JP2003027014A - Adhesive film - Google Patents
Adhesive filmInfo
- Publication number
- JP2003027014A JP2003027014A JP2001217373A JP2001217373A JP2003027014A JP 2003027014 A JP2003027014 A JP 2003027014A JP 2001217373 A JP2001217373 A JP 2001217373A JP 2001217373 A JP2001217373 A JP 2001217373A JP 2003027014 A JP2003027014 A JP 2003027014A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- polyimide
- film
- adhesive film
- solvent
- 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.)
- Pending
Links
Landscapes
- Laminated Bodies (AREA)
- 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、微細加工が求めら
れる半導体固定用接着フィルムに関する。更に詳しく
は、フレキシブル印刷回路基板、ＴＡＢ（Ｔａｐｅ Ａ
ｕｔｏｍａｔｅｄｂｏｎｄｉｎｇ）用テープ、複合リー
ドフレーム、積層材料、電子部品等の微細加工性、耐熱
性、接着性が要求される分野で有用な接着性フィルムに
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive film for semiconductor fixing, which requires fine processing. More specifically, a flexible printed circuit board, TAB (Tape A
The present invention relates to an adhesive film that is useful in fields requiring fine workability, heat resistance, and adhesiveness for automated bonding tapes, composite lead frames, laminated materials, electronic components, and the like.
【０００２】[0002]
【従来の技術】近年、電子機器の高機能化、高性能化、
小型化が進んでおり、それらに伴って用いられる電子部
品に対する小型化、軽量化が求められてきている。その
ため半導体素子パッケージ方法やそれらを実装する配線
材料または配線部品も、より高密度、高機能かつ高性能
なものが求められるようになってきた。特に、半導体パ
ッケージ、ＣＯＬおよびＬＯＣパッケージ、ＭＣＭ（Ｍ
ｕｌｔｉ Ｃｈｉｐ Ｍｏｄｕｌｅ）等の高密度実装材
料や多層ＦＰＣ等のプリント配線板材料に好適に用いる
ことのできる、微細加工が可能で良好な接着性を示す接
着材料が求められている。2. Description of the Related Art In recent years, electronic devices have become more sophisticated, have higher performance,
The miniaturization is progressing, and the miniaturization and the weight reduction of the electronic components used in association with them are demanded. Therefore, semiconductor device packaging methods and wiring materials or wiring components for mounting them have been required to have higher density, higher functionality and higher performance. In particular, semiconductor packages, COL and LOC packages, MCM (M
There is a demand for an adhesive material that can be suitably used for high-density mounting materials such as an ulti-chip module) and printed wiring board materials such as a multi-layer FPC and that can be microfabricated and that exhibits good adhesiveness.
【０００３】この分野においては、これまでポリイミド
フィルムの片面もしくは両面にフェノール系およびエポ
キシ系の接着剤、アクリル系の接着剤を積層した接着フ
ィルムが用いられていた。これらの接着フィルムはベー
スフィルムとしてポリイミドフィルムを用いるため、１
０μｍ以下の薄い接着フィルムを得ることは困難であ
る。さらに異種材料を積層しているため、加工性に差異
が生じ、微細加工が求められる用途には適していない。In this field, an adhesive film in which a phenolic or epoxy adhesive or an acrylic adhesive is laminated on one side or both sides of a polyimide film has been used. Since these adhesive films use a polyimide film as a base film, 1
It is difficult to obtain a thin adhesive film of 0 μm or less. Further, since different kinds of materials are laminated, the workability is different, and it is not suitable for applications requiring fine processing.
【０００４】また、耐熱性、電気特性等の信頼性の点で
優れる材料としてポリイミド単層フィルムがある。A polyimide single layer film is a material excellent in reliability such as heat resistance and electric characteristics.
【０００５】ポリイミドは、種々の有機ポリマーの中で
も耐熱性に優れているため、宇宙、航空分野まで幅広く
用いられ、接着材料としても用いられている。しかし、
耐熱性の高いポリイミド系接着剤は接着するために３０
０℃前後の高温と高圧力を要し、接着力もそれほど高い
とはいえない。Since polyimide has excellent heat resistance among various organic polymers, it is widely used in the fields of space and aviation, and is also used as an adhesive material. But,
It is necessary to use a polyimide adhesive with high heat resistance for bonding.
It requires high temperature around 0 ° C and high pressure, and the adhesive strength is not so high.
【０００６】[0006]
【発明が解決しようとする課題】そこで本発明者らは、
上記課題を解決し、耐熱性と接着性を保ちつつ、微細加
工が容易な接着性フィルムを提供することを目的とし、
鋭意研究を行った結果、本発明を完成するに至った。Therefore, the present inventors have found that
With the object of solving the above problems and maintaining heat resistance and adhesiveness, it is an object to provide an adhesive film that is easily microfabricated.
As a result of earnest research, the present invention has been completed.
【０００７】[0007]
【課題を解決するための手段】本発明は以下の構成から
なる新規な接着性フィルムを提供するものであり、これ
により上記目的が達成される。
１）離型性を有する保護フィルムの上に溶媒可溶性熱可
塑性ポリイミド，エポキシ樹脂および硬化剤を含有する
２００℃以下で接着可能な接着剤層を１０μｍ以下の厚
みで積層した接着性フィルム。
２）前記溶媒可溶性熱可塑性ポリイミドのガラス転移温
度が２００℃以下であり、該可溶性熱可塑性ポリイミド
に含まれる酸二無水物残基の５０モル％以上が一般式
（１）The present invention provides a novel adhesive film having the following constitution, which achieves the above object. 1) An adhesive film in which an adhesive layer containing a solvent-soluble thermoplastic polyimide, an epoxy resin, and a curing agent and capable of adhering at 200 ° C. or less is laminated to a thickness of 10 μm or less on a protective film having releasability. 2) The glass transition temperature of the solvent-soluble thermoplastic polyimide is 200 ° C. or lower, and 50 mol% or more of the acid dianhydride residues contained in the soluble thermoplastic polyimide is represented by the general formula (1).
【０００８】[0008]
【化３】
で表されるエステル酸二無水物残基であることを特徴と
する請求項１記載の接着性フィルム。
３）前記溶媒可溶性熱可塑性ポリイミドが、該ポリイミ
ドに含まれるジアミン残基のモル％以上が下記一般式
（２）[Chemical 3] The adhesive film according to claim 1, which is an ester dianhydride residue represented by: 3) The solvent-soluble thermoplastic polyimide has the following general formula (2) in which mol% or more of the diamine residues contained in the polyimide are
【０００９】[0009]
【化４】
で表されるジアミン化合物の残基であることを特徴とす
る１）または２）に記載の接着性フィルム。
４）前記離型性を有する保護フィルムが、シリコン系処
理剤で処理されたフィルムである１）〜３）のいずれか
一項に記載の接着性フィルム。
５）前記１）〜４）のいずれか一項に記載の接着性フィ
ルムを、接着層を離型性を有する保護フィルム付きの状
態で被着体に貼り合わせた後、離型性を有する保護フィ
ルムを取り除くことを特徴とする接着性フィルムの貼り
合わせ方法。[Chemical 4] The adhesive film according to 1) or 2), which is a residue of a diamine compound represented by: 4) The adhesive film according to any one of 1) to 3), wherein the protective film having releasability is a film treated with a silicon-based treating agent. 5) After the adhesive film according to any one of 1) to 4) is attached to an adherend with an adhesive layer having a protective film having releasability, it is protected with releasability. A method for laminating an adhesive film, which comprises removing the film.
【００１０】[0010]
【発明の実施の形態】本発明の接着性フィルムは、例え
ば半導体固定用接着フィルムなどに用いることができ、
離型処理を施した保護フィルムの上に溶媒可溶性熱可塑
性ポリイミド，エポキシ樹脂および硬化剤からなる２０
０℃以下で接着可能な接着剤層を１０μｍ以下の厚みで
積層して得られる。BEST MODE FOR CARRYING OUT THE INVENTION The adhesive film of the present invention can be used, for example, as an adhesive film for fixing semiconductors,
A solvent-soluble thermoplastic polyimide, an epoxy resin, and a curing agent are formed on a protective film that has been subjected to a release treatment.
