JP5671923B2 - Release agent composition, release film and adhesive film using the same - Google Patents

Release agent composition, release film and adhesive film using the same Download PDF

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JP5671923B2
JP5671923B2 JP2010226487A JP2010226487A JP5671923B2 JP 5671923 B2 JP5671923 B2 JP 5671923B2 JP 2010226487 A JP2010226487 A JP 2010226487A JP 2010226487 A JP2010226487 A JP 2010226487A JP 5671923 B2 JP5671923 B2 JP 5671923B2
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稔 長島
稔 長島
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Adhesive Tapes (AREA)
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Description

本発明は、離型剤組成物、離型フィルム及びこれを用いた接着フィルムに関し、特に、異方導電性接着フィルム等の接着フィルムの保護に好適な離型フィルム及びその離型フィルムの離型層を形成するのに有用な離型剤組成物に関する。   The present invention relates to a release agent composition, a release film, and an adhesive film using the same, and in particular, a release film suitable for protecting an adhesive film such as an anisotropic conductive adhesive film and a release film of the release film. The present invention relates to a release agent composition useful for forming a layer.

従来より、ポリエステルフィルムなどの離型ベース基材の一方の面に離型剤の塗膜（離型層）を設けた離型フィルムが、各種接着フィルムの粘着剤被膜の保護フィルムとして広範に使用されている。
一般に、接着フィルムの粘着剤被膜は、ベースフィルムの表面に反応性の粘着剤と溶剤とを含む塗液を塗工した後、加熱して溶媒を除去する方法でベースフィルム上に設けられる。 Conventionally, a release film with a release agent coating (release layer) on one side of a release base material such as polyester film has been widely used as a protective film for adhesive films of various adhesive films. Has been.
Generally, the adhesive film of the adhesive film is provided on the base film by a method in which a coating liquid containing a reactive adhesive and a solvent is applied to the surface of the base film, and then the solvent is removed by heating.

一方、この接着フィルムの表面に積層され、保護フィルムとして用いられる離型フィルムは、通常、金属酸化物などをフィラーとして用いた白色の二軸延伸ポリエステルフィルムを離型ベース基材とし、その片面もしくは両面に、溶剤に溶解した状態の硬化型シリコーン系剥離剤を塗工、乾燥、硬化させて離型層を形成することにより製造されている（特許文献１）。   On the other hand, the release film that is laminated on the surface of the adhesive film and used as a protective film is usually a white biaxially stretched polyester film using a metal oxide or the like as a filler as a release base substrate, It is manufactured by coating, drying and curing a curable silicone release agent in a state dissolved in a solvent on both sides to form a release layer (Patent Document 1).

このような硬化型シリコーン系剥離剤に使用されるシリコーンには、一般に、接着フィルムとの表面粘着を防止し、背面の離型ベース基材へのシリコーンの移行をできるだけ少なくすることが要求される。そのため、シリコーンとしては、末端に−ＯＨ基をもつポリジメチルシロキサンと末端に−Ｈ基をもつポリジメチルシロキサン（ヒドロキシポリジメチルシロキサン）を、有機錫触媒を用いて縮合反応させ、３次元架橋構造を作るタイプのものや、末端にビニル基を導入したポリジメチルシロキサンとヒドロキシポリジメチルシロキサンを白金触媒を用い付加反応させるタイプのものが主として用いられる。   In general, the silicone used for such a curable silicone release agent is required to prevent surface adhesion with the adhesive film and minimize the migration of the silicone to the release base substrate on the back surface. . Therefore, as a silicone, polydimethylsiloxane having —OH group at the end and polydimethylsiloxane having hydroxy group (hydroxypolydimethylsiloxane) at the end are subjected to a condensation reaction using an organotin catalyst to form a three-dimensional crosslinked structure. Mainly used are those of the type to be made, and those of polydimethylsiloxane having a vinyl group introduced at the terminal thereof and hydroxypolydimethylsiloxane are subjected to an addition reaction using a platinum catalyst.

