施例１〜３のポリイミドのフィル
ム接着剤の場合、５〜１０ｋｇ／ｃ１１の加圧下。In addition, in the case of the polyimide film adhesive of Examples 1 to 3, the bonding conditions were under a pressure of 5 to 10 kg/c11.
３２０℃×１０分であり、アクリルゴム系のフィルム接
着剤の場合、０．７ｋｇ／ｃｎの加圧下、室温で接着さ
せた。In the case of an acrylic rubber film adhesive, bonding was carried out at room temperature under a pressure of 0.7 kg/cm.
第１表 （単位） Ｏ印・・・外観異常なし、Ｘ印・・・変色有り。Table 1 (unit) O mark: No abnormality in appearance, X mark: Discoloration.
＊２ ：ＡＳＴＭ−Ｄ−１８７５に準じて測定口発明の
効果コ
以上の説明および第１表の結果から明らかなように、本
発明のフィルム接着剤は、耐熱性、接着性に優れ、取扱
いが容易でフレキシビリティ−があり、回路板用等に好
適なものである。*2: According to ASTM-D-1875, the effect of the measurement port invention It is easy and flexible, and is suitable for circuit boards, etc.
Claims (1)
トラカルボン酸（その無水物及び低級アルキルエステル
を含む）と（２）４，４′−オキシフタル酸（その無水
物及び低級アルキルエステルを含む）のモル比が９９／
１〜１／９９の混合物を９５モル％以上含む芳香族テト
ラカルボン酸と、 （Ｂ）一般式（ I ）又は（II） ▲数式、化学式、表等があります▼……（１） ▲数式、化学式、表等があります▼……（２） （但し、式中Ｘは、ＣＨ＿２、Ｏ、ＳＯ＿２、Ｃ（ＣＨ
＿３）＿２、Ｃ（ＣＦ＿３）＿２又はＳを、Ｒ＾１、Ｒ
＾２は、ＣＨ＾３、Ｃ＿２Ｈ＿５、ＯＣＨ＿３又はＯＣ
＿２Ｈ＿５を、Ｒ＾３、Ｒ＾４はＣ＿２Ｈ＿５を、Ｒ＿
５はフェニル基又はシクロヘキサン基を表し、Ｒ＾１〜
Ｒ＾４はいずれもＲ＾５に関してアミノ基のオルソ位に
置換されている）で示される芳香族ジアミンを１０モル
％以上含むジアミン とを反応させてなることを特徴とするフィルム接着剤。[Claims] 1(A) (1) 3,3', 4,4'-benzophenone tetracarboxylic acid (including its anhydride and lower alkyl ester) and (2) 4,4'-oxyphthalic acid ( (including its anhydride and lower alkyl ester) has a molar ratio of 99/
An aromatic tetracarboxylic acid containing 95 mol% or more of a mixture of 1 to 1/99, (B) General formula (I) or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(1) ▲Mathematical formula, There are chemical formulas, tables, etc.▼...(2) (However, in the formula, X is CH_2, O, SO_2, C(CH
_3)_2, C(CF_3)_2 or S, R^1, R
^2 is CH^3, C_2H_5, OCH_3 or OC
_2H_5, R^3, R^4 is C_2H_5, R_
5 represents a phenyl group or a cyclohexane group, R^1~
A film adhesive characterized in that it is produced by reacting a diamine containing 10 mol% or more of an aromatic diamine represented by R^4 (both R^4 is substituted at the ortho position of an amino group with respect to R^5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2050591A JP3007110B2 (en) | 1990-03-01 | 1990-03-01 | Film adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2050591A JP3007110B2 (en) | 1990-03-01 | 1990-03-01 | Film adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03252478A true JPH03252478A (en) | 1991-11-11 |
| JP3007110B2 JP3007110B2 (en) | 2000-02-07 |
Family
ID=12863213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2050591A Expired - Fee Related JP3007110B2 (en) | 1990-03-01 | 1990-03-01 | Film adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3007110B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016052491A1 (en) * | 2014-09-30 | 2016-04-07 | ソマール株式会社 | Polyimide copolymer and molded article using same |
-
1990
- 1990-03-01 JP JP2050591A patent/JP3007110B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016052491A1 (en) * | 2014-09-30 | 2016-04-07 | ソマール株式会社 | Polyimide copolymer and molded article using same |
| CN106795284A (en) * | 2014-09-30 | 2017-05-31 | 索马龙株式会社 | Polyimide copolymer and use its formed body |
| KR20170063626A (en) * | 2014-09-30 | 2017-06-08 | 소마아루 가부시끼가이샤 | Polyimide copolymer and molded article using same |
| JPWO2016052491A1 (en) * | 2014-09-30 | 2017-07-13 | ソマール株式会社 | Polyimide copolymer and molded article using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3007110B2 (en) | 2000-02-07 |
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