It is obtained by laminating adhesive layers that can be adhered at 0 ° C. or less with a thickness of 10 μm or less.
【００１１】用いる保護フィルムはＰＥＴ、ＰＥＮ、Ｐ
ＰＳ、ポリイミド等の耐熱性フィルムが望ましいがそれ
以外のフィルムであってもかまわない。厚みは５〜２０
０μｍ、好ましくは１０〜１００μｍである。これらの
保護フィルムをシリコン系処理剤で処理したフィルムも
好ましく用いられる。The protective film used is PET, PEN, P
A heat resistant film such as PS or polyimide is desirable, but other films may be used. 5-20 thickness
It is 0 μm, preferably 10 to 100 μm. Films obtained by treating these protective films with a silicone-based treating agent are also preferably used.
【００１２】接着層の厚みは１０μｍ以下であることが
重要である。好ましくは３〜７μｍである。厚いと微細
加工性に劣るものとなり、逆に薄すぎると取り扱い性が
悪くなる。It is important that the thickness of the adhesive layer is 10 μm or less. It is preferably 3 to 7 μm. If it is too thick, the fine workability is inferior, and if it is too thin, it is difficult to handle.
【００１３】本発明の半導体固定用接着フィルムは、接
着層を離型性を有する保護フィルム付きの状態で被着体
に貼り合わせた後、離型性を有する保護フィルムを剥離
し使用する。接着温度は２００℃以下であり、好ましく
は１００℃〜２００℃である。The semiconductor fixing adhesive film of the present invention is used by adhering the adhesive layer with the protective film having releasability to an adherend and then peeling off the protective film having releasability. The adhesion temperature is 200 ° C or lower, preferably 100 ° C to 200 ° C.
【００１４】また、本発明の半導体固定用接着フィルム
に用いる接着剤は、熱可塑性ポリイミド、エポキシ樹脂
および硬化剤とから構成される。該接着剤は、各接着剤
構成成分を有機溶媒に溶解させ接着剤溶液を得、離型性
のフィルム上にキャストした後、有機溶媒を加熱除去し
得られる。接着剤溶液は、有機溶媒に熱可塑性ポリイミ
ド、エポキシ樹脂および硬化剤を溶解させて得られる
が、比較的低温で溶媒を乾燥除去できるため、環状エー
テル系溶媒を含有する有機溶媒を使用するのが好まし
い。環状エーテル系溶媒としては、テトラヒドロフラン
（ＴＨＦ）、１，４−ジオキサン、ジオキソランが好ま
しく用いられ得る。また、複数の溶媒を混合した混合有
機溶媒を用いる場合には、極性有機溶媒と組み合わせた
方が好ましいが、環状エーテル系溶媒を３０重量％以
上、好ましくは５０重量％以上含有するほうが本発明の
効果が発現しやすい。なお環状エーテル系溶媒と組み合
わせる有機極性溶媒としては、ジメチルスルホキシド、
ジエチルスルホキシド等のスルホキシド系溶媒、Ｎ，Ｎ
−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミ
ド等のホルムアミド系溶媒、Ｎ，Ｎ−ジメチルアセトア
ミド、Ｎ，Ｎ−ジエチルアセトアミド等のアセトアミド
系溶媒が挙げられる。The adhesive used in the semiconductor fixing adhesive film of the present invention comprises a thermoplastic polyimide, an epoxy resin and a curing agent. The adhesive can be obtained by dissolving each adhesive constituent component in an organic solvent to obtain an adhesive solution, casting the solution on a releasable film, and then removing the organic solvent by heating. The adhesive solution can be obtained by dissolving the thermoplastic polyimide, the epoxy resin and the curing agent in an organic solvent, but since the solvent can be removed by drying at a relatively low temperature, it is recommended to use an organic solvent containing a cyclic ether solvent. preferable. Tetrahydrofuran (THF), 1,4-dioxane and dioxolane can be preferably used as the cyclic ether solvent. When a mixed organic solvent obtained by mixing a plurality of solvents is used, it is preferable to combine it with a polar organic solvent, but it is preferable that the cyclic ether solvent is contained in an amount of 30% by weight or more, preferably 50% by weight or more. The effect is easily expressed. The organic polar solvent to be combined with the cyclic ether solvent is dimethyl sulfoxide,
Sulfoxide solvents such as diethyl sulfoxide, N, N
Formamide solvents such as -dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide.
【００１５】これらの溶媒に、殆どの熱可塑性ポリイミ
ドは不溶もしくは難溶であるが、本発明の可溶性熱可塑
性ポリイミドは分子中に含まれる酸二無水物残基の５０
モル％以上が一般式（１）Most of the thermoplastic polyimides are insoluble or sparingly soluble in these solvents, but the soluble thermoplastic polyimide of the present invention contains 50 or more acid dianhydride residues contained in the molecule.
More than mol% is general formula (1)
【００１６】[0016]
【化５】
で表されるエステル酸二無水物残基であることを特徴と
しているためこれらの有機溶媒にも溶解可能である。一
般式（１）で表される酸二無水物の好ましい例として
は、２，２−ビス（４−ヒドロキシフェニル）プロパン
ジベンゾエート−３，３’，４，４’−テトラカルボン
酸二無水物、ｐ−フェニレンビス（トリメリット酸モノ
エステル無水物）、４，４’−ビフェニレンビス（トリ
メリット酸モノエステル無水物）、１，４−ナフタレン
ビス（トリメリット酸モノエステル無水物）、１，２−
エチレンビス（トリメリット酸モノエステル無水物）、
１，３−トリメチレンビス（トリメリット酸モノエステ
ル無水物）、１，４−テトラメチレンビス（トリメリッ
ト酸モノエステル無水物）、１，５−ペンタメチレンビ
ス（トリメリット酸モノエステル無水物）、１，６−ヘ
キサメチレンビス（トリメリット酸モノエステル無水
物）等が挙げられるが、式（３）[Chemical 5] Since it is characterized by being an ester dianhydride residue represented by, it can be dissolved in these organic solvents. Preferred examples of the acid dianhydride represented by the general formula (1) include 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride. , P-phenylene bis (trimellitic acid monoester anhydride), 4,4'-biphenylene bis (trimellitic acid monoester anhydride), 1,4-naphthalene bis (trimellitic acid monoester anhydride), 1, 2-
Ethylene bis (trimellitic acid monoester anhydride),
1,3-trimethylene bis (trimellitic acid monoester anhydride), 1,4-tetramethylene bis (trimellitic acid monoester anhydride), 1,5-pentamethylene bis (trimellitic acid monoester anhydride) , 1,6-hexamethylene bis (trimellitic acid monoester anhydride) and the like are represented by the formula (3)
【００１７】[0017]
【化６】
で表される２，２−ビス（４−ヒドロキシフェニル）プ
ロパンジベンゾエート−３，３’，４，４’−テトラカ
ルボン酸二無水物は特に好ましい。[Chemical 6] 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride represented by is particularly preferable.
