JP2001152123A - Heat-curable adhesive and its adhesive sheets - Google Patents
Heat-curable adhesive and its adhesive sheetsInfo
- Publication number
- JP2001152123A JP2001152123A JP33269899A JP33269899A JP2001152123A JP 2001152123 A JP2001152123 A JP 2001152123A JP 33269899 A JP33269899 A JP 33269899A JP 33269899 A JP33269899 A JP 33269899A JP 2001152123 A JP2001152123 A JP 2001152123A
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- Japan
- Prior art keywords
- parts
- curing
- weight
- epoxy resin
- meth
- 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.)
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Links
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子部品の固定用
途などに用いられる熱硬化型接着剤と、そのシ―ト状や
テ―プ状などの接着シ―ト類とに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting adhesive used for fixing electronic parts and the like, and an adhesive sheet such as a sheet or tape.
【０００２】[0002]
【従来の技術】近年、電子部品の固定用途などに、種々
の接合材料が使用されている。この種の用途では、強接
着性に加え、電子部品を基板に実装するときのハンダリ
フロ―に耐えうる高耐熱性が必要である。また、電子デ
バイスの信頼性確保の目的で、各種加湿条件に投入した
のちハンダ耐熱性などの熱試験が行われるが、接合材料
の吸水性が大きいと、熱試験時に吸湿した水分が気化・
膨張し接着面の剥離異常をきたすため、接合材料自体の
低吸水化が必要である。2. Description of the Related Art In recent years, various joining materials have been used for fixing electronic parts. In this type of application, in addition to strong adhesiveness, high heat resistance that can withstand solder reflow when mounting an electronic component on a substrate is required. In addition, for the purpose of ensuring the reliability of electronic devices, thermal tests such as solder heat resistance are performed after putting them into various humidifying conditions, but if the bonding material has a large water absorption, the moisture absorbed during the heat test will evaporate.
It is necessary to reduce the water absorption of the bonding material itself because it expands and causes abnormal peeling of the bonding surface.
【０００３】これに対し、一般の粘着シ―ト類を用いた
のでは、接着強度や耐熱性に劣り、とくに熱プレス時に
気泡の抱き込みを生じ、熱試験時に剥離や発泡などの異
常をきたしやすい。また、エポキシ／ゴム系、ポリイミ
ド系などの熱硬化型接着剤の使用が検討されているが、
エポキシ／ゴム系の熱硬化型接着剤は、低圧・短時間で
接着処理でき耐熱性も良好であるが、エポキシ樹脂の構
造上吸水率が大きく、加湿条件投入後の熱試験におい
て、接着界面で剥離異常をきたしやすい。また、ポリイ
ミド系の熱硬化型接着剤は、耐熱性の面ではすぐれてい
るが、熱接着温度での弾性率が高すぎて、接着処理に高
圧・長時間が必要で作業性が悪く、しかも吸湿率も大き
く、接着界面での信頼性に劣りやすい。[0003] On the other hand, when general adhesive sheets are used, the adhesive strength and heat resistance are inferior. In particular, bubbles are entrapped during hot pressing, and abnormalities such as peeling and foaming occur during a thermal test. Cheap. Also, the use of thermosetting adhesives such as epoxy / rubber and polyimide has been studied.
Epoxy / rubber-based thermosetting adhesives can be bonded at low pressure in a short time and have good heat resistance. It is easy to cause peeling abnormality. In addition, polyimide-based thermosetting adhesives are excellent in terms of heat resistance, but have too high an elastic modulus at the heat bonding temperature, require high pressure and long time for the bonding process, and have poor workability. It has a high moisture absorption rate and tends to have poor reliability at the bonding interface.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、このような
事情に照らし、低圧・短時間の加熱接着処理で強固な接
着強度と高耐熱性が得られ、しかも加湿条件投入後の熱
試験においても剥離異常をきたすことのない、信頼性に
すぐれた熱硬化型接着剤と、そのシ―ト状やテ―プ状な
どの接着シ―ト類を提供することを目的としている。SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a strong adhesive strength and a high heat resistance by a low-pressure, short-time heat-bonding treatment. The purpose of the present invention is to provide a highly reliable thermosetting adhesive which does not cause abnormal peeling and an adhesive sheet such as a sheet or tape.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の目
的に対して、鋭意検討した結果、特定の（メタ）アクリ
ル酸エステルを主モノマ―とするアクリル系ポリマ―に
エポキシ樹脂を加え、上記ポリマ―の架橋度を調節して
硬化前のガラス転移温度と貯蔵弾性率を特定すると、常
温で非粘着ないし弱粘着であつて熱接着時に気泡の抱き
込みを生じず、その際の流動性が適度なため、低圧・短
時間での接着処理が可能であり、しかも上記主モノマ―
自体が凝集成分として寄与し、通常凝集成分でありかつ
吸湿成分でもあるアクリル酸などの極性モノマ―の使用
量を低減できるので、上記ポリマ―の吸水率を低下で
き、これを最終加熱処理で上記エポキシ樹脂により硬化
させて硬化後の貯蔵弾性率を特定すると、強固な接着強
度と高耐熱性が得られ、かつ加湿条件投入後の熱試験で
も剥離異常をきたさない、信頼性にすぐれた熱硬化型接
着剤とその接着シ―ト類が得られることを知り、本発明
を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the above objects, and as a result, have added epoxy resin to an acrylic polymer having a specific (meth) acrylate ester as a main monomer. When the glass transition temperature and the storage elastic modulus before curing are specified by adjusting the degree of crosslinking of the above polymer, it is non-sticky or weakly sticky at room temperature and does not cause bubbles to be entrapped during thermal bonding. Suitable for low-pressure, short-time bonding, and the above-mentioned main monomer
The amount of polar monomers such as acrylic acid, which is itself a coagulant component and is also a coagulant component and a hygroscopic component, can be reduced, so that the water absorption of the polymer can be reduced, and this can be reduced by the final heat treatment. By specifying the storage elastic modulus after curing by curing with an epoxy resin, it is possible to obtain strong adhesive strength and high heat resistance, and it does not cause peeling abnormalities even in thermal tests after humidifying conditions are applied, and it has excellent reliability. Knowing that mold adhesives and their adhesive sheets could be obtained, the present invention was completed.
【０００６】すなわち、本発明は、つぎの式（１）； （式中、Ｒ1 は水素原子またはメチル基、Ｒ2 はメチレ
ン基、エチレン基またはプロピレン基、ｎ＝１〜３の整
数、φはフエニル基、モノアルキル置換フエニル基また
はジアルキル置換フエニル基である）で表される（メ
タ）アクリル酸エステルを主モノマ―とするアクリル系
ポリマ―とエポキシ樹脂を含有してなり、硬化前のガラ
ス転移温度が−１０℃以上、硬化前の貯蔵弾性率が１０
０〜２００℃の温度域で１０4 〜１０5 Ｐａ、硬化後の
貯蔵弾性率が２００〜３００℃の温度域で５×１０5 〜
１０7 Ｐａであり、かつ硬化後の３０℃，８０％ＲＨ保
存下での飽和吸水率が１．０重量％以下であることを特
徴とする熱硬化型接着剤（請求項１〜３）と、基材の片
面または両面に上記構成の熱硬化型接着剤からなる層を
有することを特徴とするシ―ト状やテ―プ状などの接着
シ―ト類（請求項４）とに係るものである。That is, the present invention provides the following formula (1): (Wherein R 1 is a hydrogen atom or a methyl group, R 2 is a methylene group, an ethylene group or a propylene group, n is an integer of 1 to 3, and φ is a phenyl group, a monoalkyl-substituted phenyl group or a dialkyl-substituted phenyl group. ) Containing an acrylic polymer having a (meth) acrylic acid ester as a main monomer and an epoxy resin, a glass transition temperature before curing of -10 ° C or more, and a storage elastic modulus before curing of 10
10 4 to 10 5 Pa in a temperature range of 0 to 200 ° C., and a storage elastic modulus after curing of 5 × 10 5 to 5 in a temperature range of 200 to 300 ° C.
