JPH03210380A - Adhesive composition - Google Patents

Adhesive composition

Info

Publication number
JPH03210380A
JPH03210380A JP2004681A JP468190A JPH03210380A JP H03210380 A JPH03210380 A JP H03210380A JP 2004681 A JP2004681 A JP 2004681A JP 468190 A JP468190 A JP 468190A JP H03210380 A JPH03210380 A JP H03210380A
Authority
JP
Japan
Prior art keywords
resin
epoxy resin
pts
adhesive composition
epoxy
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
Application number
JP2004681A
Other languages
Japanese (ja)
Other versions
JP2844235B2 (en
Inventor
Itsuro Maeda
前田 逸朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Risho Kogyo Co Ltd
Original Assignee
Risho Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Risho Kogyo Co Ltd filed Critical Risho Kogyo Co Ltd
Priority to JP2004681A priority Critical patent/JP2844235B2/en
Publication of JPH03210380A publication Critical patent/JPH03210380A/en
Application granted granted Critical
Publication of JP2844235B2 publication Critical patent/JP2844235B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Abstract

PURPOSE:To obtain an adhesive composition improved in adhesiveness, workability, resistance to soldering heat, chemical resistance, and reliability in electrical insulating properties by mixing a butyral resin, an epoxy resin, a specified OH-terminated linear polyurethane resin, a curing agent, and a cure accelerator. CONSTITUTION:100 pts.wt. butyral resin having an average degree of polymerization of 1,000 to 2,400 is mixed with 70-100 pts.wt. epoxy resin preferably comprising a bisphenol A epoxy resin and having at least two epoxy groups in the molecule, 25-70 pts.wt. OH-terminated linear polyurethane resin having an average molecular weight of 100,000 to 300,000 and an OH group content of 0.1-0.2wt.%, obtained by reacting an isocyanate with a diol, a curing agent (e.g. diaminodiphenylmethane), and a cure accelerator (e.g. 2-phenyl-4- methylimidazole).

Description

【発明の詳細な説明】 [産業上の利用分野] この発明はポリイミドフィルムと銅箔等の金属箔とを貼
り合わせて成るFPC用基板、TAB用基板に使用され
る接着剤組成物に関するものである。
[Detailed Description of the Invention] [Industrial Application Field] This invention relates to an adhesive composition used for FPC substrates and TAB substrates made by bonding polyimide films and metal foils such as copper foils. be.

「従来技術およびその問題点」 ポリイミドフィルムに銅箔等の金属箔を貼り合せて金属
張ポリイミドフィルムに形成し、この金属張ポリイミド
フィルムの金属箔の不要部をエツチングにより除去して
FPC,TAB用基板として用いる場合に、ポリイミド
フィルムと金属箔との間の貼り合せ用の接着剤の特性と
して、接着性・半田耐熱性・電気絶縁性・耐薬品性など
の特性が要求されると共に、製造過程における加熱加圧
の条件下で接着剤樹脂のフローが少ないと云う特性も要
求される。
"Prior art and its problems" A metal foil such as copper foil is bonded to a polyimide film to form a metal-clad polyimide film, and unnecessary parts of the metal foil of this metal-clad polyimide film are removed by etching for use in FPCs and TABs. When used as a substrate, the adhesive for bonding polyimide film and metal foil must have properties such as adhesiveness, soldering heat resistance, electrical insulation, and chemical resistance, as well as the manufacturing process. The adhesive resin is also required to have a property that there is little flow under the heating and pressurizing conditions.

また他方では、TAB用の回路基板において回路パター
ンのファイン化が進められ、1デバイス当たり100ビ
ンから200ビン〜400ビンに増加することにより、
回路パターン幅が50μm、回路パターン間隔が50μ
m程度にファイン化することが予定され、接着剤に対し
て接着強度、耐熱性、等の特性の優れたものが要求され
る。
On the other hand, the refinement of circuit patterns on circuit boards for TAB is progressing, increasing from 100 bins to 200 to 400 bins per device.
Circuit pattern width is 50μm, circuit pattern spacing is 50μm
It is planned that the adhesive will be made finer than 0.0 m, and adhesives with excellent properties such as adhesive strength and heat resistance will be required.

従来この種の接着剤として、アクリロニトリルゴム系、
共重合ナイロン系、ブチラール−エポキシまたはフェノ
ール系などの接着剤が用いられていた。
Conventional adhesives of this type include acrylonitrile rubber,
Adhesives such as copolymerized nylon, butyral-epoxy or phenol have been used.