【００１８】また、上記の酸二無水物と反応させるジア
ミン成分としては下記一般式（２）The diamine component to be reacted with the acid dianhydride is represented by the following general formula (2)
【００１９】[0019]
【化７】
で表されるジアミン化合物、特にビス（アミノフェノキ
シフェニル）スルフォンが好ましい。なお、一般式
（２）において、複数個のＹは各繰り返し単位間で同一
であっても異なっていても良く、各ベンゼン環の水素は
当業者の考え得る範囲内で種々の置換基で適宜置換され
得る。例えば、メチル基、エチル基等の炭化水素基やＢ
ｒ、Ｃｌ等のハロゲン基を挙げることができるが、これ
らの置換基に限定されない。さらに、一般式（２）で表
されるジアミン化合物中、メタ位にアミノ基を有するジ
アミン化合物は、それを用いた熱可塑性ポリイミドの有
機溶媒への溶解性が良好なため加工性に優れた接着剤溶
液が得られて好ましい。なお、一般式（２）で表される
ジアミン化合物は、２種以上を混合して用いても良い。[Chemical 7] A diamine compound represented by, and particularly bis (aminophenoxyphenyl) sulfone is preferable. In the general formula (2), a plurality of Y's may be the same or different in each repeating unit, and the hydrogen of each benzene ring is appropriately substituted with various substituents within the range conceivable to those skilled in the art. Can be replaced. For example, a hydrocarbon group such as a methyl group or an ethyl group, or B
Examples thereof include halogen groups such as r and Cl, but are not limited to these substituents. Further, in the diamine compound represented by the general formula (2), the diamine compound having an amino group at the meta position has excellent solubility in the organic solvent of the thermoplastic polyimide using the same, and thus has excellent processability. A drug solution is obtained, which is preferable. The diamine compound represented by the general formula (2) may be used as a mixture of two or more kinds.
【００２０】本発明のポリイミド系接着剤溶液に溶解す
る熱可塑性ポリイミドは、その前駆体であるポリアミド
酸重合体を脱水閉環して得られる。このポリアミド酸溶
液は、前記した酸二無水物と前記したジアミン化合物と
が実質的に等モルになるように使用し、有機極性溶媒中
で重合して得られる。The thermoplastic polyimide which is soluble in the polyimide adhesive solution of the present invention is obtained by dehydrating and ring-closing the polyamic acid polymer which is the precursor thereof. This polyamic acid solution is obtained by using the above-mentioned acid dianhydride and the above-mentioned diamine compound in substantially equimolar amounts and polymerizing them in an organic polar solvent.
【００２１】このポリアミド酸またはポリイミドは、ま
ず、アルゴン、窒素などの不活性雰囲気中において、ジ
アミン化合物および酸二無水物を有機極性溶媒中に溶解
または拡散させて得られるポリアミド酸重合体より得ら
れる。This polyamic acid or polyimide is obtained from a polyamic acid polymer obtained by dissolving or diffusing a diamine compound and an acid dianhydride in an organic polar solvent in an inert atmosphere such as argon or nitrogen. .
【００２２】各成分の添加順序は特に限定されず、酸二
無水物を有機極性溶媒中に先に加えておき、ジアミン化
合物を添加し、ポリアミド酸重合体の溶液としても良い
し、ジアミン化合物の一部を有機極性溶媒中に先に適量
加えて、次に酸二無水物を加え、最後に残りのジアミン
化合物を加えて、ポリアミド酸重合体の溶液としても良
い。この他にも、当業者に公知の様々な重合方法があ
る。The order of addition of each component is not particularly limited, and the acid dianhydride may be added to the organic polar solvent first, and the diamine compound may be added to form a solution of the polyamic acid polymer. It is also possible to first add a suitable amount to an organic polar solvent first, then add the acid dianhydride, and finally add the remaining diamine compound to form a solution of the polyamic acid polymer. There are various other polymerization methods known to those skilled in the art.
【００２３】ポリアミド酸溶液の生成反応に用いられる
有機極性溶媒としては、例えば、ジメチルスルホキシ
ド、ジエチルスルホキシド等のスルホキシド系溶媒、
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホル
ムアミド等のホルムアミド系溶媒、Ｎ，Ｎ−ジメチルア
セトアミド、Ｎ，Ｎ−ジエチルアセトアミド等のアセト
アミド系溶媒、Ｎ−メチル−２−ピロリドン等のピロリ
ドン系溶媒、フェノール、ｏ−，ｍ−またはｐ−クレゾ
ール、キシノール、ハロゲン化フェノール、カテコール
等のフェノール系溶媒、あるいはヘキサメチルホスホル
アミド、γ−ブチロラクトン等を挙げることができる。
更に必要に応じて、これらの有機極性溶媒とキシレンあ
るいはトルエン等の芳香族炭化水素とを組み合わせて用
いることもできる。Examples of the organic polar solvent used in the reaction for producing the polyamic acid solution include sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide,
Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone , Phenol, o-, m- or p-cresol, xynol, halogenated phenols, phenolic solvents such as catechol, hexamethylphosphoramide, γ-butyrolactone and the like.
Furthermore, if necessary, these organic polar solvents may be used in combination with an aromatic hydrocarbon such as xylene or toluene.
【００２４】上記で得られたポリアミド酸重合体を、熱
的または化学的方法により、脱水閉環し、熱可塑性ポリ
イミドを得る。イミド化の方法としては、ポリアミド酸
溶液を加熱処理して脱水する熱的方法、脱水剤を用いて
脱水する化学的方法のいずれも用いられる。The polyamic acid polymer obtained above is dehydrated and ring-closed by a thermal or chemical method to obtain a thermoplastic polyimide. As the imidization method, both a thermal method of heat-treating a polyamic acid solution for dehydration and a chemical method of dehydrating with a dehydrating agent are used.
【００２５】化学的方法による脱水剤としては、例え
ば、無水酢酸等の脂肪族酸無水物、および芳香族酸無水
物が挙げられる。また、触媒としては、トリエチルアミ
ン等の脂肪族第３級アミン類、ジメチルアニリン等の芳
香族第３級アミン類、ピリジン、イソキノリン等の複素
環第３級アミン類等が挙げられる。Examples of the dehydrating agent by the chemical method include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine and isoquinoline.
【００２６】上記のようにして得られた熱可塑性ポリイ
ミドはそのまま溶液として本発明のポリイミド系接着剤
溶液の調製に用いることができる。あるいはポリアミド
酸の重合に用いた、溶媒を良く溶かすが、ポリイミドが
溶解しにくい貧溶媒中に、ポリイミド溶液を投入して、
ポリイミド樹脂を析出させて未反応モノマーを取り除い
て精製し、乾燥させ固形のポリイミド樹脂としてから、
適宜、本発明の接着剤溶液に用いることもできる。用い
る貧溶媒としては、アセトン、メタノール、エタノー
ル、イソプロパノール、ベンゼン、メチルセロソルブ、
メチルエチルケトン等が挙げられる。The thermoplastic polyimide obtained as described above can be used as it is as a solution for preparing the polyimide adhesive solution of the present invention. Or used in the polymerization of polyamic acid, which dissolves the solvent well, but in a poor solvent in which the polyimide is difficult to dissolve, throw the polyimide solution,
Polyimide resin is precipitated to remove unreacted monomers for purification, and dried to obtain a solid polyimide resin,
It can also be used in the adhesive solution of the present invention as appropriate. As the poor solvent used, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve,
Methyl ethyl ketone and the like can be mentioned.
【００２７】熱的方法としては、例えば、ポリアミド酸
を重合した後に真空オーブン中に投入し、減圧下で加熱
することによってイミド化を行い、固形のポリイミド樹
脂として取り出す手法が挙げられる。As a thermal method, for example, a method of polymerizing a polyamic acid, then placing it in a vacuum oven, heating it under reduced pressure for imidization, and taking it out as a solid polyimide resin can be mentioned.