10 7 is Pa, and 30 ° C. after curing, thermosetting adhesives saturated water absorption under storage RH 80% is characterized in that 1.0 wt% or less (claim 1) And a sheet-like or tape-like adhesive sheet having a layer made of the thermosetting adhesive having the above structure on one or both sides of the base material. Things.
【０００７】[0007]
【発明の実施の形態】本発明におけるアクリル系ポリマ
―は、式（１）で表される（メタ）アクリル酸エステル
を主モノマ―とし、これに通常エポキシ樹脂との硬化反
応に関与するアクリル酸を加え、必要により、イソボル
ニルアクリレ―トなどの各種のアルキル（メタ）アクリ
レ―トや、カプロラクトン変性（メタ）アクリレ―ト、
スルホプロピル（メタ）アクリレ―ト、ヒドロキシアル
キル（メタ）アクリレ―ト、シアノアルキル（メタ）ア
クリレ―ト、（メタ）アクリルアミド、置換（メタ）ア
クリルアミド、Ｎ−ビニルカプロラクタム、（メタ）ア
クリロニトリル、２−メトキシエチル（メタ）アクリレ
―ト、（メタ）アクリル酸グリシジル、酢酸ビニルなど
の改質用モノマ―を全モノマ―中２０重量％以下の割合
で加えて、これらを溶液重合法、電子線や紫外線などに
よる光重合法、それらの併用法などの公知の方法で重合
処理することにより、得られるものである。BEST MODE FOR CARRYING OUT THE INVENTION The acrylic polymer used in the present invention is mainly composed of a (meth) acrylic acid ester represented by the formula (1), and the acrylic monomer usually involved in a curing reaction with an epoxy resin. If necessary, various alkyl (meth) acrylates such as isobornyl acrylate, and caprolactone-modified (meth) acrylate,
Sulfopropyl (meth) acrylate, hydroxyalkyl (meth) acrylate, cyanoalkyl (meth) acrylate, (meth) acrylamide, substituted (meth) acrylamide, N-vinylcaprolactam, (meth) acrylonitrile, 2- Modifier monomers such as methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, and vinyl acetate are added at a ratio of not more than 20% by weight of all monomers, and these are added by a solution polymerization method, electron beam or ultraviolet ray. It can be obtained by performing a polymerization treatment by a known method such as a photopolymerization method using the above method or a combination method thereof.
【０００８】式（１）で表される（メタ）アクリル酸エ
ステルとしては、たとえば、フエノキシエチル（メタ）
アクリレ―ト、フエノキシプロピル（メタ）アクリレ―
ト、ノニルフエノキシエチル（メタ）アクリレ―ト、ノ
ニルフエノキシプロピル（メタ）アクリレ―トなどが挙
げられる。また、フエノ―ル、クレゾ―ルノニルフエノ
―ルなどのエチレンオキシド付加物、プロピレンオキシ
ド付加物など（付加モル数３まで）と（メタ）アクリル
とのエステルなども好ましく用いられる。これらのエス
テルは、その１種または２種以上が用いられる。The (meth) acrylate represented by the formula (1) includes, for example, phenoxyethyl (meth)
Acrylate, phenoxypropyl (meth) acrylate
And nonylphenoxyethyl (meth) acrylate, nonylphenoxypropyl (meth) acrylate and the like. Further, esters of ethylene oxide adducts such as phenol and cresolnonyl phenol, and propylene oxide adducts (up to 3 moles added) with (meth) acrylic acid are also preferably used. One or more of these esters are used.
【０００９】アクリル酸は、エポキシ樹脂との反応性
や、ポリマ―のガラス転移温度および貯蔵弾性率を設定
するうえで、またこれに伴う接着性、耐熱性、低吸水性
などの特性の向上をはかるうえで、とくに好ましいもの
として選択されたものである。使用量は、全モノマ―中
１〜５重量％とするのがよい。１重量％より少ないと、
エポキシ樹脂による硬化反応が十分に進行せず、貯蔵弾
性率の上昇も不十分で、耐熱性も不十分となる。５重量
％より多いと、硬化後の架橋が密になりすぎて、接着強
度の著しい低下をきたし、また吸水性の低下が起こりや
すい。Acrylic acid is used to set the reactivity with the epoxy resin, the glass transition temperature and the storage modulus of the polymer, and to improve the properties such as adhesion, heat resistance and low water absorption. It has been selected as particularly preferred for the measurement. The amount used is preferably 1 to 5% by weight based on all monomers. If less than 1% by weight,
The curing reaction by the epoxy resin does not proceed sufficiently, the rise in storage modulus is insufficient, and the heat resistance is also insufficient. If the amount is more than 5% by weight, the crosslink after curing becomes too dense, resulting in a remarkable decrease in adhesive strength and a decrease in water absorption.
【００１０】本発明におけるエポキシ樹脂は、これを上
記のアクリル系ポリマ―に加えて、最終加熱処理で上記
ポリマ―を構成するアクリル酸に由来するカルボキシル
基と反応させて硬化させることにより、強固な接着強度
と高耐熱性を得るためのものである。このようなエポキ
シ樹脂としては、分子内に２個以上のエポキシ基を有す
る、ビスフエノ―ルエポキシ樹脂、フエノリツクエポキ
シ樹脂、ハロゲン化ビスフエノ―ルエポキシ樹脂などが
あり、エポキシ当量が５００以下のものが好適に用いら
れる。エポキシ当量が５００を超えると、アクリル系ポ
リマ―とエポキシ樹脂の相溶性が悪くなり、均一な接着
剤層を形成しにくい。[0010] The epoxy resin of the present invention is solid by adding it to the above-mentioned acrylic polymer and reacting it with a carboxyl group derived from acrylic acid constituting the polymer in a final heat treatment to cure the epoxy resin. This is for obtaining an adhesive strength and high heat resistance. Examples of such an epoxy resin include a bisphenol epoxy resin, a phenolic epoxy resin, a halogenated bisphenol epoxy resin having two or more epoxy groups in a molecule, and those having an epoxy equivalent of 500 or less are preferable. Used for If the epoxy equivalent exceeds 500, the compatibility between the acrylic polymer and the epoxy resin becomes poor, and it is difficult to form a uniform adhesive layer.
【００１１】エポキシ樹脂の使用量としては、アクリル
系ポリマ―１００重量部あたり、通常５〜３０重量部、
好ましくは５〜２０重量部とするのがよい。上記使用量
が５重量部未満では、硬化反応が十分に進行せず、硬化
後の貯蔵弾性率の上昇も不十分で、耐熱性に乏しくな
る。また、３０重量部を超えると、加熱硬化時の軟化、
流動により、糊はみ出しなどの外観異常をきたしやす
く、また熱硬化型接着剤としての貯蔵安定性が低下して
くるなどの問題がある。The amount of the epoxy resin used is usually 5 to 30 parts by weight per 100 parts by weight of the acrylic polymer,
Preferably, it is 5 to 20 parts by weight. If the amount is less than 5 parts by weight, the curing reaction does not proceed sufficiently, the storage elastic modulus after curing is insufficiently increased, and the heat resistance is poor. Further, if it exceeds 30 parts by weight, softening during heat curing,
Due to the flow, there is a problem that appearance abnormality such as glue sticking out easily occurs, and storage stability as a thermosetting adhesive is lowered.