しかし、上記接着剤では接着強度、耐熱性において所望
の要求を満たし得す、信頼性に欠けるという問題点があ
る。
However, the above-mentioned adhesives have a problem in that they cannot meet the desired requirements in adhesive strength and heat resistance, and lack reliability.

口問題点を解決するための手段] この発明は、上記の問題点を解決するために、(A)平
均重合度が1000〜2400のブチラール樹脂100
重量部と、(B)1分子中にエポキシ基を2個以上有す
るエポキシ樹脂70〜180重量部と、(C)イソシア
ネートとジオールとを反応させてできるヒドロキシル末
端線状ポリウレタン樹脂25〜70重量部と、(D)硬
化剤、硬化促進剤とからなる接着剤組成物に構成したの
である。
Means for Solving the Problems] In order to solve the above problems, the present invention provides (A) a butyral resin with an average degree of polymerization of 1000 to 2400.
(B) 70 to 180 parts by weight of an epoxy resin having two or more epoxy groups in one molecule, and (C) 25 to 70 parts by weight of a hydroxyl-terminated linear polyurethane resin produced by reacting isocyanate and diol. and (D) a curing agent and a curing accelerator.

本発明に用いられるブチラール樹脂は平均重合度が10
00〜2400のものを用いる。平均重合度が1000
以下では耐熱性、耐薬品性において劣るものとなる。ブ
チラール樹脂の具体例として電気化学製ブチラール#4
000.#5000、#6000などがあげられ、最も
好ましいものはブチラール#6000である。
The butyral resin used in the present invention has an average degree of polymerization of 10
00 to 2400 is used. Average degree of polymerization is 1000
Below that, the heat resistance and chemical resistance will be poor. Butyral #4 made by Denki Kagaku Co., Ltd. is a specific example of butyral resin.
000. Examples include #5000, #6000, and the most preferred is butyral #6000.

本発明に用いられるエポキシ樹脂は、分子中に2個以上
のエポキシ基を有するものであれば良いが、好ましくは
ビスフェノール型エポキシ樹脂、ノボラック型エポキシ
樹脂などのエステル型あるいはグリシジルエーテル型、
あるいは芳香族型エポキシ樹脂、環状脂肪族型エポキシ
樹脂などのエステル型あるいはグリシジルエステル型の
ものでも良い。更にはこれらのエポキシ樹脂のブレンド
系でも良い。とりわけ良好なものは、ビスフェノールA
型であり、具体的には旭化成製AER−331、AER
−337,AER−661などがあげられる。配合量に
おいてエポキシ樹脂が70重量部以下になると電気絶縁
性が低下し、180重量部を越えると接着性が低下し且
つ銅箔貼り合わせ時の接着剤のニジミが多くなり本願発
明の目的を達し得ない。
The epoxy resin used in the present invention may be one having two or more epoxy groups in the molecule, but is preferably an ester type or glycidyl ether type such as a bisphenol type epoxy resin or a novolac type epoxy resin.
Alternatively, an ester type or glycidyl ester type such as an aromatic type epoxy resin or a cycloaliphatic type epoxy resin may be used. Furthermore, a blend system of these epoxy resins may be used. Particularly good is bisphenol A
type, specifically Asahi Kasei AER-331, AER
-337, AER-661, etc. If the amount of the epoxy resin is less than 70 parts by weight, the electrical insulation properties will decrease, and if it exceeds 180 parts by weight, the adhesive will decrease and the adhesive will smear more when bonding the copper foils, so that the purpose of the present invention is not achieved. I don't get it.

本発明で用いられるヒドロキシル末端線状ポリウレタン
樹脂は、平均分子量10万〜30万、水酸基含有率0.
1〜0.2%のものが好ましく、例えば次のような分子
構造をしている。
The hydroxyl-terminated linear polyurethane resin used in the present invention has an average molecular weight of 100,000 to 300,000 and a hydroxyl group content of 0.
It is preferably 1 to 0.2%, and has, for example, the following molecular structure.

[1行余白コ 但し、 R:アルキレン基またはアリーレン基 R’ 、R“:アルキレン基 n絢10   m″f60 具体的には、住友バイエルウレタン製デスモコール50
0.51O8,530,540などが挙げられるが、接
着性、耐熱性の面からデスモコール540が最適である
[1 line margin] However, R: alkylene group or arylene group R', R": alkylene group n 10 m" f 60 Specifically, Desmocol 50 manufactured by Sumitomo Bayer Urethane
Examples include 0.51O8, 530, and 540, but Desmocol 540 is most suitable in terms of adhesiveness and heat resistance.