【００２８】本発明の接着剤に用いるエポキシ樹脂は特
に限定はなく、エピコート８２８（油化シェル社製）等
のビスフェノールＡ型樹脂、１８０Ｓ６５（油化シェル
社製）等のオルソクレゾールノボラック樹脂、１５７Ｓ
７０（油化シェル社製）等のビスフェノールＡノボラッ
ク樹脂、１０３２Ｈ６０（油化シェル社製）等のトリス
ヒドロキシフェニルメタンノボラック樹脂、ＥＳＮ３７
５等のナフタレンアラルキルノボラック樹脂、テトラフ
ェニロールエタン１０３１Ｓ（油化シェル社製）、ＹＧ
Ｄ４１４Ｓ（東都化成）、トリスヒドロキシフェニルメ
タンＥＰＰＮ５０２Ｈ（日本化薬）、特殊ビスフェノー
ルＶＧ３１０１Ｌ（三井化学）、特殊ナフトールＮＣ７
０００（日本化薬）、ＴＥＴＲＡＤ−Ｘ，ＴＥＴＲＡＤ
−Ｃ（三菱瓦斯化学社製）等のグリシジルアミン型樹脂
などが代表例として挙げられる。The epoxy resin used in the adhesive of the present invention is not particularly limited, and bisphenol A type resin such as Epicoat 828 (manufactured by Yuka Shell Co.), orthocresol novolac resin such as 180S65 (manufactured by Yuka Shell Co., Ltd.), 157S.
70 (manufactured by Yuka Shell Co., Ltd.) and other bisphenol A novolac resins, 1032H60 (manufactured by Yuka Shell Co., Ltd.) and other trishydroxyphenylmethane novolac resins, ESN37
5, naphthalene aralkyl novolac resin, tetraphenylolethane 1031S (made by Yuka Shell Co., Ltd.), YG
D414S (Tohto Kasei), Trishydroxyphenylmethane EPPN502H (Nippon Kayaku), special bisphenol VG3101L (Mitsui Chemicals), special naphthol NC7
000 (Nippon Kayaku), TETRAD-X, TETRAD
Typical examples thereof include glycidylamine type resins such as -C (manufactured by Mitsubishi Gas Chemical Co., Inc.).
【００２９】エポキシ樹脂の混合割合は、熱可塑性ポリ
イミド１００重量部に対して、１〜５０重量部、好まし
くは５〜４０重量部が望ましい。少なすぎると接着強度
が低く、多すぎると可撓性、耐熱性に劣ることがある。The mixing ratio of the epoxy resin is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the thermoplastic polyimide. If it is too small, the adhesive strength will be low, and if it is too large, the flexibility and heat resistance will be poor.
【００３０】硬化剤は、一般にエポキシ樹脂用の硬化剤
として用いられているものであれば何でも良い。硬化剤
は、吸水性、耐熱性、接着性等の向上のために接着剤に
加えられ、代表的には酸二無水物系、アミン系、イミダ
ゾール系等のエポキシ用の一般的な硬化剤、促進剤、あ
るいは種々のカップリング剤が挙げられる。The curing agent may be any one generally used as a curing agent for epoxy resins. The curing agent is added to the adhesive to improve water absorption, heat resistance, adhesiveness, etc., and is typically a general curing agent for epoxy such as acid dianhydride type, amine type, and imidazole type, Examples include accelerators and various coupling agents.
【００３１】以上、本発明の半導体固定用接着フィルム
に用いる接着剤の各組成についての説明をしたが、離型
性を有する保護フィルム上に接着層を形成する際の接着
剤溶液の濃度は溶液重量を分母とする固形分（熱可塑性
ポリイミド＋エポキシ樹脂＋硬化剤）量で５〜５０重量
％、好ましくは１０〜４０重量％、特に好ましくは１５
〜３０重量％である。また、溶解の手順等は作業性等を
考慮し適宜決めればよい。The composition of the adhesive used for the semiconductor fixing adhesive film of the present invention has been described above. The concentration of the adhesive solution when forming the adhesive layer on the protective film having releasability is the solution. The solid content (thermoplastic polyimide + epoxy resin + curing agent) with the weight as the denominator is 5 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 15
~ 30% by weight. Further, the dissolution procedure and the like may be appropriately determined in consideration of workability and the like.
【００３２】上記のようにして得られる本発明にかかる
半導体固定接着フィルムは、ＴＡＢ用テープ、複合リー
ドフレーム、積層材料等に好適に用いられ得る特性を有
する。具体的には、薄い構成であるため微細加工性に優
れ、耐熱性、接着性ともに優れており、２００℃以下の
低温で接着しうる等、使用に際し加工性に優れる。この
場合の接着条件の一例を挙げると、加熱温度１５０℃〜
２００℃、圧力０．１〜１０ＭＰａで加熱時間５〜２０
分程度の条件である。The semiconductor fixing adhesive film according to the present invention obtained as described above has characteristics that it can be suitably used for a TAB tape, a composite lead frame, a laminated material and the like. Specifically, since it has a thin structure, it has excellent fine workability, heat resistance and adhesiveness, and can be bonded at a low temperature of 200 ° C. or less. An example of the bonding conditions in this case is a heating temperature of 150 ° C.
200 ° C., pressure 0.1 to 10 MPa, heating time 5 to 20
The condition is about a minute.
【００３３】[0033]
【実施例】（実施例１） 容量１０００ｍｌのガラス製
フラスコにジメチルホルムアミド（以下、ＤＭＦとい
う）２６３ｇに３，３’−ビス（アミノフェノキシフェ
ニル）スルフォン（以下、ＢＡＰＳ−Ｍという）０．１
１２ｍｏｌを加え、窒素雰囲気下で攪拌しながら、２，
２−ビス（４−ヒドロキシフェニル）プロパンジベンゾ
エート−３，３’，４，４’−テトラカルボン酸二無水
物（以下、ＥＳＤＡという）０．１１２ｍｏｌを徐々に
添加した。氷浴下で３０分間攪拌し、粘度が１５００ｐ
ｏｉｓｅに達したところで攪拌をやめ、ポリアミド酸溶
液を得た。Example 1 In a glass flask having a capacity of 1000 ml, 263 g of dimethylformamide (hereinafter referred to as DMF) was added with 3,3′-bis (aminophenoxyphenyl) sulfone (hereinafter referred to as BAPS-M) 0.1.
Add 12 mol and stir in a nitrogen atmosphere while stirring 2.
0.112 mol of 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) was gradually added. Stir in an ice bath for 30 minutes and the viscosity becomes 1500p
When reaching the oise, the stirring was stopped to obtain a polyamic acid solution.
【００３４】このポリアミド酸溶液にＤＭＦ１１３ｇ、
β−ピコリン２６ｇ、無水酢酸４５ｇを加え３０分間撹
拌した後、さらに１００℃下で１時間撹拌し、イミド化
させた。その後、高速で撹拌したメタノール中にこの溶
液を少しづつ垂らした。メタノール中に析出した糸状の
ポリイミドをミキサーで粉砕し、メタノールでソックス
レー洗浄を行い、１１０℃で２時間乾燥させ、ポリイミ
ド粉末を得た。113 g of DMF was added to this polyamic acid solution,
After adding 26 g of β-picoline and 45 g of acetic anhydride and stirring for 30 minutes, the mixture was further stirred at 100 ° C. for 1 hour for imidization. Then, this solution was dripped little by little in the methanol stirred at high speed. The filamentous polyimide precipitated in methanol was crushed with a mixer, washed with Soxhlet in methanol, and dried at 110 ° C. for 2 hours to obtain a polyimide powder.
【００３５】上記で得たポリイミド粉末を２０ｇ、エピ
コート１０３２Ｈ６０（油化シェル社製）を５ｇ、４，
４’−ジアミノジフェニルスルフォン（硬化剤）１．５
ｇを１０２ｇのジオキソランに添加し、攪拌を行って溶
解させ、ポリイミド系接着剤溶液を得た（固形分濃度：
ＳＣ＝２０％）。20 g of the polyimide powder obtained above and 5 g of Epicoat 1032H60 (produced by Yuka Shell Co., Ltd.)
4'-diaminodiphenyl sulfone (curing agent) 1.5
g was added to 102 g of dioxolane and dissolved by stirring to obtain a polyimide-based adhesive solution (solid content concentration:
SC = 20%).