【００１２】本発明では、上記のアクリル系ポリマ―に
エポキシ樹脂を混合した状態で上記ポリマ―を架橋処理
しその架橋度を調節して、最終的にエポキシ樹脂により
硬化させる前の状態において、ガラス転移温度が−１０
℃以上、好適には−１０℃〜２０℃となり、貯蔵弾性率
が１００〜２００℃の温度域で１０4 〜１０5 Ｐａとな
るようにする。このように設定することで、常温で非粘
着ないし弱粘着であつて、熱接着時に気泡の抱き込みを
生じず、かつその際の流動性が適度なものとなつて、低
圧・短時間での接着処理が可能となり、しかも最終加熱
処理時に軟化や劣化などによる糊はみだしも生じず、す
ぐれた加工性や接着作業性を実現することができる。上
記ガラス転移温度が−１０℃より低いと、常温で粘着性
を有して熱接着時に気泡の抱き込みを生じやすく、上記
貯蔵弾性率が１０4 Ｐａ未満では、熱接着時に流動を起
こして糊はみだしの原因となり、また１０5 Ｐａを超え
ると、熱接着処理に長時間を必要とする。In the present invention, the acrylic polymer is mixed with an epoxy resin, the polymer is cross-linked, the degree of cross-linking is adjusted, and the glass is finally cured before being cured with the epoxy resin. Transition temperature -10
° C or more, preferably -10 ° C to 20 ° C, and the storage modulus is 10 4 to 10 5 Pa in a temperature range of 100 to 200 ° C. By setting in this way, it is non-adhesive or weakly adhering at room temperature, does not generate air bubbles at the time of thermal bonding, and has an appropriate fluidity at that time, and has a low pressure and a short time. Adhesion can be performed, and glue due to softening or deterioration does not occur at the time of final heat treatment, and excellent workability and bonding workability can be realized. When the glass transition temperature is lower than −10 ° C., the resin has tackiness at room temperature and easily embraces air bubbles during thermal bonding. When the storage elastic modulus is less than 10 4 Pa, it causes a flow during thermal bonding and paste. If the pressure exceeds 10 5 Pa, a long time is required for the heat bonding treatment.
【００１３】架橋処理の方法としては、アクリル系ポリ
マ―の合成に際し内部架橋剤（交叉結合剤）を加えて架
橋処理する方法が有効である。内部架橋剤には、トリメ
チロ―ルプロパントリ（メタ）アクリレ―ト、ペンタエ
リスリト―ルテトラ（メタ）アクリレ―ト、１，２−エ
チレングリコ―ルジ（メタ）アクリレ―ト、１，６−ヘ
キサジオ―ルジ（メタ）アクリレ―ト、１，１２−ドデ
カンジオ―ル（メタ）アクリレ―トなどの多官能（メ
タ）アクリレ―トが用いられる。As a method of the crosslinking treatment, a method of adding an internal crosslinking agent (crosslinking agent) in the synthesis of the acrylic polymer and carrying out the crosslinking treatment is effective. Internal crosslinkers include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexadiol Polyfunctional (meth) acrylates such as (meth) acrylate and 1,12-dodecanddiol (meth) acrylate are used.
【００１４】架橋処理の他の有効な方法としては、アク
リル系ポリマ―の合成後に外部架橋剤を加えて加熱など
により架橋処理する方法がある。外部架橋剤には、イソ
シアネ―ト系架橋剤として、エチレンジイソシアネ―
ト、ブチレンジイソシアネ―ト、ヘキサメチレンジイソ
シアネ―トなどの低級脂肪族ポリイソシアネ―ト類、シ
クロペンチレンジイソシアネ―ト、シクロヘキシレンジ
イソシアネ―ト、イソホロンジイソシアネ―トなどの脂
環族ポリイソシアネ―ト類、２，４−トリレンジイソシ
アネ―ト、４，４′−ジフエニルメタンジイソシアネ―
ト、キシレンジイソシアネ―トなどの芳香族ポリイソシ
アネ―ト類、トリメチロ―ルプロパン／トリレンジイソ
シアネ―ト付加物などが挙げられる。また、エポキシ系
架橋剤として、エチレングリコ―ルグリシジルエ―テ
ル、プロピレングリコ―ルジグリシジルエ―テルなどの
分子内に２個以上のエポキシ基を含有する化合物などが
挙げられる。さらに、アジリジン系架橋剤として、トリ
ス−２，４，６−（１−アジリジニル）−１，３，５−
トリアジン、トリス〔１−（２−メチル）アジリジニ
ル〕フオスフインオキシド、ヘキサ〔１−（２−メチ
ル）−アジリジニル〕トリフオスフアトリアジンなどを
挙げることができる。As another effective method of the cross-linking treatment, there is a method of adding an external cross-linking agent after the synthesis of the acrylic polymer and performing a cross-linking treatment by heating or the like. The external cross-linking agent includes ethylene diisocyanate as an isocyanate cross-linking agent.
, Butylene diisocyanate, lower aliphatic polyisocyanates such as hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, etc. Alicyclic polyisocyanates, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate
And aromatic polyisocyanates such as xylylene diisocyanate, and trimethylolpropane / tolylene diisocyanate adduct. Examples of the epoxy-based crosslinking agent include compounds containing two or more epoxy groups in a molecule, such as ethylene glycol glycidyl ether and propylene glycol diglycidyl ether. Further, as an aziridine-based crosslinking agent, tris-2,4,6- (1-aziridinyl) -1,3,5-
Triazine, tris [1- (2-methyl) aziridinyl] phosphine oxide, hexa [1- (2-methyl) -aziridinyl] triphosphoatriazine and the like can be mentioned.
【００１５】これらの内部架橋剤および外部架橋剤は、
その１種を単独で用いてもよいし、２種以上を併用して
もよい。これらの使用量は、その種類により異なるが、
前記特定範囲のガラス転移温度や貯蔵弾性率に設定して
前記効果を奏しうるように、アクリル系ポリマ―（この
ポリマ―を構成するモノマ―混合物）１００重量部あた
り、通常０．０２〜５重量部、好適には０．２〜３重量
部とするのがよい。These internal and external cross-linking agents are
One of these may be used alone, or two or more may be used in combination. These amounts vary depending on the type,
Usually, 0.02 to 5 parts by weight per 100 parts by weight of an acrylic polymer (monomer mixture constituting the polymer) so that the above effects can be obtained by setting the glass transition temperature and the storage elastic modulus in the specific range. Parts, preferably 0.2 to 3 parts by weight.
【００１６】本発明の熱硬化型接着剤は、上記のよう
に、前記アクリル系ポリマ―に対してエポキシ樹脂を混
合し、上記ポリマ―を架橋処理して、硬化前のガラス転
移温度および貯蔵弾性率を前記特定範囲に設定してなる
ものであり、この接着剤には、低吸水化、熱伝導率の増
大による接着時間・硬化時間の短縮、加工性の向上など
を目的として、無機充填剤を添加することができる。ま
た、さらに必要により、シランカツプリング剤、粘着付
与剤、可塑剤、軟化剤、顔料、染料、老化防止剤などの
公知の各種添加剤を配合することもできる。As described above, the thermosetting adhesive of the present invention is obtained by mixing the acrylic polymer with an epoxy resin and subjecting the polymer to a crosslinking treatment to obtain a glass transition temperature and a storage elasticity before curing. Rate is set in the specific range, the adhesive has an inorganic filler for the purpose of reducing water absorption, shortening the bonding time and curing time by increasing the thermal conductivity, improving the workability, and the like. Can be added. Further, if necessary, various known additives such as a silane coupling agent, a tackifier, a plasticizer, a softener, a pigment, a dye, and an antioxidant can be blended.