配分量はヒドロキシル末端線状ポリウレタン樹脂が25
重量部以下になると接着性が低下し70重量部を越える
と耐熱性、電気絶縁性などが低下し、本願発明の目的を
達し得なくなる。
The distribution amount is 25% of the hydroxyl-terminated linear polyurethane resin.
If the amount is less than 70 parts by weight, the adhesiveness will decrease, and if it exceeds 70 parts by weight, the heat resistance, electrical insulation properties, etc. will decrease, making it impossible to achieve the object of the present invention.

本願発明に用いられる硬化剤は、脂肪族および芳香族ポ
リアミン、酸無水物、イミダゾール誘導体、ジシアンジ
アミドなどが代表例としてあげることができる。とりわ
け良好なものの具体例をあげれば、ジアミノジフェニル
メタン、ジアミノジフェニルスルホンなどである。また
硬化を促進するためにイミダゾール誘導体を硬化促進剤
として併用することができる。具体的には、2−フェニ
ルイミダゾール、4−フェニルイミダゾール、2.4−
ジフェニルイミダゾール、2−フェニル−4−メチルイ
ミダゾール、2−フェニル−4−エチルイミタゾール、
1−ベンジルイミダゾールなどがあげられる。好ましく
は 2−フェニル−4−メチルイミダゾールである。
Typical examples of the curing agent used in the present invention include aliphatic and aromatic polyamines, acid anhydrides, imidazole derivatives, and dicyandiamide. Specific examples of particularly good ones include diaminodiphenylmethane and diaminodiphenyl sulfone. Further, in order to accelerate curing, an imidazole derivative can be used in combination as a curing accelerator. Specifically, 2-phenylimidazole, 4-phenylimidazole, 2.4-
diphenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-ethylimitazole,
Examples include 1-benzylimidazole. Preferably it is 2-phenyl-4-methylimidazole.

[実施例1〜6] 先ず、ブチラール樹脂の所定量をアセトン/トルエン=
1:1溶剤に溶解して20%溶液を作成する。これに、
エポキシ樹脂をメチルエチルケトン(MEK)に溶解さ
せたものを添加し、更に、ヒドロキシル末端線状ポリウ
レタン樹脂をアセトンに溶解させた10%溶液を加える
。この溶液に所定量のジアミノジフェニルスルフォン(
DDS)および2フエニル4メチルイミダゾール(2P
4MZ)を溶解したメチルセルソルブ溶液を加えて接着
剤組成物を得た。
[Examples 1 to 6] First, a predetermined amount of butyral resin was mixed with acetone/toluene=
Dissolve in 1:1 solvent to make a 20% solution. to this,
An epoxy resin dissolved in methyl ethyl ketone (MEK) is added, followed by a 10% solution of a hydroxyl-terminated linear polyurethane resin dissolved in acetone. Add a predetermined amount of diaminodiphenylsulfone (
DDS) and 2 phenyl 4 methylimidazole (2P
A methylcellosolve solution in which 4MZ) was dissolved was added to obtain an adhesive composition.

これを75μm厚のポリイミドフィルム(宇部興産製ユ
ービレックスSタイプ)に20μmの塗工厚になるよう
にコンマバー塗工し150℃で4分間乾燥させ、その後
に35μm厚の銅箔を重ね合せて130℃に加熱した熱
ロールを用いロール圧3kgf/−で加圧し2時間硬化
させて銅張ポリイミドフィルムを作成した。その際の接
着剤組成の配合割合は第1表に示す通りである。接着剤
組成の各種の配合割合の銅張ポリイミドフィルムについ
て、接着性、半田耐熱性、耐薬品性、電気絶縁性の試験
を行いその結果を第1表に併せて示した。
This was coated with a comma bar to a 75 μm thick polyimide film (Ubilex S type manufactured by Ube Industries) to a coating thickness of 20 μm, dried at 150°C for 4 minutes, and then overlaid with 35 μm thick copper foil to give a coating thickness of 130 μm. A copper-clad polyimide film was prepared by applying pressure with a roll pressure of 3 kgf/- using a hot roll heated to .degree. C. and curing for 2 hours. The blending ratio of the adhesive composition at that time is as shown in Table 1. Tests for adhesion, soldering heat resistance, chemical resistance, and electrical insulation were conducted on copper-clad polyimide films with various blending ratios of adhesive compositions, and the results are also shown in Table 1.