【００３６】得られたポリイミド系接着剤溶液を２５μ
ｍ厚の離型処理ＰＥＴフィルム（セラピールＢＬ，東洋
メタライジング社製）に乾燥後厚みが５μｍになるよう
に流延し、１００℃で１０分間乾燥後、１２０℃で１０
分間乾燥し、接着フィルムを得た。25 μm of the obtained polyimide adhesive solution
An m-thick release-treated PET film (CeraPeel BL, manufactured by Toyo Metalizing Co., Ltd.) was cast to a thickness of 5 μm after drying, dried at 100 ° C. for 10 minutes, and then at 120 ° C. for 10 minutes.
After drying for a minute, an adhesive film was obtained.
【００３７】（実施例２） 酸成分をＴＭＥＧにする以
外は実施例１と同様に可溶性熱可塑性ポリイミドを得
た。上記で得たポリイミド粉末を２０ｇ、エピコート１
０３２Ｈ６０（油化シェル社製）を５ｇ、４，４’−ジ
アミノジフェニルスルフォン（硬化剤）１．５ｇを１０
２ｇのジオキソランに添加し、攪拌を行って溶解させ、
ポリイミド系接着剤溶液を得た（固形分濃度：ＳＣ＝２
０％）。Example 2 A soluble thermoplastic polyimide was obtained in the same manner as in Example 1 except that TMEG was used as the acid component. 20 g of the polyimide powder obtained above, Epicoat 1
5 g of 032H60 (produced by Yuka Shell Co., Ltd.) and 10 g of 1.5 g of 4,4′-diaminodiphenyl sulfone (curing agent)
Add to 2 g of dioxolane and stir to dissolve,
A polyimide adhesive solution was obtained (solid content concentration: SC = 2
0%).
【００３８】得られたポリイミド系接着剤溶液を２５μ
ｍ厚の離型処理ＰＥＴフィルム（セラピールＢＬ，東洋
メタライジング社製）に乾燥後厚みが５μｍになるよう
に流延し、１００℃で１０分間乾燥後、１２０℃で１０
分間乾燥し、接着フィルムを得た。25 μm of the obtained polyimide adhesive solution
An m-thick release-treated PET film (CeraPeel BL, manufactured by Toyo Metalizing Co., Ltd.) was cast to a thickness of 5 μm after drying, dried at 100 ° C. for 10 minutes, and then at 120 ° C. for 10 minutes.
After drying for a minute, an adhesive film was obtained.
【００３９】（実施例３） アミン成分をＡＰＢにする
以外は実施例１と同様に可溶性熱可塑性ポリイミドを得
た。上記で得たポリイミド粉末を２０ｇ、エピコート１
０３２Ｈ６０（油化シェル社製）を５ｇ、４，４’−ジ
アミノジフェニルスルフォン（硬化剤）１．５ｇを１０
２ｇのジオキソランに添加し、攪拌を行って溶解させ、
ポリイミド系接着剤溶液を得た（固形分濃度：ＳＣ＝２
０％）。Example 3 A soluble thermoplastic polyimide was obtained in the same manner as in Example 1 except that APB was used as the amine component. 20 g of the polyimide powder obtained above, Epicoat 1
5 g of 032H60 (produced by Yuka Shell Co., Ltd.) and 10 g of 1.5 g of 4,4′-diaminodiphenyl sulfone (curing agent)
Add to 2 g of dioxolane and stir to dissolve,
A polyimide adhesive solution was obtained (solid content concentration: SC = 2
0%).
【００４０】得られたポリイミド系接着剤溶液を２５μ
ｍ厚の離型処理ＰＥＴフィルム（セラピールＢＬ，東洋
メタライジング社製）に乾燥後厚みが５μｍになるよう
に流延し、１００℃で１０分間乾燥後、１２０℃で１０
分間乾燥し、接着フィルムを得た。25 μm of the obtained polyimide adhesive solution
An m-thick release-treated PET film (CeraPeel BL, manufactured by Toyo Metalizing Co., Ltd.) was cast to a thickness of 5 μm after drying, dried at 100 ° C. for 10 minutes, and then at 120 ° C. for 10 minutes.
After drying for a minute, an adhesive film was obtained.
【００４１】（実施例４）酸成分をＴＭＥＧ、アミン成
分をＡＰＢにする以外は実施例１と同様に可溶性熱可塑
性ポリイミドを得た。上記で得たポリイミド粉末を２０
ｇ、エピコート１０３２Ｈ６０（油化シェル社製）を５
ｇ、４，４’−ジアミノジフェニルスルフォン（硬化
剤）１．５ｇを１０２ｇのジオキソランに添加し、攪拌
を行って溶解させ、ポリイミド系接着剤溶液を得た（固
形分濃度：ＳＣ＝２０％）。Example 4 A soluble thermoplastic polyimide was obtained in the same manner as in Example 1 except that TMEG was used as the acid component and APB was used as the amine component. 20% of the polyimide powder obtained above
g, Epicoat 1032H60 (made by Yuka Shell Co., Ltd.) 5
1.5 g of 4,4'-diaminodiphenyl sulfone (curing agent) was added to 102 g of dioxolane, and the mixture was stirred and dissolved to obtain a polyimide adhesive solution (solid content concentration: SC = 20%). .
【００４２】得られたポリイミド系接着剤溶液を２５μ
ｍ厚の離型処理ＰＥＴフィルム（セラピールＢＬ，東洋
メタライジング社製）に乾燥後厚みが５μｍになるよう
に流延し、１００℃で１０分間乾燥後、１２０℃で１０
分間乾燥し、接着フィルムを得た。25 μm of the obtained polyimide adhesive solution
An m-thick release-treated PET film (CeraPeel BL, manufactured by Toyo Metalizing Co., Ltd.) was cast to a thickness of 5 μm after drying, dried at 100 ° C. for 10 minutes, and then at 120 ° C. for 10 minutes.
After drying for a minute, an adhesive film was obtained.
【００４３】（実施例５）実施例１で得られたポリイミ
ド粉末を２０ｇ、ＴＥＴＲＡＤ−Ｃ（三菱瓦斯化学社
製）を５ｇ、４，４’−ジアミノジフェニルスルフォン
（硬化剤）１．５ｇを１０２ｇのジオキソランに添加
し、攪拌を行って溶解させ、ポリイミド系接着剤溶液を
得た（固形分濃度：ＳＣ＝２０％）。(Example 5) 20 g of the polyimide powder obtained in Example 1, 5 g of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.), and 102 g of 1.5 g of 4,4'-diaminodiphenyl sulfone (curing agent). Was added to the dioxolane, and dissolved by stirring to obtain a polyimide adhesive solution (solid content concentration: SC = 20%).
【００４４】得られたポリイミド系接着剤溶液を２５μ
ｍ厚の離型処理ＰＥＴフィルム（セラピールＢＬ，東洋
メタライジング社製）に乾燥後厚みが５μｍになるよう
に流延し、１００℃で１０分間乾燥後、１２０℃で１０
分間乾燥し、接着フィルムを得た。25 μm of the obtained polyimide adhesive solution
An m-thick release-treated PET film (CeraPeel BL, manufactured by Toyo Metalizing Co., Ltd.) was cast to a thickness of 5 μm after drying, dried at 100 ° C. for 10 minutes, and then at 120 ° C. for 10 minutes.
After drying for a minute, an adhesive film was obtained.
【００４５】（比較例１） 実施例１で得られたポリイ
ミド系接着剤溶液を２５μｍ厚の離型処理ＰＥＴフィル
ム（セラピールＱ−１，東洋メタライジング社製）に乾
燥後厚みが１５μｍになるように流延し、１００℃で１
０分間乾燥後、１２０℃で１０分間乾燥し、接着フィル
ムを得た。Comparative Example 1 The polyimide adhesive solution obtained in Example 1 was dried on a 25 μm thick release-treated PET film (Cerapeal Q-1, manufactured by Toyo Metalizing Co., Ltd.) so that the thickness would be 15 μm. Cast at 100 ° C for 1
After drying for 0 minutes, it was dried at 120 ° C. for 10 minutes to obtain an adhesive film.