【００１７】上記の無機充填剤には、シリカ、アルミ
ナ、炭酸カルシウム、三酸化アンチモン、酸化チタンな
どが用いられ、通常は、０．５〜２５０μｍ、好ましく
は１〜１００μｍ、より好ましくは５〜３０μｍの平均
粒子径を有しているのがよい。粒子形状は、球状、針
状、フレ―ク状、スタ―状などのいかなる形状でもよ
い。形状の選択は最終的な熱硬化型接着剤のレオロジカ
ルな性質により決められる。使用量としては、アクリル
系ポリマ―１００重量部に対し、通常１０〜１００重量
部、好ましくは１０〜５０重量部とするのがよい。１０
重量部未満では、吸水率低下などの効果が乏しく、また
１００重量部を超えると、接着性が阻害され、とくに高
温下での接着力が大きく低下し、接着固定力に乏しくな
る。As the above-mentioned inorganic filler, silica, alumina, calcium carbonate, antimony trioxide, titanium oxide and the like are used, and usually 0.5 to 250 μm, preferably 1 to 100 μm, more preferably 5 to 30 μm. The average particle diameter is preferably The particle shape may be any shape such as a spherical shape, a needle shape, a flake shape, and a star shape. The choice of shape is determined by the rheological properties of the final thermoset adhesive. The amount used is usually 10 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the acrylic polymer. 10
If the amount is less than 100 parts by weight, the effect of lowering the water absorption is poor. If the amount is more than 100 parts by weight, the adhesiveness is impaired, and the adhesive strength at high temperatures is greatly reduced, and the adhesive fixing power is poor.
【００１８】本発明の接着シ―ト類は、このような熱硬
化型接着剤からなる層を基材の片面または両面に設け
て、シ―ト状やテ―プ状などの形態としたものである。
基材上への上記層の形成は、基材上に熱硬化型接着剤を
塗工したのち、必要により加熱などにより架橋処理する
方式、紫外線照射による重合方式など従来公知の方式で
行うことができる。基材には、ポリエステルフイルムな
どの合成樹脂フイルムや繊維基材などの非剥離性基材を
使用でき、また剥離紙などの剥離性基材を使用してもよ
い。剥離性基材では、この上に形成した熱硬化型接着剤
からなる層を非剥離性基材上に転写してもよい。本発明
の接着シ―ト類には、基材として非剥離性基材を用いた
ものと、剥離性基材を用いたものとの両方が含まれる。The adhesive sheets of the present invention are obtained by providing a layer made of such a thermosetting adhesive on one or both sides of a base material to form a sheet or tape. It is.
The formation of the above-mentioned layer on the base material may be performed by a conventionally known method such as a method of applying a thermosetting adhesive on the base material and then performing a crosslinking treatment by heating or the like as necessary, a polymerization method by ultraviolet irradiation, or the like. it can. As the base material, a non-peelable base material such as a synthetic resin film such as a polyester film or a fiber base material may be used, or a peelable base material such as a release paper may be used. In the case of a peelable substrate, a layer made of a thermosetting adhesive formed thereon may be transferred onto a non-peelable substrate. The adhesive sheets of the present invention include both those using a non-peelable substrate and those using a peelable substrate.
【００１９】本発明の熱硬化型接着剤とその接着シ―ト
類は、被着体への接着使用に際し、最終的に加熱処理し
て、アクリル系ポリマ―（に含まれるカルボキシル基）
とエポキシ樹脂との反応により、硬化させる。この硬化
後の貯蔵弾性率は、アクリル系ポリマ―の組成や架橋度
に応じて、エポキシ樹脂の種類や使用量を選択して、２
００〜３００℃の温度域で５×１０5 〜１０7 Ｐａとな
るようにする。また、このように硬化させたのちの吸水
率は、上記ポリマ―の特性と相まつて、３０℃，８０％
ＲＨ保存下での飽和吸水率が１．０重量％以下となり、
これによつて強固な接着強度と高耐熱性、とくに１００
℃以上の高温での使用やハンダ付け工程での使用に耐え
る高耐熱性が得られ、しかも加湿条件投入後の熱試験で
も剥離異常をきたさない、信頼性にすぐれたものとな
る。The thermosetting adhesive of the present invention and the adhesive sheet thereof are finally subjected to a heat treatment when used for bonding to an adherend, so that the acrylic polymer (carboxyl group contained in the acrylic polymer) is used.
Is cured by the reaction between the resin and the epoxy resin. The storage modulus after curing can be determined by selecting the type and amount of epoxy resin to be used according to the composition and the degree of crosslinking of the acrylic polymer.
The pressure is set to 5 × 10 5 to 10 7 Pa in a temperature range of 00 to 300 ° C. The water absorption after curing as described above is 30 ° C., 80%
The saturated water absorption under RH storage becomes 1.0% by weight or less,
As a result, a strong adhesive strength and high heat resistance, especially 100
High heat resistance that can withstand use at a high temperature of ℃ or more or use in the soldering process is obtained, and furthermore, there is no peeling abnormality even in a heat test after humidifying conditions have been introduced, and it is excellent in reliability.
【００２０】最終加熱処理による硬化後の上記貯蔵弾性
率が５×１０5 Ｐａ未満となると、加熱処理時の吸湿水
分の気化・膨張による発生応力の緩和には有利である
が、接着剤のバルクでの破壊が起こりやすく、またこの
破壊が起こらないまでも、低弾性体のために接着剤の変
形により応力を緩和するため、電子部品などの位置ずれ
を引き起こしやすい。また、硬化後の上記貯蔵弾性率が
１０7 Ｐａを超えてしまうと、応力緩和効果が少なく、
応力集中を起こして接着界面で破壊する問題がある。さ
らに、硬化後の飽和吸水率が１．０重量％を超えると、
加湿条件投入後の熱試験で剥離異常などの支障をきたし
やすい。When the above storage elastic modulus after curing by the final heat treatment is less than 5 × 10 5 Pa, it is advantageous for relieving the stress generated by the vaporization and expansion of the moisture absorbed during the heat treatment. Even if this breakage does not occur, the stress is reduced by deformation of the adhesive due to the low elasticity, so that the electronic components and the like are easily displaced. Further, if the storage elastic modulus after curing exceeds 10 7 Pa, the stress relaxation effect is small,
There is a problem of causing stress concentration and breaking at the bonding interface. Further, when the saturated water absorption after curing exceeds 1.0% by weight,
It is easy to cause troubles such as peeling abnormalities in the thermal test after the humidification condition is applied.
【００２１】[0021]
【実施例】つぎに、本発明の実施例を記載して、より具
体的に説明する。なお、以下において部とあるのは重量
部を意味するものとする。Next, an embodiment of the present invention will be described in more detail. In the following, “parts” means “parts by weight”.
【００２２】実施例１ 冷却管、窒素導入管、温度計、撹拌機を備えた反応容器
に、酢酸エチル２１０部を溶媒として、フエノキシエチ
ルアクリレ―ト９５部、アクリル酸５部、過酸化ベンゾ
イル０．３部を入れ、窒素気流中で重合処理して、固形
分が約３０重量％のアクリル系ポリマ―の溶液を得た。
この溶液に、その固形分１００部あたり、エポキシ樹脂
（油化シエルエポキシ社製の商品名「エピコ―ト８２
８」）１５部、多官能イソシアネ―ト系架橋剤１部を均
一に混合し、熱硬化型接着剤溶液を調製した。この接着
剤溶液セパレ―タ上に塗布し、１３０℃で５分間乾燥処
理して、厚さが１００μｍの熱硬化型接着剤層を形成
し、接着シ―トを得た。Example 1 In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 95 parts of phenoxyethyl acrylate, 5 parts of acrylic acid, and 210 parts of ethyl acetate as a solvent were used. 0.3 parts of benzoyl oxide was added and polymerized in a stream of nitrogen to obtain a solution of an acrylic polymer having a solid content of about 30% by weight.
To this solution was added an epoxy resin (trade name “Epicoat 82” manufactured by Yuka Shell Epoxy Co., Ltd.) per 100 parts of the solid content.
8 ") 15 parts and 1 part of a polyfunctional isocyanate-based crosslinking agent were uniformly mixed to prepare a thermosetting adhesive solution. The composition was applied on the adhesive solution separator and dried at 130 ° C. for 5 minutes to form a thermosetting adhesive layer having a thickness of 100 μm, thereby obtaining an adhesive sheet.
