JPH07173449A - Acrylic adhesive composition and adhesive film made thereof - Google Patents
Acrylic adhesive composition and adhesive film made thereofInfo
- Publication number
- JPH07173449A JPH07173449A JP34320993A JP34320993A JPH07173449A JP H07173449 A JPH07173449 A JP H07173449A JP 34320993 A JP34320993 A JP 34320993A JP 34320993 A JP34320993 A JP 34320993A JP H07173449 A JPH07173449 A JP H07173449A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銅箔光沢面との接着性
に優れ、かつ耐熱性、回路埋込後の平担性（フロー性）
を兼ね備えたアクリル系接着剤組成物及びこれを用いた
接着フィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent adhesiveness to a copper foil glossy surface, heat resistance, and flatness (flowability) after circuit embedding.
And an adhesive film using the same.
【０００２】[0002]
【従来の技術】アクリル系接着剤組成物は、電気特性、
耐熱性、耐溶剤性などの優れた特性を有することから、
特開平３−１８１５８０号公報に示されているように、
フレキシブル印刷配線板（以下ＦＰＣと略す）のベース
フィルムと銅箔とを接着する分野をはじめ広く用いられ
ているが、近年の電子機器の高密度化、高機能化にとも
ない、その信頼性を向上させるために、より高度の接着
強度、特に銅箔光沢面との接着強度、耐熱性、電気特性
などを有する接着剤組成物が求められるようになった。
また、接着剤組成物をフィルム化した接着シートに関し
ても前記特性の他、回路埋め込み性やハンドリング性の
向上が要求されている。2. Description of the Related Art Acrylic adhesive compositions have electrical properties,
Since it has excellent properties such as heat resistance and solvent resistance,
As disclosed in Japanese Patent Laid-Open No. 3-181580,
Widely used in the field of adhering a base film of a flexible printed wiring board (hereinafter abbreviated as FPC) to a copper foil, but its reliability has been improved with the recent increase in density and functionality of electronic devices. Therefore, an adhesive composition having higher adhesive strength, in particular, adhesive strength with a glossy surface of copper foil, heat resistance, and electrical characteristics has been demanded.
Further, in addition to the above-mentioned characteristics, improvement in circuit embedding property and handling property is also required for the adhesive sheet formed by filming the adhesive composition.
【０００３】しかしながら、これらの要求特性の中で特
に銅箔光沢面との接着性、フロー性、更には接着フィル
ムとしてのハンドリング性を同時に満足せしめる接着剤
組成物を求めることは極めて困難であった。However, among these required characteristics, it has been extremely difficult to find an adhesive composition which can simultaneously satisfy the adhesiveness with a glossy surface of a copper foil, the flowability, and the handling property as an adhesive film at the same time. .
【０００４】例えば、接着剤組成物として広く用いられ
ているエポキシ樹脂組成物の場合、可撓性に劣るため接
着剤組成物をフィルム化することは困難であり可塑剤な
どを併用しても、上記特性を同時に満足することは極め
て困難である。For example, in the case of an epoxy resin composition which is widely used as an adhesive composition, it is difficult to form an adhesive composition into a film because of its poor flexibility, and even if a plasticizer is used in combination, It is extremely difficult to satisfy the above characteristics at the same time.
【０００５】また、特開平３−１８１５８０号公報に示
されるアクリル系接着剤組成物は、銅箔粗化面との接着
性には優れるものの、光沢面との接着性が低いという問
題点があった。また、アクリル系接着剤組成物をフィル
ム化した接着シートは、可撓性には優れるものの、伸び
やすいためにハンドリング性に劣るという問題点があっ
た。Further, the acrylic adhesive composition disclosed in Japanese Patent Laid-Open No. 3-181580 has excellent adhesion to the roughened surface of the copper foil, but has a problem of low adhesion to the glossy surface. It was Further, the adhesive sheet formed of a film of the acrylic adhesive composition is excellent in flexibility, but has a problem that it is inferior in handleability because it is easily stretched.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、銅箔光沢面
との接着性、フロー性及び接着フィルムとしてのハンド
リング性を同時に満足するアクリル系接着剤組成物を提
供するものである。DISCLOSURE OF THE INVENTION The present invention provides an acrylic adhesive composition which simultaneously satisfies the adhesiveness to a copper foil glossy surface, the flowability and the handling property as an adhesive film.
【０００７】本発明は、また、上記アクリル系接着剤組
成物をフィルム化してなるハンドリング性に優れた接着
フィルムを提供するものである。The present invention also provides an adhesive film having excellent handling property, which is obtained by forming the acrylic adhesive composition into a film.