接着性は銅箔の両側に切り込みを入れ基板面に対して9
0度の方向に引き剥す際に必要な力を測定した。
Adhesiveness is determined by making cuts on both sides of the copper foil and attaching it to the board surface.
The force required to peel off in the 0 degree direction was measured.

半田耐熱性は300℃の半田浴に2分間フロートさせた
後の銅箔の基材よりの剥離を観察し判定した。
Solder heat resistance was determined by observing peeling of the copper foil from the base material after floating it in a 300° C. solder bath for 2 minutes.

耐薬品性は常温で15分間各種の薬品に浸漬後の接着剤
の外観を観察し良否を判定した。
Chemical resistance was determined by observing the appearance of the adhesive after immersing it in various chemicals for 15 minutes at room temperature.

電気絶縁性は5龍巾の銅箔を1u間隔に形成して銅箔間
に100■の電圧を印加したときの絶縁抵抗を測定した
The electrical insulation property was measured by forming copper foils of 5 widths at intervals of 1 μ and measuring the insulation resistance when a voltage of 100 μ was applied between the copper foils.

[以下11行余白] [発明の効果] 本発明の接着剤組成物は上述したように(A)ブチラー
ル樹脂(B)エポキシ樹脂(C)ヒドロキシル末端線状
ポリウレタン樹脂および(D)硬化剤から構成すること
により、接着性・加工性・半田耐熱性耐薬品性・電気絶
縁性に優れた効果を発揮するものとなり、ポリイミドフ
ィルムと銅箔等金属箔と貼り合わせて成る回路基板用と
して好適に使用することができるものである。
[11 blank lines below] [Effects of the Invention] As described above, the adhesive composition of the present invention is composed of (A) a butyral resin, (B) an epoxy resin, (C) a hydroxyl-terminated linear polyurethane resin, and (D) a curing agent. As a result, it exhibits excellent adhesion, processability, soldering heat resistance, chemical resistance, and electrical insulation properties, making it suitable for use in circuit boards made by laminating polyimide film and metal foil such as copper foil. It is something that can be done.

Claims (1)

【特許請求の範囲】[Claims] (A)平均重合度が1000〜2400のブチラール樹
脂100重量部と、(B)1分子中にエポキシ基を2個
以上有するエポキシ樹脂70〜180重量部と、(C)
イソシアネートとジオールとを反応させてできるヒドロ
キシル末端線状ポリウレタン樹脂25〜70重量部と、
(D)硬化剤および硬化促進剤とからなる接着剤組成物
(A) 100 parts by weight of a butyral resin with an average degree of polymerization of 1000 to 2400; (B) 70 to 180 parts by weight of an epoxy resin having two or more epoxy groups in one molecule; (C)
25 to 70 parts by weight of a hydroxyl-terminated linear polyurethane resin produced by reacting an isocyanate and a diol;
(D) An adhesive composition comprising a curing agent and a curing accelerator.
JP2004681A 1990-01-12 1990-01-12 Adhesive composition Expired - Fee Related JP2844235B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004681A JP2844235B2 (en) 1990-01-12 1990-01-12 Adhesive composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004681A JP2844235B2 (en) 1990-01-12 1990-01-12 Adhesive composition

Publications (2)

Publication Number Publication Date
JPH03210380A true JPH03210380A (en) 1991-09-13
JP2844235B2 JP2844235B2 (en) 1999-01-06

Family

ID=11590636

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004681A Expired - Fee Related JP2844235B2 (en) 1990-01-12 1990-01-12 Adhesive composition

Country Status (1)

Country Link
JP (1) JP2844235B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845866A (en) * 2021-11-18 2021-12-28 广州联茂电子科技有限公司 Epoxy compound adhesive, covering film and preparation method
WO2024005072A1 (en) * 2022-06-28 2024-01-04 株式会社寺岡製作所 Adhesive composition, adhesive layer including adhesive composition, and adhesive sheet comprising adhesive layer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845866A (en) * 2021-11-18 2021-12-28 广州联茂电子科技有限公司 Epoxy compound adhesive, covering film and preparation method
WO2024005072A1 (en) * 2022-06-28 2024-01-04 株式会社寺岡製作所 Adhesive composition, adhesive layer including adhesive composition, and adhesive sheet comprising adhesive layer

Also Published As

Publication number Publication date
JP2844235B2 (en) 1999-01-06

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