【００２３】実施例２ 四つ口フラスコに、フエノキシエチルアクリレ―ト９０
部、イソボルニルアクリレ―ト５部、アクリル酸５部、
２，２−ジメトキシ−２−フエニルアセトフエノン０．
０５部を投入し、窒素雰囲気下、紫外線を照射して部分
的に光重合させることにより、粘度が約３０ポイズのシ
ロツプを得た。この部分重合したシロツプ１００部に、
エポキシ樹脂（油化シエルエポキシ社製の商品名「エピ
コ―ト８２８」）１５部、交叉結合剤としての１，６−
ヘキサンジオ―ルジアクリレ―ト０．３部を均一に混合
し、光重合性組成物を調製した。この光重合性組成物を
セパレ―タ上に塗布し、９００ｍｊ／cm2 の紫外線を照
射して光重合させ、厚さが１００μｍの熱硬化型接着剤
層を形成し、接着シ―トを得た。Example 2 In a four-necked flask, phenoxyethyl acrylate 90 was added.
Parts, isobornyl acrylate 5 parts, acrylic acid 5 parts,
2,2-dimethoxy-2-phenylacetophenone 0.
The mixture was irradiated with ultraviolet rays in a nitrogen atmosphere and partially polymerized by partial irradiation to obtain a syrup having a viscosity of about 30 poise. In 100 parts of this partially polymerized syrup,
15 parts of epoxy resin (trade name "Epiccoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.), 1,6- as a cross-linking agent
0.3 parts of hexanediol diacrylate was uniformly mixed to prepare a photopolymerizable composition. This photopolymerizable composition is applied on a separator and irradiated with 900 mj / cm 2 of ultraviolet light to be photopolymerized to form a thermosetting adhesive layer having a thickness of 100 μm to obtain an adhesive sheet. Was.
【００２４】実施例３ フエノキシエチルアクリレ―ト９０部に代えて、クレゾ
―ルのエチレンオキシド付加物（付加モル数１）とアク
リル酸とのエステルを用いた以外は、実施例２と同様に
して光重合性組成物を調製し、これを用いて実施例２と
同様にして厚さが１００μｍの熱硬化型接着剤層を形成
し、接着シ―トを得た。Example 3 The same procedure as in Example 2 was carried out except that an ester of cresol ethylene oxide adduct (additional mole number: 1) and acrylic acid was used in place of 90 parts of phenoxyethyl acrylate. A thermosetting adhesive layer having a thickness of 100 μm was formed in the same manner as in Example 2 to obtain an adhesive sheet.
【００２５】実施例４ 四つ口フラスコに、フエノキシエチルアクリレ―ト９０
部、イソボルニルアクリレ―ト５部、アクリル酸５部、
２，２−ジメトキシ−２−フエニルアセトフエノン０．
０５部を投入し、窒素雰囲気下、紫外線を照射して部分
的に光重合させることにより、粘度が約３０ポイズのシ
ロツプを得た。この部分重合したシロツプ１００部に、
エポキシ樹脂（油化シエルエポキシ社製の商品名「エピ
コ―ト８２８」）１０部、シリカ粉末（株式会社アドマ
テツクス製の商品名「アドマフアインＳＯ−Ｅ５」）５
０部、交叉結合剤としての１，６−ヘキサンジオ―ルジ
アクリレ―ト０．３部を均一に混合し、光重合性組成物
を調製した。この光重合性組成物をセパレ―タ上に塗布
し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、
厚さが１００μｍの熱硬化型接着剤層を形成し、接着シ
―トを得た。Example 4 In a four-necked flask, phenoxyethyl acrylate 90 was added.
Parts, isobornyl acrylate 5 parts, acrylic acid 5 parts,
2,2-dimethoxy-2-phenylacetophenone 0.
The mixture was irradiated with ultraviolet rays in a nitrogen atmosphere and partially polymerized by partial irradiation to obtain a syrup having a viscosity of about 30 poise. In 100 parts of this partially polymerized syrup,
10 parts of epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and 5 silica powders (trade name “Admafine SO-E5” manufactured by Admatex Co., Ltd.)
0 parts and 0.3 part of 1,6-hexanediol diacrylate as a crosslinking agent were uniformly mixed to prepare a photopolymerizable composition. This photopolymerizable composition is coated on a separator and irradiated with 900 mj / cm 2 of ultraviolet light to be photopolymerized.
A thermosetting adhesive layer having a thickness of 100 μm was formed to obtain an adhesive sheet.
【００２６】実施例５ 四つ口フラスコに、フエノキシエチルアクリレ―ト９５
部、アクリル酸５部、２，２−ジメトキシ−２−フエニ
ルアセトフエノン０．０５部を投入し、窒素雰囲気下、
紫外線を照射して部分的に光重合させることにより、粘
度が約３０ポイズのシロツプを得た。この部分重合した
シロツプ１００部に、アルミナ粉末（株式会社アドマテ
ツクス製の商品名「アドマフアインＡＯ−８０９）」）
１００部、エポキシ樹脂（油化シエルエポキシ社製の商
品名「エピコ―ト８１５」）１０部、交叉結合剤として
のトリメチロ―ルプロパントリアクリレ―ト０．２部を
均一に混合し、光重合性組成物を調製した。この光重合
性組成物をセパレ―タ上に塗布し、９００ｍｊ／cm2 の
紫外線を照射して光重合させ、厚さが１００μｍの熱硬
化型接着剤層を形成し、接着シ―トを得た。Example 5 Phenoxyethyl acrylate 95 was placed in a four-necked flask.
Parts, 5 parts of acrylic acid, and 0.05 parts of 2,2-dimethoxy-2-phenylacetophenone were added, and under a nitrogen atmosphere,
By irradiating ultraviolet rays and partially performing photopolymerization, a syrup having a viscosity of about 30 poise was obtained. Alumina powder (trade name “Admafine AO-809” manufactured by Admatex Co., Ltd.) is added to 100 parts of the partially polymerized syrup.
100 parts, 10 parts of an epoxy resin (trade name "Epiccoat 815" manufactured by Yuka Shell Epoxy Co., Ltd.), and 0.2 part of trimethylolpropane triacrylate as a cross-linking agent were uniformly mixed, A polymerizable composition was prepared. This photopolymerizable composition is applied on a separator and irradiated with 900 mj / cm 2 of ultraviolet light to be photopolymerized to form a thermosetting adhesive layer having a thickness of 100 μm to obtain an adhesive sheet. Was.
【００２７】比較例１ 冷却管、窒素導入管、温度計、撹拌機を備えた反応容器
に、酢酸エチル２１０部を溶媒として、ブチルアクリレ
―ト９５部、アクリル酸５部、過酸化ベンゾイル０．３
部を入れ、窒素気流中で重合処理して、固形分が約３０
重量％のアクリル系ポリマ―の溶液を得た。この溶液
に、その固形分１００部あたり、エポキシ樹脂（油化シ
エルエポキシ社製の商品名「エピコ―ト８２８」）１５
部、多官能イソシアネ―ト系架橋剤１部を均一に混合
し、熱硬化型接着剤溶液を調製した。この接着剤溶液を
セパレ―タ上に塗布し、１３０℃で５分間乾燥処理し
て、厚さが１００μｍの熱硬化型接着剤層を形成し、接
着シ―トを得た。Comparative Example 1 95 parts of butyl acrylate, 5 parts of acrylic acid and 0.3 part of benzoyl peroxide were placed in a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer, using 210 parts of ethyl acetate as a solvent.
And polymerized in a stream of nitrogen to give a solids content of about 30
A solution of a weight% of an acrylic polymer was obtained. An epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) per 100 parts of the solid content was added to this solution.