【００４６】（比較例２） 容量１０００ｍｌのガラス
製フラスコにジメチルホルムアミド（以下、ＤＭＦとい
う）２６３ｇに３，３’−ビス（アミノフェノキシフェ
ニル）スルフォン（以下、ＢＡＰＳ−Ｍという）０．１
１２ｍｏｌを加え、窒素雰囲気下で攪拌しながら、ビフ
ェニルテトラカルボン酸二無水物（以下、ＢＰＤＡとい
う）０．１１２ｍｏｌを徐々に添加した。氷浴下で３０
分間攪拌し、粘度が１５００ｐｏｉｓｅに達したところ
で攪拌をやめ、ポリアミド酸溶液を得た。Comparative Example 2 In a glass flask having a capacity of 1000 ml, 263 g of dimethylformamide (hereinafter referred to as DMF) and 3,3′-bis (aminophenoxyphenyl) sulfone (hereinafter referred to as BAPS-M) 0.1 were added.
12 mol was added, and 0.112 mol of biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) was gradually added with stirring under a nitrogen atmosphere. 30 in an ice bath
After stirring for 1 minute, the stirring was stopped when the viscosity reached 1500 poise to obtain a polyamic acid solution.
【００４７】このポリアミド酸溶液にＤＭＦ１１３ｇ、
β−ピコリン２６ｇ、無水酢酸４５ｇを加え３０分間撹
拌した後、さらに１００℃下で１時間撹拌し、イミド化
させた。その後、高速で撹拌したメタノール中にこの溶
液を少しづつ垂らした。メタノール中に析出した糸状の
ポリイミドをミキサーで粉砕し、メタノールでソックス
レー洗浄を行い、１１０℃で２時間乾燥させ、ポリイミ
ド粉末を得た。113 g of DMF was added to this polyamic acid solution.
After adding 26 g of β-picoline and 45 g of acetic anhydride and stirring for 30 minutes, the mixture was further stirred at 100 ° C. for 1 hour for imidization. Then, this solution was dripped little by little in the methanol stirred at high speed. The filamentous polyimide precipitated in methanol was crushed with a mixer, washed with Soxhlet in methanol, and dried at 110 ° C. for 2 hours to obtain a polyimide powder.
【００４８】上記で得たポリイミド粉末はジオキソラン
に溶解させることができなかった。（固形分濃度：ＳＣ
＝２０％）。The polyimide powder obtained above could not be dissolved in dioxolane. (Solid content concentration: SC
= 20%).
【００４９】（比較例３）容量１０００ｍｌのガラス製
フラスコにジメチルホルムアミド（以下、ＤＭＦとい
う）２６３ｇにオキシジアニリン（以下、ＯＤＡとい
う）０．１１２ｍｏｌを加え、窒素雰囲気下で攪拌しな
がら、２，２−ビス（４−ヒドロキシフェニル）プロパ
ンジベンゾエート−３，３’，４，４’−テトラカルボ
ン酸二無水物（以下、ＥＳＤＡという）０．１１２ｍｏ
ｌを徐々に添加した。氷浴下で３０分間攪拌し、粘度が
１５００ｐｏｉｓｅに達したところで攪拌をやめ、ポリ
アミド酸溶液を得た。Comparative Example 3 In a glass flask having a capacity of 1000 ml, 263 g of dimethylformamide (hereinafter, referred to as DMF) was added with 0.112 mol of oxydianiline (hereinafter, referred to as ODA), and the mixture was stirred under a nitrogen atmosphere while 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) 0.112mo
1 was added slowly. The mixture was stirred in an ice bath for 30 minutes, and when the viscosity reached 1500 poise, the stirring was stopped to obtain a polyamic acid solution.
【００５０】このポリアミド酸溶液にＤＭＦ１１３ｇ、
β−ピコリン２６ｇ、無水酢酸４５ｇを加え３０分間撹
拌した後、さらに１００℃下で１時間撹拌し、イミド化
させた。その後、高速で撹拌したメタノール中にこの溶
液を少しづつ垂らした。メタノール中に析出した糸状の
ポリイミドをミキサーで粉砕し、メタノールでソックス
レー洗浄を行い、１１０℃で２時間乾燥させ、ポリイミ
ド粉末を得た。To this polyamic acid solution, 113 g of DMF,
After adding 26 g of β-picoline and 45 g of acetic anhydride and stirring for 30 minutes, the mixture was further stirred at 100 ° C. for 1 hour for imidization. Then, this solution was dripped little by little in the methanol stirred at high speed. The filamentous polyimide precipitated in methanol was crushed with a mixer, washed with Soxhlet in methanol, and dried at 110 ° C. for 2 hours to obtain a polyimide powder.
【００５１】上記で得たポリイミド粉末はジオキソラン
に溶解させることができなかった（固形分濃度：ＳＣ＝
２０％）。The polyimide powder obtained above could not be dissolved in dioxolane (solid content concentration: SC =
20%).
【００５２】（比較例４）実施例１で得られた可溶性熱
可塑性ポリイミド２０ｇをＴＨＦに溶解させ可溶性熱可
塑性ポリイミド溶液を得た。得られた溶液を２５μｍ厚
の離型処理ＰＥＴフィルム（セラピールＱ−１，東洋メ
タライジング社製）に乾燥後厚みが５μｍになるように
流延し、１００℃で１０分間乾燥後、１２０℃で１０分
間乾燥し、接着フィルムを得た。Comparative Example 4 20 g of the soluble thermoplastic polyimide obtained in Example 1 was dissolved in THF to obtain a soluble thermoplastic polyimide solution. The obtained solution was cast on a release-treated PET film having a thickness of 25 μm (CeraPeel Q-1, manufactured by Toyo Metalizing Co., Ltd.) so that the thickness would be 5 μm, dried at 100 ° C. for 10 minutes, and then at 120 ° C. After drying for 10 minutes, an adhesive film was obtained.
【００５３】（比較例５） プラタボンドＭ１２７６
（共重合ナイロン、日本リルサン社製）を１０ｇ、エピ
コート１０３２Ｈ６０（油化シェル社製）を２０ｇ、ジ
アミノジフェニルサルフォン１ｇを８３ｇのジオキソラ
ンに溶解し、接着剤溶液を得た。得られた溶液を２５μ
ｍ厚の離型処理ＰＥＴフィルム（セラピールＱ−１，東
洋メタライジング社製）に乾燥後厚みが５μｍになるよ
うに流延し、１００℃で１０分間乾燥後、１２０℃で１
０分間乾燥し、接着フィルムを得た。(Comparative Example 5) Platabond M1276
(Copolymerized nylon, manufactured by Nippon Rilsan Co., Ltd.), 10 g of Epicoat 1032H60 (manufactured by Yuka Shell Co., Ltd.) and 1 g of diaminodiphenyl sulfone were dissolved in 83 g of dioxolane to obtain an adhesive solution. 25μ of the obtained solution
m-thick release-treated PET film (CeraPeel Q-1, manufactured by Toyo Metalizing Co., Ltd.) was cast to a thickness of 5 μm after drying, dried at 100 ° C. for 10 minutes, and then at 120 ° C. for 1 minute.
After drying for 0 minutes, an adhesive film was obtained.
【００５４】（フィルム状積層部材の特性評価）
１．微細加工性
以下の条件でレーザー加工し、ＳＥＭにて形状観察を行
った。(Characteristic evaluation of film-like laminated member) 1. Fine machinability Laser processing was performed under the following conditions, and the shape was observed by SEM.
【００５５】テーパーの度合いを三段階で評価した。The degree of taper was evaluated in three levels.