【０００８】[0008]
【課題を解決するための手段】本発明者らは上記目的を
達成し得る接着剤組成物について鋭意検討した結果、ア
クリル系接着剤組成物に、ビスマレイミド化合物を添加
してなる系が、前記問題を解決し得ることを見い出し、
この知見に基づいて、本発明を完成するに至った。Means for Solving the Problems As a result of intensive investigations by the present inventors on an adhesive composition that can achieve the above-mentioned objects, a system obtained by adding a bismaleimide compound to an acrylic adhesive composition has Find that you can solve the problem,
The present invention has been completed based on this finding.
【０００９】すなわち、本発明は、ａ）エチルアクリレ
ート、ブチルアクリレート又はこれらの混合物５８〜８
０重量％、ｂ）アクリロニトリル１８〜４０重量％及び
ｃ）官能基モノマーとしてグリシジルメタクリレート２
〜６重量％を共重合させて得られる共重合物で、Ｔｇが
−１０℃以上で、かつ重量平均分子量が８００，０００
以上であるアクリルエラストマー（Ａ）、アルキル変性
フェノール樹脂（Ｂ）、エポキシ樹脂（Ｃ）及びイミダ
ゾール系硬化剤（Ｄ）から成る組成物に、前記組成物１
００重量部に対してビスマレイミド化合物を２０〜４０
重量部添加してなることを特徴とするアクリル系接着剤
組成物を提供するものである。That is, the present invention comprises: a) ethyl acrylate, butyl acrylate or mixtures 58-8 thereof.
0% by weight, b) 18-40% by weight of acrylonitrile and c) glycidyl methacrylate 2 as a functional group monomer
A copolymer obtained by copolymerizing 6 to 6% by weight, having a Tg of −10 ° C. or higher and a weight average molecular weight of 800,000.
The above composition 1 is added to the composition comprising the acrylic elastomer (A), the alkyl-modified phenol resin (B), the epoxy resin (C) and the imidazole-based curing agent (D).
20-40 parts of bismaleimide compound to 100 parts by weight
The present invention provides an acrylic adhesive composition characterized by being added in parts by weight.
【００１０】次に、本発明を詳しく説明する。本発明に
用いる（Ａ）成分のアクリルエラストマーとしては、Ｔ
ｇを−１０℃以上に分子設計する必要がある。すなわ
ち、Ｔｇが−１０℃未満のアクリルエラストマーを用い
ると粘着性（タック性）が高くなりすぎてしまい、接着
剤組成物をフィルム化した際のハンドリング性が極端に
低下してしまう。Ｔｇの好ましい範囲は−１０〜１０℃
である。また、アクリルエラストマーの分子量は、重量
平均分子量で８００，０００以上とする必要がある。重
量平均分子量が８００，０００未満のアクリルエラスト
マーを用いると、可撓性が低下すると共に、フロー性が
大きくなりすぎてしまい接着剤組成物のしみ出し量のコ
ントロールが困難になってしまう。重量平均分子量の好
ましい範囲は８００，０００〜２，０００，０００であ
る。Next, the present invention will be described in detail. The (A) component acrylic elastomer used in the present invention includes T
It is necessary to molecularly design g to be -10 ° C or higher. That is, when an acrylic elastomer having a Tg of less than -10 ° C is used, the tackiness becomes too high, and the handling property when the adhesive composition is formed into a film is extremely deteriorated. The preferable range of Tg is −10 to 10 ° C.
Is. The molecular weight of the acrylic elastomer needs to be 800,000 or more in terms of weight average molecular weight. When an acrylic elastomer having a weight average molecular weight of less than 800,000 is used, the flexibility is lowered and the flowability becomes too large, which makes it difficult to control the amount of the adhesive composition exuded. The preferable range of the weight average molecular weight is 800,000 to 2,000,000.