また、離型フィルムが積層された接着フィルムの使用方法としては、例えば、その接着フィルムが、粘着剤被膜として異方性導電膜を有する異方性導電フィルムである場合、液晶パネルのＩＴＯ電極とＴＡＢとを接続するときに、通常、まず異方性導電フィルムの片面の離型フィルムを剥離し、液晶パネルのＩＴＯ電極上に異方性導電膜を加熱加圧（予備圧着）し、次に異方性導電フィルムの他面の離型ベースフィルムを剥離し、予備圧着した接着フィルム上にＴＡＢを加熱加圧（本圧着）して、液晶パネルとＴＡＢとを確実に接合する。この際、接着フィルムの走行、供給、剥離を安定して行うために、離型フィルムは重要な役割を演ずる。   Moreover, as a usage method of the adhesive film on which the release film is laminated, for example, when the adhesive film is an anisotropic conductive film having an anisotropic conductive film as a pressure-sensitive adhesive film, When connecting to TAB, usually, the release film on one side of the anisotropic conductive film is first peeled off, and the anisotropic conductive film is heated and pressed (preliminary pressure bonding) on the ITO electrode of the liquid crystal panel, and then The release base film on the other surface of the anisotropic conductive film is peeled off, and the TAB is heated and pressed (main pressure bonding) on the pre-bonded adhesive film to securely bond the liquid crystal panel and the TAB. At this time, the release film plays an important role in order to stably run, supply and peel the adhesive film.

離型フィルムの離型層の形成には、一般に、その表面エネルギーを小さくするためにシリコーン系の離型剤が用いられる。しかしながら、一般的なシリコーンを用いた場合、離型層とその上に塗設された粘着剤被膜との親和性が悪く、離型層と粘着剤被膜との接着力は、全体として弱いながらも、双方の剥離開始部分では強く、剥離開始から剥離終了までの間に安定しないという所謂ジャーキー現象が現れる。ジャーキー現象が現れると、大きな剥離力が必要とされる部分で、粘着剤被膜の一部が剥離フィルム側から離型層側に剥ぎ取られるという問題が生じる。   In forming the release layer of the release film, a silicone release agent is generally used to reduce the surface energy. However, when general silicone is used, the affinity between the release layer and the pressure-sensitive adhesive film applied thereon is poor, and the adhesive force between the release layer and the pressure-sensitive adhesive film is weak overall. The so-called jerky phenomenon appears to be strong at both peeling start portions and not stable between the start of peeling and the end of peeling. When the jerky phenomenon appears, there arises a problem that a part of the pressure-sensitive adhesive film is peeled off from the release film side to the release layer side at a portion where a large peeling force is required.

この問題を解決するには離型作用の小さい特殊な離型フィルムを用いることも考えられるが、その場合、剥離作用が小さすぎてカバーとなる離型フィルムに転着する所謂ブロッキング現象が発生することがあり、これにより接着フィルムの安定走行、供給を妨げてしまうばかりでなく、剥離能力の不安定化を招き、接着フィルムとしての性能を大きく損なうという問題があった。   In order to solve this problem, it is conceivable to use a special release film having a small release action, but in this case, a so-called blocking phenomenon occurs in which the release action is too small to transfer to the release film as a cover. In some cases, this not only hinders the stable running and supply of the adhesive film, but also causes destabilization of the peeling ability and greatly impairs the performance as an adhesive film.

特開２００２−２２０４３１号公報Japanese Patent Laid-Open No. 2002-220431

本発明は、このような従来の技術の課題を解決するためになされたもので、その目的とするところは、接着フィルムから離型フィルムを剥離するに際し、ジャーキー現象を起こすことなく円滑に剥離することができ、かつ、離型フィルムの離型層が接着フィルムの接着剤層に添着するブロッキング現象が起こらず、接着フィルムの性能を損なうことのない剥離フィルムを提供することにある。   The present invention has been made in order to solve the above-described problems of the prior art, and the object of the present invention is to smoothly peel off a release film from an adhesive film without causing a jerky phenomenon. Another object of the present invention is to provide a release film that does not impair the performance of the adhesive film without causing a blocking phenomenon in which the release layer of the release film adheres to the adhesive layer of the adhesive film.

本発明者は、この問題を解決するため鋭意に研究を重ねた結果、剥離フィルムの離型層を形成する剥離剤組成物にシリコーン樹脂とアルコキシ基含有シラン変性ポリウレタン樹脂を含有させると、これを成膜した場合に、主剤となるシリコーン樹脂が連続相となっている海の中にシリカ−ポリウレタンハイブリッド複合体の多数の島が分散しているいわゆる海島構造が得られ、これにより部分的に離型層と接着フィルムとの親和性が向上して所望の剥離強度が得られ、ジャーキー現象やブロッキング現象を改善できることを見出し、本発明を完成するに到った。   As a result of intensive research to solve this problem, the present inventor has incorporated a silicone resin and an alkoxy group-containing silane-modified polyurethane resin into a release agent composition that forms a release layer of a release film. When the film is formed, a so-called sea-island structure is obtained in which a large number of islands of the silica-polyurethane hybrid composite are dispersed in the sea in which the silicone resin as the main agent is a continuous phase. It has been found that the affinity between the mold layer and the adhesive film is improved to obtain a desired peel strength and that the jerky phenomenon and the blocking phenomenon can be improved, and the present invention has been completed.