Parts and one part of a polyfunctional isocyanate-based crosslinking agent were uniformly mixed to prepare a thermosetting adhesive solution. This adhesive solution was applied on a separator and dried at 130 ° C. for 5 minutes to form a thermosetting adhesive layer having a thickness of 100 μm, thereby obtaining an adhesive sheet.
【００２８】比較例２ 冷却管、窒素導入管、温度計、撹拌機を備えた反応容器
に、酢酸エチル２１０部を溶媒として、ブチルアクリレ
―ト６０部、アクリロニトリル３５部、アクリル酸５
部、過酸化ベンゾイル０．３部を入れ、窒素気流中で重
合処理して、固形分が約３０重量％のアクリル系ポリマ
―の溶液を得た。この溶液に、その固形分１００部あた
り、エポキシ樹脂（油化シエルエポキシ社製の商品名
「エピコ―ト８２８」）１５部、多官能イソシアネ―ト
系架橋剤１部を均一に混合し、熱硬化型接着剤溶液を調
製した。この接着剤溶液をセパレ―タ上に塗布し、１３
０℃で５分間乾燥処理して、厚さが１００μｍの熱硬化
型接着剤層を形成し、接着シ―トを得た。Comparative Example 2 60 parts of butyl acrylate, 35 parts of acrylonitrile, and 5 parts of acrylic acid were placed in a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer, and a stirrer, using 210 parts of ethyl acetate as a solvent.
And benzoyl peroxide in an amount of 0.3 part, and polymerized in a nitrogen stream to obtain a solution of an acrylic polymer having a solid content of about 30% by weight. 15 parts of an epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and 1 part of a polyfunctional isocyanate-based cross-linking agent were uniformly mixed with 100 parts of the solid content in the solution. A curable adhesive solution was prepared. This adhesive solution was applied on a separator, and 13
A drying treatment was performed at 0 ° C. for 5 minutes to form a thermosetting adhesive layer having a thickness of 100 μm, thereby obtaining an adhesive sheet.
【００２９】比較例３ 四つ口フラスコに、イソオクチルアクリレ―ト８０部、
アクリル酸２０部、２，２−ジメトキシ−２−フエニル
アセトフエノン０．０５部を投入し、窒素雰囲気下、紫
外線を照射して部分的に光重合させることにより、粘度
が約３０ポイズのシロツプを得た。この部分重合したシ
ロツプ１００部に、エポキシ樹脂（油化シエルエポキシ
社製の商品名「エピコ―ト８２８」）１０部、交叉結合
剤としての１，６−ヘキサンジオ―ルジアクリレ―ト
０．３部を均一に混合し、光重合性組成物を調製した。
この光重合性組成物をセパレ―タ上に塗布し、９００ｍ
ｊ／cm2 の紫外線を照射して光重合させ、厚さが１００
μｍの熱硬化型接着剤層を形成し、接着シ―トを得た。Comparative Example 3 A four-necked flask was charged with 80 parts of isooctyl acrylate,
Acrylic acid (20 parts) and 2,2-dimethoxy-2-phenylacetophenone (0.05 part) are charged, and ultraviolet light is irradiated under a nitrogen atmosphere to partially perform photopolymerization, thereby obtaining a viscosity of about 30 poise. I got a syrup. To 100 parts of the partially polymerized syrup, 10 parts of an epoxy resin (trade name "Epiccoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.) and 0.3 part of 1,6-hexanediol diacrylate as a cross-linking agent are added. The mixture was uniformly mixed to prepare a photopolymerizable composition.
This photopolymerizable composition was applied on a separator, and 900 m
Irradiation of ultraviolet rays of j / cm 2 causes photopolymerization, resulting in a thickness of 100
A thermosetting adhesive layer having a thickness of μm was formed to obtain an adhesive sheet.
【００３０】比較例４ 四つ口フラスコに、フエノキシエチルアクリレ―ト９０
部、イソボルニルアクリレ―ト８部、アクリル酸２部、
２，２−ジメトキシ−２−フエニルアセトフエノン０．
０５部を投入し、窒素雰囲気下、紫外線を照射して部分
的に光重合させることにより、粘度が約３０ポイズのシ
ロツプを得た。この部分重合したシロツプ１００部に、
エポキシ樹脂（油化シエルエポキシ社製の商品名「エピ
コ―ト８２８」）３部、シリカ粉末（株式会社アドマテ
ツクス製の商品名「アドマフアインＳＯ−Ｅ５」）５０
部、交叉結合剤としての１，６−ヘキサンジオ―ルジア
クリレ―ト０．３部を均一に混合し、光重合性組成物を
調製した。この光重合性組成物をセパレ―タ上に塗布
し、９００ｍｊ／cm2 の紫外線を照射して光重合させ、
厚さが１００μｍの熱硬化型接着剤層を形成し、接着シ
―トを得た。Comparative Example 4 In a four-necked flask, phenoxyethyl acrylate 90 was added.
Parts, isobornyl acrylate 8 parts, acrylic acid 2 parts,
2,2-dimethoxy-2-phenylacetophenone 0.
The mixture was irradiated with ultraviolet rays in a nitrogen atmosphere and partially polymerized by partial irradiation to obtain a syrup having a viscosity of about 30 poise. In 100 parts of this partially polymerized syrup,
3 parts of epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and 50 parts of silica powder (trade name “Admafine SO-E5” manufactured by Admatex Co., Ltd.)
Parts and 0.3 part of 1,6-hexanediol diacrylate as a crosslinking agent were uniformly mixed to prepare a photopolymerizable composition. This photopolymerizable composition is coated on a separator and irradiated with 900 mj / cm 2 of ultraviolet light to be photopolymerized.
A thermosetting adhesive layer having a thickness of 100 μm was formed to obtain an adhesive sheet.
【００３１】上記の実施例１〜５および比較例１〜４の
各接着シ―トの熱硬化型接着剤層について、硬化前のガ
ラス転移温度、硬化前および硬化後の貯蔵弾性率、硬化
後の吸水率を、下記の方法により、測定した。また、上
記の各接着シ―トについて、貼り付け性試験および硬化
後の加湿耐熱試験を、下記の方法により調べた。これら
の結果は、表１および表２に示されるとおりであつた。For the thermosetting adhesive layers of the adhesive sheets of Examples 1 to 5 and Comparative Examples 1 to 4, the glass transition temperature before curing, the storage elastic modulus before and after curing, and the after curing Was measured by the following method. Further, for each of the above-mentioned adhesive sheets, a sticking property test and a humidification heat resistance test after curing were examined by the following methods. These results were as shown in Tables 1 and 2.
【００３２】＜ガラス転移温度、貯蔵弾性率の測定＞レ
オメトリツク社製の粘弾性スペクトルメ―タ（ＲＤＳ−
II）により、熱硬化型接着剤層について、硬化前のガラ
ス転移温度を測定し、また１００〜２００℃の範囲での
硬化前の貯蔵弾性率と、２００〜３００℃の範囲での硬
化後（１５０℃で２時間）の貯蔵弾性率を、周波数１ヘ
ルツの条件下で、測定した。<Measurement of Glass Transition Temperature and Storage Elastic Modulus> A viscoelastic spectrum meter (RDS-
According to II), the glass transition temperature of the thermosetting adhesive layer before curing was measured, and the storage elastic modulus before curing in the range of 100 to 200 ° C and the storage modulus after curing in the range of 200 to 300 ° C ( The storage elastic modulus (at 150 ° C. for 2 hours) was measured under the condition of a frequency of 1 Hz.
【００３３】＜吸水率＞１５０℃で２時間の硬化処理を
施した接着シ―トについて、セパレ―タを剥がして熱硬
化型接着剤層のみの初期重量（Ｙ１）を測定したのち、
３０℃，８０％ＲＨに１６８時間放置したのちの重量
（Ｙ２）を測定する。この両測定値より、吸水率（重量
％）＝〔（Ｙ２−Ｙ１）／Ｙ１〕×１００、として求め
た。<Water absorption> With respect to the adhesive sheet subjected to the curing treatment at 150 ° C. for 2 hours, the separator was peeled off, and the initial weight (Y1) of the thermosetting adhesive layer alone was measured.