【００１１】アクリルエラストマー中の組成において、
アクリロニトリル量は１８〜４０重量％であることが必
要である。１８重量％未満では、耐溶剤性に劣るため、
各種後工程において接着剤組成物が溶剤に侵されてしま
う。また、４０重量％を超えると、他成分との相溶性が
低下するとともに重合も困難である。官能基モノマーと
しては、グリシジルメタクリレートが用いられる。この
官能基が、カルボン酸タイプのアクリル酸や水酸基タイ
プのヒドロキシエチルメタクリレートなどを用いると、
銅箔光沢面との接着性が低下してしまうと共に、他成分
との相溶性も低下してしまう。官能基モノマーの量は、
２〜６重量％必要である。２重量％未満では、良好な接
着力が得られず、また６重量％を超えると接着剤組成物
がゲル化しやすくなるため適当でない。エチルアクリレ
ート、ブチルアクリレート又はそれらの混合物の量は、
５８〜８０重量％必要であり、上記組成を基にして、ア
クリルエラストマーが所定のＴｇになる様に重合する。
その重合方法は、パール重合、乳化重合などが挙げられ
るが、特に限定されるものではない。In the composition in the acrylic elastomer,
The amount of acrylonitrile needs to be 18 to 40% by weight. If it is less than 18% by weight, the solvent resistance is poor,
The adhesive composition is attacked by the solvent in various post-processes. On the other hand, if it exceeds 40% by weight, the compatibility with other components is lowered and the polymerization is also difficult. Glycidyl methacrylate is used as the functional group monomer. If this functional group uses carboxylic acid type acrylic acid or hydroxyl group type hydroxyethyl methacrylate,
The adhesiveness with the glossy surface of the copper foil is reduced, and the compatibility with other components is also reduced. The amount of functional group monomer is
2 to 6% by weight is required. If it is less than 2% by weight, good adhesive strength cannot be obtained, and if it exceeds 6% by weight, the adhesive composition tends to gel, which is not suitable. The amount of ethyl acrylate, butyl acrylate or mixtures thereof is
It is required to be 58 to 80% by weight, and based on the above composition, the acrylic elastomer is polymerized to have a predetermined Tg.
Examples of the polymerization method include pearl polymerization and emulsion polymerization, but are not particularly limited.
【００１２】（Ｂ）成分のアルキル変性フェノール樹脂
の製造に用いられるアルキルフェノール類としてはｐ−
ブチルフェノール等のｐ−置換アルキルフェノールなど
が使用される。例えば、日立化成工業株式会社製フェノ
ール樹脂ヒタノール２１８０、２４００、２４１０など
が使用できる。Alkylphenols used in the production of the alkyl-modified phenolic resin as the component (B) are p-
A p-substituted alkylphenol such as butylphenol is used. For example, the phenolic resin hitanol 2180, 2400, 2410 manufactured by Hitachi Chemical Co., Ltd. can be used.
【００１３】（Ｃ）成分のエポキシ樹脂としては、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
及びこれらの混合物が好適に使用される。As the epoxy resin as the component (C), bisphenol type epoxy resins, novolac type epoxy resins and mixtures thereof are preferably used.
【００１４】（Ｄ）成分のイミダゾール系硬化剤として
は、例えば、四国化成工業株式会社製キュアゾール２Ｍ
Ｚ−ＣＮＳ（１−シアノエチル−２−メチルイミダゾリ
ウムトリメリテート）、２Ｅ４ＭＺ−ＣＮＳ（１−シア
ノエチル−２−エチル−４−メチルイミダゾリウムトリ
メリテート）、２ＰＺ−ＣＮＳ（１−シアノエチル−２
−フェニルイミダゾリウムトリメリテート）などが好適
に使用される。（Ｄ）成分の添加量としては、（Ｃ）成
分のエポキシ樹脂１００重量部に対して、通常、０．５
〜１０重量部、好ましくは、１〜５重量部の範囲であ
る。Examples of the imidazole type curing agent as the component (D) include Curesol 2M manufactured by Shikoku Chemicals Co., Ltd.
Z-CNS (1-cyanoethyl-2-methylimidazolium trimellitate), 2E4MZ-CNS (1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate), 2PZ-CNS (1-cyanoethyl-2)
-Phenyl imidazolium trimellitate) and the like are preferably used. The addition amount of the component (D) is usually 0.5 with respect to 100 parts by weight of the epoxy resin of the component (C).
The range is from 10 to 10 parts by weight, preferably from 1 to 5 parts by weight.
【００１５】アクリルエラストマーとアルキル変性フェ
ノールの配合量比（重量比）は、通常、５５／４５〜９
５／５程度であるが、アクリルエラストマーの配合量
が、多すぎると耐熱性が低下してしまい、また少ないと
良好な接着力が得られない。好ましくは、７５／２５〜
８５／１５の範囲である。アクリルエラストマーとエポ
キシ樹脂の配合量比（重量比）は、通常、６５／３５〜
９５／５程度である。エポキシ樹脂の配合量が多すぎる
と、可撓性が低下し成膜性に劣る。また、少なすぎる
と、良好な耐熱性が得られない。The amount ratio (weight ratio) of the acrylic elastomer and the alkyl-modified phenol is usually 55 / 45-9.
Although it is about 5/5, if the blending amount of the acrylic elastomer is too large, the heat resistance is lowered, and if it is too small, a good adhesive force cannot be obtained. Preferably from 75/25
The range is 85/15. The blending ratio (weight ratio) of the acrylic elastomer and the epoxy resin is usually 65/35 to
It is about 95/5. If the blending amount of the epoxy resin is too large, the flexibility is lowered and the film formability is deteriorated. If it is too small, good heat resistance cannot be obtained.