かかる知見に基づきなされた本発明は、シリコーン樹脂とアルコキシ基含有シラン変性ポリウレタン樹脂と溶媒とを含有する離型剤組成物である。
この離型剤組成物では、前記アルコキシ基含有シラン変性ポリウレタン樹脂が、固形分比率で０、５重量％以上５０重量％以下が好ましく、１．２５重量％以上２０重量％以下である場合により効果的である。 This invention made | formed based on this knowledge is a mold release agent composition containing a silicone resin, an alkoxy group containing silane modified polyurethane resin, and a solvent.
In this release agent composition, the alkoxy group-containing silane-modified polyurethane resin is preferably in the range of 0 to 5% by weight to 50% by weight, more preferably 1.25% to 20% by weight in terms of solid content. Is.

また、本発明の離型フィルムは、離型ベース基材と、該離型ベース基材の一方の面に設けられた離型層を有する離型フィルムであって、離型層が、上述の離型剤組成物の硬化膜となっているものである。   The release film of the present invention is a release film having a release base substrate and a release layer provided on one surface of the release base substrate, wherein the release layer is the above-mentioned release layer. This is a cured film of the release agent composition.

本発明の接着フィルムは、離型ベース基材と、該離型ベース基材の一方の面上に設けられた離型層と、該離型層に設けられた接着剤層とを有する接着フィルムであって、離型層が、上述の離型剤組成物の硬化膜となっているものである。この接着フィルムの好ましい態様としては、接着剤層が、結着樹脂中に導電粒子が分散された異方導電性接着剤からなる態様をあげることができる。   The adhesive film of the present invention includes a release base substrate, a release layer provided on one surface of the release base substrate, and an adhesive layer provided on the release layer. The release layer is a cured film of the above-described release agent composition. As a preferred embodiment of the adhesive film, an embodiment in which the adhesive layer is made of an anisotropic conductive adhesive in which conductive particles are dispersed in a binder resin can be exemplified.

本発明の離型フィルムの製造方法は、シリコーン樹脂と、アルコキシ基含有シラン変性ポリウレタン樹脂と溶媒とを含有する離型剤組成物を離型ベース基材上に塗布し、硬化させて離型層を形成する方法である。   The method for producing a release film according to the present invention comprises applying a release agent composition containing a silicone resin, an alkoxy group-containing silane-modified polyurethane resin, and a solvent onto a release base substrate and curing the release agent composition. It is a method of forming.

本発明の離型剤組成物を離型ベース基材上に成膜して離型層を形成すると、離型層は、シリコーン樹脂の連続相の海の中に、シリカ−ポリウレタンハイブリッド複合体から形成された熱可塑性樹脂の多数の島が存在する海島構造が構成される。その結果、離型層において部分的に接着フィルムとの親和性が向上する。これにより、接着フィルムから離型フィルムを剥離するに際し、ジャーキー現象を起こすことなく円滑に剥離することができ、かつ、離型フィルムの離型層が接着フィルムの接着剤層に添着するブロッキング現象が起こらず、接着フィルムとしての性能を損なうことなく離型フィルムの離型層を接着フィルムの接着剤層から剥離することができる。
また、本発明の離型剤組成物によれば、アルコキシ基含有シラン変性ポリウレタン樹脂の添加量の調整により所望の剥離強度を得ることが可能となる。 When the release agent composition of the present invention is formed on a release base substrate to form a release layer, the release layer is formed from the silica-polyurethane hybrid composite in the sea of the silicone resin continuous phase. A sea-island structure in which a large number of islands of the formed thermoplastic resin exist is formed. As a result, the affinity for the adhesive film is partially improved in the release layer. As a result, when peeling the release film from the adhesive film, the release film can be smoothly peeled without causing a jerky phenomenon, and there is a blocking phenomenon in which the release layer of the release film adheres to the adhesive layer of the adhesive film. It does not occur and the release layer of the release film can be peeled from the adhesive layer of the adhesive film without impairing the performance as an adhesive film.
Moreover, according to the mold release agent composition of this invention, it becomes possible to obtain desired peeling strength by adjusting the addition amount of an alkoxy group containing silane modified polyurethane resin.