The weight (Y2) after standing at 30 ° C. and 80% RH for 168 hours is measured. From these two measured values, water absorption (% by weight) = [(Y2−Y1) / Y1] × 100 was determined.
【００３４】＜貼り付け性試験＞接着シ―トをプレス機
（温度：１５０℃、時間：１秒、圧力：５Kg／cm2 ）に
よりガラス板に貼り合わせ、このときの接着界面の状態
を観察し、気泡混入なしを〇、気泡混入ありを×、と評
価した。<Adhesion test> The adhesive sheet was adhered to a glass plate by a press machine (temperature: 150 ° C., time: 1 second, pressure: 5 kg / cm 2 ), and the state of the adhesive interface at this time was observed. The sample was evaluated as “混入” without air bubbles and “×” when air bubbles were mixed.
【００３５】＜加湿耐熱試験＞接着シ―トを厚さが７５
μｍのポリイミドフイルムにラミネ―タ（温度：１００
℃、圧力：５Kg／cm、速度：２ｍ／分）により貼り合わ
せ、これを３０mm角のＳＵＳ３０４にプレス機（温度：
１５０℃、時間：１秒、圧力：５Kg／cm2 ）で貼り合わ
せた。このサンプルについて、１５０℃で２時間の加熱
処理を施して、熱硬化型接着剤層を硬化させたのち、３
０℃，８０％ＲＨの加湿条件下で１６８時間放置し、そ
の後、このサンプルのＳＵＳ３０４面を２６０℃に加熱
したホツトプレ―ト上に放置し、６０秒間処理し、この
ときの外観変化を観察し、上記変化がないものを〇、剥
離異常が発生したものを×、と評価した。<Humidification and heat resistance test>
A laminator (temperature: 100)
° C, pressure: 5 kg / cm, speed: 2 m / min), and this was pressed into a 30 mm square SUS304 press machine (temperature:
At 150 ° C., time: 1 second, pressure: 5 kg / cm 2 ). This sample was subjected to a heat treatment at 150 ° C. for 2 hours to cure the thermosetting adhesive layer.
The sample was left for 168 hours under the humidified condition of 0 ° C. and 80% RH. Then, the SUS304 surface of this sample was left on a hot plate heated to 260 ° C., treated for 60 seconds, and the appearance change at this time was observed. The sample having no change was evaluated as Δ, and the sample having abnormal peeling was evaluated as x.
【００３６】 [0036]
【００３７】 [0037]
【００３８】上記表１の結果から明らかなように、実施
例１〜５の各接着シ―トは、硬化前のガラス転移温度が
−１０℃以上、硬化前の貯蔵弾性率が１００〜２００℃
の温度域で１０4 〜１０5 Ｐａ、硬化後の貯蔵弾性率が
２００〜３００℃の温度域で５×１０5 〜１０7 Ｐａで
あり、かつ硬化後の３０℃，８０％ＲＨ保存下での飽和
吸水率が１．０重量％以下であり、良好な貼り付け性を
示して、接着性と耐熱性を満足させることができ、とく
に加湿条件投入後の熱試験でも剥離異常をきたさない、
信頼性にすぐれたものであることがわかる。As is clear from the results shown in Table 1, each of the adhesive sheets of Examples 1 to 5 had a glass transition temperature before curing of -10 ° C. or more and a storage elastic modulus before curing of 100 to 200 ° C.
Temperature range at 10 4 to 10 5 Pa, a storage elastic modulus 200 to 300 [° C. temperature range at 5 × 10 5 ~10 7 Pa after hardened, and 30 ° C. after curing, under storage RH 80% Has a saturated water absorption of 1.0% by weight or less, exhibits good adhesive properties, and can satisfy adhesiveness and heat resistance. In particular, it does not cause peeling abnormality even in a thermal test after humidification conditions are applied.
It turns out that it is excellent in reliability.
【００３９】これに対し、上記表２の結果から明らかな
ように、比較例１〜３の各接着シ―トは、（メタ）アク
リル酸アルキルエステルを主モノマ―としたアクリル系
ポリマ―を使用したものであつて、上記主モノマ―と共
重合させるモノマ―組成を種々変更しても、硬化前のガ
ラス転移温度、硬化前および硬化後の貯蔵弾性率、硬化
後の吸水率のすべてを本発明の範囲内に設定することが
難しく、結果として、接着性と耐熱性のバランスをとり
にくく、とくに硬化前の貯蔵弾性率が高すぎる比較例２
の接着シ―トでは低圧・短時間での接着処理すら困難で
ある。また、比較例４の接着シ―トは、本発明と同様の
アクリル系ポリマ―を使用したものであるが、エポキシ
樹脂による硬化処理後の貯蔵弾性率が低すぎるため、加
湿耐熱試験において剥離異常をきたし、信頼性に劣つた
ものとなる。On the other hand, as is clear from the results in Table 2 above, each of the adhesive sheets of Comparative Examples 1 to 3 uses an acrylic polymer whose main monomer is an alkyl (meth) acrylate. Even if the composition of the monomer to be copolymerized with the above-mentioned main monomer is variously changed, the glass transition temperature before curing, the storage elastic modulus before and after curing, and the water absorption after curing are all determined. It is difficult to set within the range of the invention, and as a result, it is difficult to balance the adhesiveness and the heat resistance, and in particular, the storage modulus before curing is too high in Comparative Example 2.
It is difficult to perform even low-pressure, short-time bonding with the above-mentioned bonding sheet. The adhesive sheet of Comparative Example 4 used the same acrylic polymer as that of the present invention. However, since the storage elastic modulus after curing treatment with an epoxy resin was too low, peeling abnormalities in a humidification heat test were observed. And have poor reliability.