【００１６】前述の様にして得られた接着剤組成物に、
ビスマレイミド樹脂を添加することにより、本発明の接
着剤組成物を調製する。In the adhesive composition obtained as described above,
The adhesive composition of the present invention is prepared by adding a bismaleimide resin.
【００１７】添加するビスマレイミド化合物としては、
下記一般式（１）で示されるものが好適に用いられる。As the bismaleimide compound to be added,
Those represented by the following general formula (1) are preferably used.
【００１８】[0018]
【化１】 （式中、Ｒは２価の基を表わす。） ビスマレイミド化合物の具体例としては、Ｎ，Ｎ′−ｍ
−フェニレンビスマレイミド、Ｎ，Ｎ′−ｐ−フェニレ
ンビスマレイミド、Ｎ，Ｎ′−（オキシジ−ｐ−フェニ
レン）ビスマレイミド、Ｎ，Ｎ′−（メチレンジ−ｐ−
フェニレン）ビスマレイミド、２，２−ビス（マレイミ
ドフェノキシフェニル）プロパン等を挙げることができ
るが、これに何等限定されるものではない。また、その
添加量は、前記（Ａ）〜（Ｄ）成分の組成物１００重量
部に対し、２０〜４０重量部とする。２０重量部より少
ないと、ビスマレイミド化合物の添加による１）銅箔光
沢面との接着力向上、２）フィルム化した時のハンドリ
ング性向上の効果が不十分であり、また４０重量部を超
えるとアクリル成分との相溶性が低下してしまい、均一
な塗膜が得られない。ビスマレイミド化合物の添加に際
しては、予めＤＭＦなどの溶剤にビスマレイミド化合物
を均一に分散させておいたものを添加した方が、相溶性
の点において好ましい。[Chemical 1] (In the formula, R represents a divalent group.) Specific examples of the bismaleimide compound include N, N'-m.
-Phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N '-(oxydi-p-phenylene) bismaleimide, N, N'-(methylenedi-p-
Examples thereof include phenylene) bismaleimide and 2,2-bis (maleimidophenoxyphenyl) propane, but are not limited thereto. Moreover, the addition amount is 20 to 40 parts by weight with respect to 100 parts by weight of the composition of the components (A) to (D). If the amount is less than 20 parts by weight, the effect of 1) improving the adhesive force to the glossy surface of the copper foil by adding the bismaleimide compound, and 2) improving the handling property when formed into a film is insufficient, and if it exceeds 40 parts by weight. The compatibility with the acrylic component decreases, and a uniform coating film cannot be obtained. When adding the bismaleimide compound, it is preferable to add a bismaleimide compound uniformly dispersed in a solvent such as DMF in terms of compatibility.
【００１９】ビスマレイミド化合物の架橋を促進させる
点で、ジアミノジフェニルエーテル（ＤＤＥ）やジアミ
ノジフェニルメタン（ＤＤＭ）などのジアミン成分を、
ビスマレイミド化合物１００重量部に対し、５〜３０重
量部添加することも好適である。但し、３０重量部を超
えると接着剤組成物としての流動性がなくなり、また、
耐熱性が低下することがある。In order to accelerate the crosslinking of the bismaleimide compound, a diamine component such as diaminodiphenyl ether (DDE) or diaminodiphenylmethane (DDM) is added.
It is also suitable to add 5 to 30 parts by weight to 100 parts by weight of the bismaleimide compound. However, when it exceeds 30 parts by weight, the fluidity of the adhesive composition is lost, and
The heat resistance may decrease.
【００２０】このようにして得られたアクリル系接着剤
組成物を用いる用途としては、１）ＦＰＣ用カバーレイ
フィルムや２）接着フィルムなどが挙げられているが、
これに限定されるものではない。Applications of the acrylic adhesive composition thus obtained include 1) FPC coverlay films and 2) adhesive films.
It is not limited to this.