本発明に係る離型フィルムの例を示す断面図である。It is sectional drawing which shows the example of the release film which concerns on this invention. 本発明に係る接着フィルムの例を示す断面図である。It is sectional drawing which shows the example of the adhesive film which concerns on this invention. ＡＣＦ剥離強度のシリカ−ポリウレタンハイブリッド複合体の添加量依存性を示すグラフである。It is a graph which shows the addition amount dependence of the silica-polyurethane hybrid composite of ACF peeling strength. ＡＣＦ剥離強度のエチルセルロース溶液の添加量依存性を示すグラフである。It is a graph which shows the addition amount dependence of the ethylcellulose solution of ACF peeling strength. ＡＣＦ残留接着率のアルコキシ基含有シラン変性ポリウレタン樹脂溶液の添加量依存性を示すグラフである。It is a graph which shows the addition amount dependence of the alkoxy group containing silane modified polyurethane resin solution of ACF residual adhesive rate. ＡＣＦ残留接着率のエチルセルロース溶液の添加量依存性を示すグラフである。It is a graph which shows the addition amount dependence of the ethylcellulose solution of ACF residual adhesive rate.

以下、本発明の好ましい実施の形態を図面を参照して詳細に説明する。
本発明に係る離型剤組成物は、シリコーン樹脂と、アルコキシ基含有シラン変性ポリウレタン樹脂と溶剤を含有してなり、好ましくはこれらの樹脂成分は溶媒に溶解されているものである。
本発明に用いるシリコーン樹脂としては、特に限定されることはないが、反応性及び安定性の観点からは、付加反応型のシリコーン樹脂を好適に用いることができる。付加反応型のシリコーン樹脂としては、例えば、分子中にアルケニル基(例えばビニル基、ヘキセニル基など)を有する公知のポリジメチルシロキサン等を挙げることができる。付加反応型シリコーンの具体例としては、信越化学工業株式会社の商品名Ｘ５２−９２０１Ｂ、ＫＳ８４７、ＫＳ８３０等の材料が挙げられる。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
The release agent composition according to the present invention contains a silicone resin, an alkoxy group-containing silane-modified polyurethane resin, and a solvent. Preferably, these resin components are dissolved in a solvent.
The silicone resin used in the present invention is not particularly limited, but an addition reaction type silicone resin can be suitably used from the viewpoint of reactivity and stability. Examples of the addition reaction type silicone resin include known polydimethylsiloxane having an alkenyl group (for example, vinyl group, hexenyl group, etc.) in the molecule. Specific examples of the addition reaction type silicone include materials such as trade names X52-9201B, KS847, and KS830 manufactured by Shin-Etsu Chemical Co., Ltd.

また、本発明の離型剤組成物は、付加反応型シリコーンの硬化触媒として、従来より用いられているものを含有することができ、例えば、公知の白金系の硬化触媒を好ましく挙げることができる。白金系の硬化触媒の例としては、塩化白金酸、塩化白金酸とオレフィン類との錯塩、塩化白金酸とアルコール類との化合物等が挙げられる。   Further, the release agent composition of the present invention can contain those conventionally used as a curing catalyst for addition reaction type silicone, and for example, a known platinum curing catalyst can be preferably mentioned. . Examples of platinum-based curing catalysts include chloroplatinic acid, complex salts of chloroplatinic acid and olefins, and compounds of chloroplatinic acid and alcohols.

本発明に用いるアルコキシ基含有シラン変性ポリウレタン樹脂としては、特願２００２−２２０４３１号公報に記載されたものを好適に用いることができる。なかでも、ポリウレタン樹脂がポリエーテル系ポリウレタン樹脂、ポリカーボネート系ポリウレタン、ポリエステル系ポリウレタン等であるものを使用することができる。
このアルコキシ基を含有するシラン変性ポリウレタン樹脂は、その硬化物が、ゲル化した微細なシリカ部位（シロキサン結合の高次網目構造）を有するものである。 As the alkoxy group-containing silane-modified polyurethane resin used in the present invention, those described in Japanese Patent Application No. 2002-220431 can be suitably used. Among them, those in which the polyurethane resin is a polyether polyurethane resin, a polycarbonate polyurethane, a polyester polyurethane, or the like can be used.
The cured product of the silane-modified polyurethane resin containing an alkoxy group has a fine gelled silica portion (a high-order network structure of siloxane bonds).