【００５６】〇使用機器：ＵＶ個体レーザー（ＹＡＧ第
３高調波），λ＝３５５ｎｍ
〇穴径：４０μｍ
〇速度：１００穴／ｓｅｃ
〇レーザー発振：２０ｋＨｚ
○・・テーパー、穴ともに良好
△・・穴はあいているがバリが残っている
×・・穴があいていない部分がある
２．引剥強度 以下の手順で積層部材と銅箔を接着した
ときの引剥強度の測定を行った。〇 Equipment used: UV solid laser (YAG third harmonic), λ = 355 nm 〇 Hole diameter: 40 μm 〇 Speed: 100 holes / sec 〇 Laser oscillation: 20 kHz ○ ・ ・ Taper and hole are both good △ ・ ・ hole It is open, but there are burrs. Peeling strength The peeling strength when the laminated member and the copper foil were bonded was measured by the following procedure.
【００５７】半導体固定用接着フィルムをポリイミドフ
ィルム（アピカル２５ＡＨ，鐘淵化学工業株式会社社
製）と１８μｍの電解銅箔の間に挟み、温度２００℃、
圧力３ＭＰａで２０分間加熱加圧し、銅張フレキシブル
積層板を得た。得られた銅張りフレキシブル積層板の引
き剥し強度を、ＪＩＳ Ｃ６４８１に従って測定した。
但し導体幅は３ｍｍで測定した。The semiconductor fixing adhesive film was sandwiched between a polyimide film (Apical 25AH, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) and 18 μm electrolytic copper foil, and the temperature was 200 ° C.
It was heated and pressed at a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate. The peel strength of the obtained copper-clad flexible laminate was measured according to JIS C6481.
However, the conductor width was measured at 3 mm.
【００５８】３．耐熱性
２で得られた銅張積層板を用い、１５０℃×１０００時
間後の引き剥し強度を、ＪＩＳ Ｃ６４８１に従って測
定した。但し導体幅は３ｍｍで測定した。3. The peel strength after 150 ° C. × 1000 hours was measured according to JIS C6481 using the copper clad laminate obtained in Heat resistance 2. However, the conductor width was measured at 3 mm.
【００５９】実施例および比較例のフィルム状積層部材
の特性評価結果を表１に示す。Table 1 shows the characteristic evaluation results of the film-like laminated members of Examples and Comparative Examples.
【００６０】[0060]
【表１】 [Table 1]
【００６１】[0061]
【発明の効果】本発明の半導体固定用接着フィルムは、
離型性を有した保護フィルムの上に溶媒可溶性熱可塑性
ポリイミド，エポキシ樹脂および硬化剤からなる２００
℃以下で接着可能な接着剤層を積層した構成を有し、総
厚みを１０μｍ以下にすることで、優れた微細加工性を
実現することができる。また、接着層を可溶性熱可塑性
ポリイミド樹脂、エポキシ樹脂及びその硬化剤で構成す
ることにより、優れた接着性及び耐熱性を併せ持つこと
ができる。The adhesive film for fixing a semiconductor of the present invention comprises:
200 comprising a solvent-soluble thermoplastic polyimide, an epoxy resin and a curing agent on a protective film having releasability
By having a structure in which adhesive layers that can be adhered at a temperature of not more than 0 ° C. are laminated and the total thickness is 10 μm or less, excellent fine workability can be realized. Further, by forming the adhesive layer with a soluble thermoplastic polyimide resin, an epoxy resin, and a curing agent thereof, it is possible to have excellent adhesiveness and heat resistance.
フロントページの続き Ｆターム(参考） 4F100 AK01A AK49B AK53B AT00A BA02 CA02B CA02H CB01B JB16B JJ03 JL01 JL11 JL14A YY00B 4J004 AA02 AA11 AA13 AA17 AB05 BA02 CA06 CD06 DA04 FA05 GA01 4J040 EC061 EC071 EC081 EC121 EH031 HB47 HC01 HC24 JA09 JB02 KA16 LA02 LA06 LA08 MA02 MA10 NA20 Continued front page F term (reference) 4F100 AK01A AK49B AK53B AT00A BA02 CA02B CA02H CB01B JB16B JJ03 JL01 JL11 JL14A YY00B 4J004 AA02 AA11 AA13 AA17 AB05 BA02 CA06 CD06 DA04 FA05 GA01 4J040 EC061 EC071 EC081 EC121 EH031 HB47 HC01 HC24 JA09 JB02 KA16 LA02 LA06 LA08 MA02 MA10 NA20
Claims (5)
可溶性熱可塑性ポリイミド，エポキシ樹脂および硬化剤
を含有する２００℃以下で接着可能な接着剤層を１０μ
ｍ以下の厚みで積層した接着性フィルム。1. An adhesive layer containing a solvent-soluble thermoplastic polyimide, an epoxy resin and a curing agent, which can be adhered at a temperature of 200 ° C. or less, on a protective film having releasability.
An adhesive film laminated with a thickness of m or less.
ラス転移温度が２００℃以下であり、該可溶性熱可塑性
ポリイミドに含まれる酸二無水物残基の５０モル％以上
が一般式（１） 【化１】 で表されるエステル酸二無水物残基であることを特徴と
する請求項１記載の接着性フィルム。2. The glass transition temperature of the solvent-soluble thermoplastic polyimide is 200 ° C. or lower, and 50 mol% or more of the acid dianhydride residues contained in the soluble thermoplastic polyimide is represented by the general formula (1): ] The adhesive film according to claim 1, which is an ester dianhydride residue represented by:
該ポリイミドに含まれるジアミン残基の５０モル％以上
が下記一般式（２） 【化２】 で表されるジアミン化合物の残基であることを特徴とす
る請求項１または２に記載の接着性フィルム。3. The solvent-soluble thermoplastic polyimide is
50 mol% or more of the diamine residues contained in the polyimide are represented by the following general formula (2): The adhesive film according to claim 1 or 2, which is a residue of a diamine compound represented by:
コン系処理剤で処理されたフィルムである請求項１〜３
のいずれか一項に記載の接着性フィルム。4. The protective film having releasability is a film treated with a silicon-based treating agent.
The adhesive film according to any one of 1.