【００２１】ＦＰＣ用カバーレイフィルムに用いる場合
は、アクリル系接着剤組成物をメチルエチルケトン（Ｍ
ＥＫ）やトルエン又は混合溶媒中に、固形分１５〜２５
重量％になる様に調整し、基材上に塗布、乾燥する。基
材フィルムとしては、ポリイミドやポリエステルなどの
フィルムが使用されるが、特に限定されるものではな
い。また、基材との接着力を高めるためには、機械的又
は化学的処理を行うことが好ましい。その表面処理の例
としては、ブラシ研磨、サンドブラスト処理、カップリ
ング剤処理、プラズマ処理、コロナ処理、アルカリ処
理、酸処理等がある。この様にして得られたカバーレイ
フィルムを、回路加工したＦＰＣに熱圧着するが、熱圧
着前の接着剤組成物中の残留揮発分は、３重量％以下に
なる様に乾燥する必要がある。３重量％を超えると、熱
圧着時のふくれや、はんだ耐熱性低下の原因となる。When used in a coverlay film for FPC, an acrylic adhesive composition is used as methyl ethyl ketone (M
EK), toluene or a mixed solvent, solid content 15-25
It is adjusted so that the weight% is reached, and it is coated on a substrate and dried. A film of polyimide, polyester, or the like is used as the base film, but is not particularly limited. In addition, mechanical or chemical treatment is preferably performed in order to increase the adhesive force with the substrate. Examples of the surface treatment include brush polishing, sandblast treatment, coupling agent treatment, plasma treatment, corona treatment, alkali treatment, acid treatment and the like. The cover lay film thus obtained is thermocompression-bonded to a circuit-processed FPC, but it is necessary to dry it so that the residual volatile content in the adhesive composition before thermocompression bonding is 3% by weight or less. . If it exceeds 3% by weight, it may cause blistering during thermocompression bonding and lower solder heat resistance.
【００２２】接着フィルムとして用いる場合は、前述の
様に調製したアクリル系接着剤組成物をテフロンフィル
ムや離型処理したポリエステルフィルムなどの離型フィ
ルム上に、塗布、乾燥し、使用時に基材から剥離させて
フィルム化しアクリル系接着剤組成物のみの好ましくは
厚さ２０〜５０μｍのフィルムとして、各種被着体の接
着に用いる。用途の一例としては、印刷配線板を多層化
する際の層間接着フィルムなどが挙げられるが、これに
限定されるものではない。When used as an adhesive film, the acrylic adhesive composition prepared as described above is applied onto a release film such as a Teflon film or a release-treated polyester film, dried, and then used from the substrate at the time of use. The acrylic adhesive composition alone is peeled off to form a film, which is preferably used as a film having a thickness of 20 to 50 μm for adhesion of various adherends. Examples of applications include, but are not limited to, an interlayer adhesive film when a printed wiring board is multilayered.
【００２３】[0023]
【実施例】以下、本発明を実施例及びその比較例によっ
て更に具体的に説明するが、本発明はこれらに限定され
るものではない。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples thereof, but the present invention is not limited thereto.
【００２４】配合例１ （Ａ）ａ）エチルアクレート２９．２５重量部、ブチル
アクリレート３９．２５重量部、ｂ）アクリロニトリル
３０重量部、ｃ）グリシジルメタクリレート３重量部を
公知のパール重合法によって重合して得られた、ガラス
転移温度−６．９℃、重量平均分子量１，０００，００
０のアクリルエラストマー１３４重量部 ［固形分比７２．００重量％］ （Ｂ）ヒタノール２４００（アルキルフェノール樹脂、
日立化成工業（株）製）２４重量部［固形分比１２．６
４重量％］ （Ｃ）ＹＤ−７０１１（エピビス型エポキシ樹脂、東都
化成（株）製）１１重量部［固形分比６重量％］、及び
ＥＰＰＮ−２０１（フェノールノボラック型エポキシ樹
脂、日本化薬（株）製）１７重量部［固形分比８．９６
重量％］ （Ｄ）２ＰＺ−ＣＮＳ（１−シアノエチル−２−フェニ
ルイミダゾリウムトリメリテート、四国化成（株）製）
０．８重量部［固形分比０．４３重量％］を予めＤＭＦ
７．１重量部に溶解させた溶液からなる組成物を、ＭＥ
Ｋ８００重量部に溶解させて接着剤組成物を得た。Formulation Example 1 (A) A) 29.25 parts by weight of ethyl acrylate, 39.25 parts by weight of butyl acrylate, b) 30 parts by weight of acrylonitrile, and c) 3 parts by weight of glycidyl methacrylate are polymerized by a known pearl polymerization method. The glass transition temperature of -6.9 ° C and the weight average molecular weight of 1,000,000,000
No. 0 acrylic elastomer 134 parts by weight [solid content ratio 72.00% by weight] (B) Hitanol 2400 (alkylphenol resin,
Hitachi Chemical Co., Ltd.) 24 parts by weight [solid content ratio 12.6
4% by weight] (C) YD-7011 (epibis type epoxy resin, manufactured by Tohto Kasei Co., Ltd.) 11 parts by weight [solid content ratio 6% by weight], and EPPN-201 (phenol novolac type epoxy resin, Nippon Kayaku ( Co., Ltd.) 17 parts by weight [solid content ratio 8.96]
Wt%] (D) 2PZ-CNS (1-cyanoethyl-2-phenylimidazolium trimellitate, manufactured by Shikoku Kasei Co., Ltd.)