【００４０】[0040]
【発明の効果】以上のように、本発明においては、特定
の（メタ）アクリル酸エステルを主モノマ―とするアク
リル系ポリマ―にエポキシ樹脂を加え、上記ポリマ―の
架橋度を調節して硬化前のガラス転移温度および貯蔵弾
性率を特定し、かつ硬化後の貯蔵弾性率および吸水率を
特定する構成としたことにより、接着処理に際しては、
常温で非粘着ないし弱粘着のため、熱接着時に気泡の抱
き込みを生じず、低圧・短時間での接着処理が可能であ
り、これを最終的に加熱処理して硬化させることによ
り、強固な接着強度と高耐熱性が得られ、かつ加湿条件
投入後の熱試験でも剥離異常をきたさない、信頼性にす
ぐれた熱硬化型接着剤と、これをシ―ト状やテ―プ状な
どの形態とした接着シ―ト類とを提供することができ
る。As described above, according to the present invention, an epoxy resin is added to an acrylic polymer having a specific (meth) acrylic acid ester as a main monomer, and the degree of crosslinking of the polymer is adjusted to cure the polymer. By specifying the glass transition temperature and storage modulus before curing, and by specifying the storage modulus and water absorption after curing, during the bonding process,
Because it is non-adhesive or weakly adhesive at room temperature, it does not generate air bubbles during thermal bonding and can be bonded at low pressure and in a short time. A highly-reliable thermosetting adhesive that has adhesive strength and high heat resistance and does not cause abnormal peeling even after a thermal test after humidifying conditions have been applied. An adhesive sheet in a form can be provided.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J004 AA02 AA10 AA13 AA18 AB05 CA06 CB01 CC02 DB02 EA05 FA05 FA08 4J040 DF061 DN061 EC062 EC072 EC152 EC231 GA05 GA07 GA08 GA13 GA22 GA25 HA136 HA196 HA306 JA09 JB02 KA01 KA03 KA16 KA42 LA02 LA03 LA05 LA06 LA07 NA19 NA20 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J004 AA02 AA10 AA13 AA18 AB05 CA06 CB01 CC02 DB02 EA05 FA05 FA08 4J040 DF061 DN061 EC062 EC072 EC152 EC231 GA05 GA07 GA08 GA13 GA22 GA25 HA136 HA196 HA306 JA09 JB02 KA03 KA03 LA03 LA06 LA07 NA19 NA20
Claims (4)
ン基、エチレン基またはプロピレン基、ｎ＝１〜３の整
数、φはフエニル基、モノアルキル置換フエニル基また
はジアルキル置換フエニル基である）で表される（メ
タ）アクリル酸エステルを主モノマ―とするアクリル系
ポリマ―とエポキシ樹脂を含有してなり、硬化前のガラ
ス転移温度が−１０℃以上、硬化前の貯蔵弾性率が１０
０〜２００℃の温度域で１０4 〜１０5 Ｐａ、硬化後の
貯蔵弾性率が２００〜３００℃の温度域で５×１０5 〜
１０7 Ｐａであり、かつ硬化後の３０℃，８０％ＲＨ保
存下での飽和吸水率が１．０重量％以下であることを特
徴とする熱硬化型接着剤。1. The following equation (1): (Wherein R 1 is a hydrogen atom or a methyl group, R 2 is a methylene group, an ethylene group or a propylene group, n is an integer of 1 to 3, and φ is a phenyl group, a monoalkyl-substituted phenyl group or a dialkyl-substituted phenyl group. ) Containing an acrylic polymer having a (meth) acrylic acid ester as a main monomer and an epoxy resin, a glass transition temperature before curing of -10 ° C or more, and a storage elastic modulus before curing of 10
10 4 to 10 5 Pa in a temperature range of 0 to 200 ° C., and a storage elastic modulus after curing of 5 × 10 5 to 5 in a temperature range of 200 to 300 ° C.
A thermosetting adhesive characterized by having a pressure of 10 7 Pa and a saturated water absorption of 1.0% by weight or less after storage at 30 ° C. and 80% RH.
る（メタ）アクリル酸エステルに全モノマ―中１〜５重
量％のアクリル酸を加えたモノマ―混合物の共重合体か
らなり、かつエポキシ樹脂がエポキシ当量５００以下の
エポキシ樹脂からなり、上記アクリル系ポリマ―１００
重量部あたり、上記エポキシ樹脂が５〜３０重量部であ
る請求項１に記載の熱硬化型接着剤。2. An acrylic polymer comprising a copolymer of a monomer mixture obtained by adding 1 to 5% by weight of acrylic acid in all monomers to a (meth) acrylate represented by the formula (1), And the epoxy resin comprises an epoxy resin having an epoxy equivalent of 500 or less, and the acrylic polymer 100
The thermosetting adhesive according to claim 1, wherein the epoxy resin is 5 to 30 parts by weight per part by weight.
り、無機充填剤１０〜１００重量部を含有する請求項１
または２に記載の熱硬化型接着剤。3. An acrylic polymer containing 10 to 100 parts by weight of an inorganic filler per 100 parts by weight of an acrylic polymer.
Or the thermosetting adhesive according to 2.
いずれかに記載の熱硬化型接着剤からなる層を有するこ
とを特徴とする接着シ―ト類。4. An adhesive sheet having a layer comprising the thermosetting adhesive according to claim 1 on one or both sides of a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33269899A JP4607270B2 (en) | 1999-11-24 | 1999-11-24 | Thermosetting adhesive and its adhesive sheets |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33269899A JP4607270B2 (en) | 1999-11-24 | 1999-11-24 | Thermosetting adhesive and its adhesive sheets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001152123A true JP2001152123A (en) | 2001-06-05 |
| JP4607270B2 JP4607270B2 (en) | 2011-01-05 |
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ID=18257889
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33269899A Expired - Fee Related JP4607270B2 (en) | 1999-11-24 | 1999-11-24 | Thermosetting adhesive and its adhesive sheets |
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| Country | Link |
|---|---|
| JP (1) | JP4607270B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055632A (en) * | 2001-08-21 | 2003-02-26 | Lintec Corp | Pressure-sensitive adhesive tape |
| JP2004352855A (en) * | 2003-05-29 | 2004-12-16 | Toray Ind Inc | Adhesive-coated tape for semiconductor, substrate for connection of semiconductor integrated circuit, and semiconductor device |
| JP2008231358A (en) * | 2007-03-23 | 2008-10-02 | Dic Corp | Image display module for electronic terminal and pressure-sensitive adhesive sheet for whole surface lamination |
| JP2009286996A (en) * | 2008-04-30 | 2009-12-10 | Hitachi Chem Co Ltd | Adhesive film, adhesive sheet, semiconductor device, and manufacturing method of it |
| JP2009295951A (en) * | 2008-05-09 | 2009-12-17 | Hitachi Chem Co Ltd | Adhesive film, adhesive sheet, semiconductor device, and method for manufacturing semiconductor device |
| JP2010265453A (en) * | 2009-04-17 | 2010-11-25 | Furukawa Electric Co Ltd:The | Adhesive film and tape for wafer processing |
| JP2013077855A (en) * | 2013-01-31 | 2013-04-25 | Lintec Corp | Adhesive used for manufacturing method of semiconductor device |
| CN113727844A (en) * | 2019-04-26 | 2021-11-30 | 三井化学东赛璐株式会社 | Adhesive film and method for manufacturing electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310680A (en) * | 1986-07-01 | 1988-01-18 | Yokohama Rubber Co Ltd:The | Tacky adhesive composition |
| WO1997043352A1 (en) * | 1996-05-16 | 1997-11-20 | Minnesota Mining And Manufacturing Company | Adhesive compositions and methods of use |
-
1999
- 1999-11-24 JP JP33269899A patent/JP4607270B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310680A (en) * | 1986-07-01 | 1988-01-18 | Yokohama Rubber Co Ltd:The | Tacky adhesive composition |
| WO1997043352A1 (en) * | 1996-05-16 | 1997-11-20 | Minnesota Mining And Manufacturing Company | Adhesive compositions and methods of use |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055632A (en) * | 2001-08-21 | 2003-02-26 | Lintec Corp | Pressure-sensitive adhesive tape |
| JP2004352855A (en) * | 2003-05-29 | 2004-12-16 | Toray Ind Inc | Adhesive-coated tape for semiconductor, substrate for connection of semiconductor integrated circuit, and semiconductor device |
| JP4547866B2 (en) * | 2003-05-29 | 2010-09-22 | 東レ株式会社 | Tape with adhesive for semiconductor, substrate for semiconductor connection, and semiconductor device |
| JP2008231358A (en) * | 2007-03-23 | 2008-10-02 | Dic Corp | Image display module for electronic terminal and pressure-sensitive adhesive sheet for whole surface lamination |
| JP2009286996A (en) * | 2008-04-30 | 2009-12-10 | Hitachi Chem Co Ltd | Adhesive film, adhesive sheet, semiconductor device, and manufacturing method of it |
| JP2009295951A (en) * | 2008-05-09 | 2009-12-17 | Hitachi Chem Co Ltd | Adhesive film, adhesive sheet, semiconductor device, and method for manufacturing semiconductor device |
| JP2010265453A (en) * | 2009-04-17 | 2010-11-25 | Furukawa Electric Co Ltd:The | Adhesive film and tape for wafer processing |
| JP2013077855A (en) * | 2013-01-31 | 2013-04-25 | Lintec Corp | Adhesive used for manufacturing method of semiconductor device |
| CN113727844A (en) * | 2019-04-26 | 2021-11-30 | 三井化学东赛璐株式会社 | Adhesive film and method for manufacturing electronic device |
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