着性フィルムを、接着層を離型性を有する保護フィルム
付きの状態で被着体に貼り合わせた後、離型性を有する
保護フィルムを取り除くことを特徴とする接着性フィル
ムの貼り合わせ方法。5. The releasability of the adhesive film according to any one of claims 1 to 4 is applied to an adherend with an adhesive layer having a protective film having releasability attached to an adherend. A method for laminating an adhesive film, which comprises removing the protective film which the adhesive film has.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001217373A JP2003027014A (en) | 2001-07-17 | 2001-07-17 | Adhesive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001217373A JP2003027014A (en) | 2001-07-17 | 2001-07-17 | Adhesive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003027014A true JP2003027014A (en) | 2003-01-29 |
Family
ID=19051709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001217373A Pending JP2003027014A (en) | 2001-07-17 | 2001-07-17 | Adhesive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003027014A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101701A1 (en) * | 2003-05-14 | 2004-11-25 | Mitsui Chemicals, Inc. | Adhesive resin composition and adhesive agent in film form, and semiconductor device using the same |
| EP1614535A1 (en) | 2004-07-09 | 2006-01-11 | DuPont-Toray Company, Ltd. | Multi-layer polyimide films and flexible circuit substrates therefrom |
| JP2006346521A (en) * | 2005-06-13 | 2006-12-28 | Mitsui Chemicals Inc | Method for coating resin, film, and its use |
| JP2007036047A (en) * | 2005-07-28 | 2007-02-08 | Kaneka Corp | Manufacturing method of thin flexible metal plated laminate of good appearance |
| US7452610B2 (en) | 2005-06-29 | 2008-11-18 | Du Pont Toray Company Limited | Multi-layer polyimide films and flexible circuit substrates therefrom |
| JP4976380B2 (en) * | 2006-04-03 | 2012-07-18 | 三井化学株式会社 | Metal laminate |
| JP2012162680A (en) * | 2011-02-08 | 2012-08-30 | Hitachi Chemical Co Ltd | Adhesive film for semiconductor, adhesive sheet, semiconductor wafer, and semiconductor device |
| JP2014091763A (en) * | 2012-11-01 | 2014-05-19 | Hitachi Chemical Co Ltd | Release polyimide film and method for producing multilayer printed wiring board |
| JP2016191049A (en) * | 2015-03-30 | 2016-11-10 | 荒川化学工業株式会社 | Polyimide-based adhesive, film adhesive, adhesive layer, adhesive sheet, copper-clad laminate and printed wiring board, and multi-layer wiring board and its manufacturing method |
| JP2016194055A (en) * | 2015-03-31 | 2016-11-17 | 荒川化学工業株式会社 | Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, flexible copper-clad laminate, printed circuit board, flexible printed circuit board, multilayer wiring board, printed circuit board, and flexible printed circuit board |
| KR20170038741A (en) * | 2015-09-30 | 2017-04-07 | 아라까와 가가꾸 고교 가부시끼가이샤 | Modified polyimide, adhesive composition, copper foil with resin, copper-clad laminate, printed wiring board and multilayer board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11131041A (en) * | 1997-10-30 | 1999-05-18 | Sumitomo Bakelite Co Ltd | Flame resistant resin adhesive and substrate for flexible printed circuit by using the same |
| JPH11157002A (en) * | 1997-11-25 | 1999-06-15 | Sumitomo Bakelite Co Ltd | Metal-resin composite body, manufacture thereof and flexible board for circuit wiring board |
| JPH11209729A (en) * | 1998-01-30 | 1999-08-03 | Hitachi Chem Co Ltd | Bonding film, its production, supporting member and semiconductor device with bonding film |
| JP2000109645A (en) * | 1998-10-05 | 2000-04-18 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| JP2000144092A (en) * | 1998-11-16 | 2000-05-26 | Kanegafuchi Chem Ind Co Ltd | Adhesive for cover lay and cover lay film |
| JP2000143981A (en) * | 1998-11-12 | 2000-05-26 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
-
2001
- 2001-07-17 JP JP2001217373A patent/JP2003027014A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11131041A (en) * | 1997-10-30 | 1999-05-18 | Sumitomo Bakelite Co Ltd | Flame resistant resin adhesive and substrate for flexible printed circuit by using the same |
| JPH11157002A (en) * | 1997-11-25 | 1999-06-15 | Sumitomo Bakelite Co Ltd | Metal-resin composite body, manufacture thereof and flexible board for circuit wiring board |
| JPH11209729A (en) * | 1998-01-30 | 1999-08-03 | Hitachi Chem Co Ltd | Bonding film, its production, supporting member and semiconductor device with bonding film |
| JP2000109645A (en) * | 1998-10-05 | 2000-04-18 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| JP2000143981A (en) * | 1998-11-12 | 2000-05-26 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| JP2000144092A (en) * | 1998-11-16 | 2000-05-26 | Kanegafuchi Chem Ind Co Ltd | Adhesive for cover lay and cover lay film |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101701A1 (en) * | 2003-05-14 | 2004-11-25 | Mitsui Chemicals, Inc. | Adhesive resin composition and adhesive agent in film form, and semiconductor device using the same |
| US7488532B2 (en) | 2003-05-14 | 2009-02-10 | Mitsui Chemicals, Inc. | Adhesive resin composition and adhesive agent in film form, and semiconductor device using the same |
| EP1614535A1 (en) | 2004-07-09 | 2006-01-11 | DuPont-Toray Company, Ltd. | Multi-layer polyimide films and flexible circuit substrates therefrom |
| JP2006346521A (en) * | 2005-06-13 | 2006-12-28 | Mitsui Chemicals Inc | Method for coating resin, film, and its use |
| US7452610B2 (en) | 2005-06-29 | 2008-11-18 | Du Pont Toray Company Limited | Multi-layer polyimide films and flexible circuit substrates therefrom |
| JP2007036047A (en) * | 2005-07-28 | 2007-02-08 | Kaneka Corp | Manufacturing method of thin flexible metal plated laminate of good appearance |
| JP4976380B2 (en) * | 2006-04-03 | 2012-07-18 | 三井化学株式会社 | Metal laminate |
| JP2012162680A (en) * | 2011-02-08 | 2012-08-30 | Hitachi Chemical Co Ltd | Adhesive film for semiconductor, adhesive sheet, semiconductor wafer, and semiconductor device |
| JP2014091763A (en) * | 2012-11-01 | 2014-05-19 | Hitachi Chemical Co Ltd | Release polyimide film and method for producing multilayer printed wiring board |
| JP2016191049A (en) * | 2015-03-30 | 2016-11-10 | 荒川化学工業株式会社 | Polyimide-based adhesive, film adhesive, adhesive layer, adhesive sheet, copper-clad laminate and printed wiring board, and multi-layer wiring board and its manufacturing method |
| JP2016194055A (en) * | 2015-03-31 | 2016-11-17 | 荒川化学工業株式会社 | Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, flexible copper-clad laminate, printed circuit board, flexible printed circuit board, multilayer wiring board, printed circuit board, and flexible printed circuit board |
| KR20170038741A (en) * | 2015-09-30 | 2017-04-07 | 아라까와 가가꾸 고교 가부시끼가이샤 | Modified polyimide, adhesive composition, copper foil with resin, copper-clad laminate, printed wiring board and multilayer board |
| KR102653701B1 (en) | 2015-09-30 | 2024-04-01 | 아라까와 가가꾸 고교 가부시끼가이샤 | Modified polyimide, adhesive composition, copper foil with resin, copper-clad laminate, printed wiring board and multilayer board |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI716524B (en) | Copper clad laminate and printed circuit board | |
| KR102211591B1 (en) | Polyimide, polyimide-based adhesive, film-shaped adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate and printed wiring board, and multi-layer board and manufacturing method thereof | |
| TWI400268B (en) | Thermosetting resin composition and use thereof | |
| JP4221290B2 (en) | Resin composition | |
| CN108690194B (en) | Polyimide, adhesive material, adhesive layer, adhesive sheet, copper foil, copper-clad laminate, wiring board, and method for producing same | |
| KR20160037793A (en) | Polyimide resin composition, adhesive composition, primer composition, laminate, and resin attached copper foil | |
| TW201710454A (en) | Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, flexible copper-clad laminate, printed circuit board, flexible printed circuit board, multilayer wiring board | |
| JPWO2003076515A1 (en) | Thermosetting resin composition, laminated body using the same, and circuit board | |
| JP2017165909A (en) | Polyimide, resin film, and metal clad laminate | |
| JP2003027014A (en) | Adhesive film | |
| JP4875794B2 (en) | Resin composition | |
| JP4109500B2 (en) | Thermosetting resin composition, thermosetting resin solution, and thermosetting resin sheet | |
| JP5522426B2 (en) | Adhesive for multilayer flexible substrate, multilayer flexible substrate material using the same, laminate and printed wiring board | |
| JP4017029B2 (en) | Coverlay adhesive and coverlay film | |
| JP4071958B2 (en) | Polyimide resin composition | |
| JP4976380B2 (en) | Metal laminate | |
| JP4169978B2 (en) | Low dielectric adhesive and film-like joining member comprising the same | |
| JPH11228715A (en) | Polyimide film having improved adhesiveness and its production | |
| JP2009001793A (en) | Adhesive | |
| JP2003027034A (en) | Adherent cover film | |
| JP4620834B2 (en) | Bonding sheet | |
| JP2000143981A (en) | Resin composition | |
| JP2003011308A (en) | Film-shaped laminated member | |
| JP2002069420A (en) | Adhesive film for fpc reinforcing sheet | |
| JP2002060620A (en) | Polyimide solution excellent in storage stability, polyimide-based adhesive solution and film-like laminated member obtained using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080118 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110118 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110201 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110712 |