0.8 parts by weight [solid content ratio 0.43% by weight] was previously added to DMF.
A composition comprising a solution dissolved in 7.1 parts by weight was added to ME.
K was dissolved in 800 parts by weight to obtain an adhesive composition.
【００２５】配合例２ 配合例１の接着剤組成物固形分１００重量部に対し２０
重量部にあたる３８重量部のＮ，Ｎ′−（メチレンジ−
ｐ−フェニレン）ビスマレイミド（以下ＢＭＩと略す）
を予めＤＭＦ１５２重量部に分散させておいた溶液を添
加した他は、配合例１と同様にして接着剤組成物を得
た。Formulation Example 2 20 per 100 parts by weight of the solid content of the adhesive composition of Formulation Example 1
38 parts by weight of N, N '-(methylenedi-
p-phenylene) bismaleimide (hereinafter abbreviated as BMI)
Was added to 152 parts by weight of DMF in advance, and an adhesive composition was obtained in the same manner as in Formulation Example 1 except that a solution was added.
【００２６】配合例３ ＢＭＩの添加量を、配合例１の接着剤組成物固形分１０
０重量部に対し４０重量部にあたる７６重量部とした他
は、配合例２と同様にして接着剤組成物を得た。Formulation Example 3 The amount of BMI added was changed to 10% of the solid content of the adhesive composition of Formulation Example 1.
An adhesive composition was obtained in the same manner as in Formulation Example 2 except that the amount was 76 parts by weight, which is 40 parts by weight relative to 0 parts by weight.
【００２７】配合例４ ＢＭＩの添加量を、配合例１の接着剤組成物固形分１０
０重量部に対し６０重量部にあたる１１４重量部とした
他は、配合例２と同様にして接着剤組成物を得た。Formulation Example 4 The amount of BMI added was changed to 10% of the solid content of the adhesive composition of Formulation Example 1.
An adhesive composition was obtained in the same manner as in Formulation Example 2 except that 114 parts by weight, which was 60 parts by weight with respect to 0 parts by weight, was used.
【００２８】配合例５ 配合例２の接着剤組成物中に、ＢＭＩ１００重量部に対
し２０重量部にあたる７．６重量部の４−４′ジアミノ
ジフェニルエーテルを予めＤＭＦ３０．４重量部に溶解
させておいた溶液を添加した他は、配合例２と同様にし
て接着剤組成物を得た。Formulation Example 5 In the adhesive composition of Formulation Example 2, 7.6 parts by weight of 4-4 'diaminodiphenyl ether, which is 20 parts by weight per 100 parts by weight of BMI, was dissolved in advance in 30.4 parts by weight of DMF. An adhesive composition was obtained in the same manner as in Formulation Example 2 except that the above solution was added.
【００２９】配合例６ （Ａ）ＨＴＲ−７００（アクリルエラストマー、帝国化
学産業（株）製）８３重量部［固形分比３７．５１重量
％］、ＷＳ−０２３Ｂ（アクリルエラストマー、帝国化
学産業（株）製）３７重量部［固形分比１６．７０重量
％］ （Ｂ）ヒタノール２４１０（アルキルフェノール樹脂、
日立化成工業（株）製）３７重量部［固形分比１６．７
０重量％］ （Ｃ）ＢＲＥＮ−Ｓ（ノボラック型臭素化エポキシ樹
脂、日本化薬（株）製）６３重量部［固形分比２８．４
１重量％］ （Ｄ）２ＰＺ−ＣＮＳ（１−シアノエチル−２−フェニ
ルイミダゾリウムトリメリテート、四国化成（株）製）
１．５重量部を予めジメチルホルムアミド１３．５重量
部に溶解させた溶液［固形分比０．６８重量％］からな
る組成物を、ＭＥＫ：トルエン＝１／１の混合溶媒８６
０重量部に溶解させて接着剤組成物を得た。Formulation Example 6 (A) HTR-700 (acrylic elastomer, manufactured by Teikoku Chemical Industry Co., Ltd.) 83 parts by weight [solid content ratio 37.51% by weight], WS-023B (acrylic elastomer, Teikoku Chemical Industry Co., Ltd. )) 37 parts by weight [solid content ratio 16.70% by weight] (B) Hitanol 2410 (alkylphenol resin,
Hitachi Chemical Co., Ltd.) 37 parts by weight [solid content ratio 16.7
0% by weight] (C) BREN-S (novolak type brominated epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) 63 parts by weight [solid content ratio 28.4
1% by weight] (D) 2PZ-CNS (1-cyanoethyl-2-phenylimidazolium trimellitate, manufactured by Shikoku Kasei Co., Ltd.)
A composition comprising a solution [solid content ratio of 0.68% by weight] prepared by dissolving 1.5 parts by weight of 13.5 parts by weight of dimethylformamide in advance was added to a mixed solvent 86 of MEK: toluene = 1/1.
It was dissolved in 0 parts by weight to obtain an adhesive composition.
【００３０】実施例１〜３ ニトフロン ８０μｍ（テフロンフィルム、日東電工
（株）製）上に、配合例２、３、５で調製した接着剤組
成物を塗工機を用いて均一に塗布し、１４０℃、１６０
℃でそれぞれ４分間ずつ乾燥し、更に１５０℃で２０分
間乾燥した後に、テフロンフィルムより接着剤組成物を
剥離して、厚さ３０μｍの接着フィルムを作製した。Examples 1 to 3 Nitoflon 80 μm (Teflon film, manufactured by Nitto Denko Co., Ltd.) was uniformly coated with the adhesive composition prepared in Formulation Examples 2, 3 and 5 using a coating machine, 140 ° C, 160
After drying each at 4 ° C. for 4 minutes and further at 150 ° C. for 20 minutes, the adhesive composition was peeled off from the Teflon film to prepare an adhesive film having a thickness of 30 μm.
【００３１】この接着フィルムを銅箔光沢面、３本
／ｍｍに回路加工（銅箔厚み３５μｍ）を施したＭＣＦ
ー５０００Ｉ（二層フレキシブル銅張積層板、日立化成
工業（株）製）の回路面の間にはさんで、１７０℃ー４
０ｋｇｆ／ｃｍ2、３０分間熱圧着した。諸特性を表１
に示す。MCF in which this adhesive film has been subjected to circuit processing (copper foil thickness 35 μm) on a copper foil glossy surface of 3 pieces / mm.
-It is sandwiched between the circuit surfaces of 5000I (2-layer flexible copper clad laminate, Hitachi Chemical Co., Ltd.), 170 ° C-4
Thermocompression bonding was carried out for 30 minutes at 0 kgf / cm 2 . Table 1 shows various characteristics
Shown in.
【００３２】比較例１〜３ 配合例１、４、６で調製した接着剤組成物を用いた他
は、実施例１〜３と同様にして接着フィルムを作製、評
価した。諸特性を表１に示す。Comparative Examples 1 to 3 Adhesive films were prepared and evaluated in the same manner as in Examples 1 to 3 except that the adhesive compositions prepared in Formulation Examples 1, 4, and 6 were used. Table 1 shows various characteristics.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【発明の効果】本発明によれば、銅箔光沢面との接着
性、フロー性及び耐熱性に優れ、かつ接着フィルムとし
てのハンドリング性を向上できる接着剤組成物を容易に
製造することができる。EFFECTS OF THE INVENTION According to the present invention, it is possible to easily produce an adhesive composition which is excellent in adhesiveness to a copper foil glossy surface, flowability and heat resistance, and which can improve the handling property as an adhesive film. .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 161/06 ＪＥＳ (72)発明者 今泉 純一 茨城県下館市大字五所宮1150番地 日立化 成工業株式会社五所宮工場内 (72)発明者 塩貝 進 茨城県下館市大字五所宮1150番地 日立化 成工業株式会社五所宮工場内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number in the agency FI Technical indication location C09J 161/06 JES (72) Inventor Junichi Imaizumi 1150 Goshomiya, Shimodate-shi, Ibaraki Hitachi Chemical Co., Ltd. Inside the Goshomiya Plant (72) Inventor Susumu Shiogai 1150 Gotomiya, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Inside the Goshomiya Plant
Claims (2)
レート又はこれらの混合物５８〜８０重量％、ｂ）アク
リロニトリル１８〜４０重量％及びｃ）官能基モノマー
としてグリシジルメタクリレート２〜６重量％を共重合
させて得られる共重合物で、Ｔｇが−１０℃以上で、か
つ重量平均分子量が８００，０００以上であるアクリル
エラストマー（Ａ）、アルキル変性フェノール樹脂
（Ｂ）、エポキシ樹脂（Ｃ）及びイミダゾール系硬化剤
（Ｄ）から成る組成物に、前記組成物１００重量部に対
してビスマレイミド化合物を２０〜４０重量部添加して
なることを特徴とするアクリル系接着剤組成物。1. Obtained by copolymerizing a) 58-80% by weight of ethyl acrylate, butyl acrylate or a mixture thereof, b) 18-40% by weight of acrylonitrile and c) 2-6% by weight of glycidyl methacrylate as a functional group monomer. A copolymer obtained, having an Tg of −10 ° C. or higher and a weight average molecular weight of 800,000 or higher, an acrylic elastomer (A), an alkyl-modified phenol resin (B), an epoxy resin (C), and an imidazole curing agent ( An acrylic adhesive composition comprising a composition comprising D) and 20 to 40 parts by weight of a bismaleimide compound added to 100 parts by weight of the composition.
化してなる接着フィルム。2. An adhesive film obtained by film-forming the adhesive composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34320993A JPH07173449A (en) | 1993-12-17 | 1993-12-17 | Acrylic adhesive composition and adhesive film made thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34320993A JPH07173449A (en) | 1993-12-17 | 1993-12-17 | Acrylic adhesive composition and adhesive film made thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07173449A true JPH07173449A (en) | 1995-07-11 |
Family
ID=18359764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34320993A Pending JPH07173449A (en) | 1993-12-17 | 1993-12-17 | Acrylic adhesive composition and adhesive film made thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07173449A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998015975A1 (en) * | 1996-10-08 | 1998-04-16 | Hitachi Chemical Company, Ltd. | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| WO2000078887A1 (en) * | 1999-06-18 | 2000-12-28 | Hitachi Chemical Company, Ltd. | Adhesive, adhesive member, circuit substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same |
| EP1167483A1 (en) * | 2000-06-20 | 2002-01-02 | Saehan Industries, Inc. | Adhesive tape for electronic parts |
| JP2003096426A (en) * | 2001-09-26 | 2003-04-03 | Hitachi Chem Co Ltd | Adhesive member |
| KR100607372B1 (en) * | 2000-04-20 | 2006-08-02 | 도레이새한 주식회사 | Adhesive tape for the electronic parts |
| CN100454493C (en) * | 2003-06-06 | 2009-01-21 | 日立化成工业株式会社 | Adhesive sheet, dicing tape intergrated type adhesive sheet, and semiconductor device producing method |
| JP2010006941A (en) * | 2008-06-26 | 2010-01-14 | Hitachi Chem Co Ltd | Method for producing acrylic copolymer |
| CN102002325A (en) * | 2010-12-10 | 2011-04-06 | 浙江华正新材料股份有限公司 | Method to manufacture insulating bonding sheet |
-
1993
- 1993-12-17 JP JP34320993A patent/JPH07173449A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6621170B2 (en) | 1996-10-08 | 2003-09-16 | Hitachi Chemical Company, Ltd. | Semiconductor device, substrate for mounting semiconductor chip, processes for their production, adhesive, and double-sided adhesive film |
| EP0959498A1 (en) * | 1996-10-08 | 1999-11-24 | Hitachi Chemical Company, Ltd. | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| US6265782B1 (en) | 1996-10-08 | 2001-07-24 | Hitachi Chemical Co., Ltd. | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| WO1998015975A1 (en) * | 1996-10-08 | 1998-04-16 | Hitachi Chemical Company, Ltd. | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| EP0959498A4 (en) * | 1996-10-08 | 2006-03-22 | Hitachi Chemical Co Ltd | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| WO2000078887A1 (en) * | 1999-06-18 | 2000-12-28 | Hitachi Chemical Company, Ltd. | Adhesive, adhesive member, circuit substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same |
| US6838170B2 (en) | 1999-06-18 | 2005-01-04 | Hitachi Chemical Company, Ltd. | Adhesive, adhesive member, interconnecting substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same |
| KR100607372B1 (en) * | 2000-04-20 | 2006-08-02 | 도레이새한 주식회사 | Adhesive tape for the electronic parts |
| EP1167483A1 (en) * | 2000-06-20 | 2002-01-02 | Saehan Industries, Inc. | Adhesive tape for electronic parts |
| JP2003096426A (en) * | 2001-09-26 | 2003-04-03 | Hitachi Chem Co Ltd | Adhesive member |
| CN100454493C (en) * | 2003-06-06 | 2009-01-21 | 日立化成工业株式会社 | Adhesive sheet, dicing tape intergrated type adhesive sheet, and semiconductor device producing method |
| JP2010006941A (en) * | 2008-06-26 | 2010-01-14 | Hitachi Chem Co Ltd | Method for producing acrylic copolymer |
| CN102002325A (en) * | 2010-12-10 | 2011-04-06 | 浙江华正新材料股份有限公司 | Method to manufacture insulating bonding sheet |
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