本発明の離型剤組成物におけるアルコキシ基含有シラン変性ポリウレタン樹脂の含有量は、特に限定されることはないが、本発明の効果を確実に達成する観点からは、アルコキシ基含有シラン変性ポリウレタン樹脂が固形分比率で０．５重量％以上５０重量％以下が好ましく、１．２５重量％以上２０重量％以下であることがより好ましく、さらに好ましくは２．５重量％以上１２．５重量％以下であり、特に２．５重量％以上７．５重量％以下である。
アルコキシ基含有シラン変性ポリウレタン樹脂シリカ−ポリウレタンハイブリッド複合体の含有量が少なすぎると、接着フィルムとの親和性が十分でなくブロッキング現象を防止できず、他方、多すぎると塗膜性及び離型性が劣化するおそれがあるので好ましくない。 The content of the alkoxy group-containing silane-modified polyurethane resin in the release agent composition of the present invention is not particularly limited, but from the viewpoint of reliably achieving the effects of the present invention, the alkoxy group-containing silane-modified polyurethane resin Is preferably 0.5 wt% or more and 50 wt% or less, more preferably 1.25 wt% or more and 20 wt% or less, and further preferably 2.5 wt% or more and 12.5 wt% or less. In particular, it is 2.5 to 7.5% by weight.
When the content of the alkoxy group-containing silane-modified polyurethane resin silica-polyurethane hybrid composite is too small, the affinity with the adhesive film is not sufficient and the blocking phenomenon cannot be prevented. Is not preferable because it may deteriorate.

また、本発明の離型剤組成物には、シリカ−ポリウレタンハイブリッド複合体を形成するアルコキシ基含有シラン変性ポリウレタン樹脂の他、他のシリカハイブリッド有機ポリマーを形成するシラン変性樹脂も用いることもできる。例えば、エポキシ系樹脂、フェノール系樹脂、ポパール系樹脂、アクリル系樹脂、ポリスチレン系樹脂、ポリ酢酸ビニル系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂等からなるものを用いることもできる。   In addition, in addition to the alkoxy group-containing silane-modified polyurethane resin that forms the silica-polyurethane hybrid composite, a silane-modified resin that forms another silica hybrid organic polymer can also be used in the release agent composition of the present invention. For example, an epoxy resin, a phenol resin, a popal resin, an acrylic resin, a polystyrene resin, a polyvinyl acetate resin, a polyimide resin, a polyamideimide resin, or the like can be used.

また、本発明の離型剤組成物には、溶剤、剥離コントロール剤、充填剤等の添加剤を含有させることができる。溶媒としては、特に限定されることはないが、良好な溶解性及び成膜性を確保する観点からは、トルエン、ＭＥＫ（メチルエチルケトン）、ＩＰＡ、ブタノール、アセトン、ＭＩＢＫ等を適宜組み合わせて用いることができる。   Further, the release agent composition of the present invention may contain additives such as a solvent, a release control agent, and a filler. Although it does not specifically limit as a solvent, From a viewpoint of ensuring favorable solubility and film-forming property, using toluene, MEK (methyl ethyl ketone), IPA, butanol, acetone, MIBK, etc. suitably combining them. it can.

本発明の離型剤組成物は、上述した成分を常法により均一に混合することにより調製することができる。   The release agent composition of the present invention can be prepared by uniformly mixing the above-described components by a conventional method.

本発明の離型フィルムは、上述の本発明の離型剤組成物の硬化膜が離型ベース基材の片面に形成されているものであり、図１は、本発明に係る離型フィルムの一例を示す断面図である。
図１に示すように、本例の離型フィルム１は、離型ベース基材２と、この離型ベース基材２の一方の面上に離型層３が設けられて構成される。
ここで、離型ベース基材２としては、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＯＰＰ（２軸延伸ポリプロピレン）等を好適に用いることができる。 In the release film of the present invention, a cured film of the above-described release agent composition of the present invention is formed on one side of a release base substrate, and FIG. 1 shows the release film according to the present invention. It is sectional drawing which shows an example.
As shown in FIG. 1, the release film 1 of this example is configured by providing a release base substrate 2 and a release layer 3 on one surface of the release base substrate 2.
Here, as the release base substrate 2, for example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), OPP (biaxially stretched polypropylene) or the like can be suitably used.

離型層３は、離型ベース基材２上に上述した本発明の離型剤組成物を塗布し、これを適宜、乾燥、加熱して硬化させることによって形成することができる。
本発明の離型剤組成物が硬化した離型層３は、シリコーン樹脂の連続相の海の中に、シリカ−ポリウレタンハイブリッド複合体から形成された熱可塑性樹脂の多数の島が分散した海島構造を有する。そのため、この離型層３は、シリカ−ポリウレタンハイブリッド複合体による島が分散していない離型層に比して、接着フィルムとの親和性が向上したものとなる。 The release layer 3 can be formed by applying the above-described release agent composition of the present invention on the release base substrate 2, and drying and heating it appropriately.
The release layer 3 obtained by curing the release agent composition of the present invention has a sea-island structure in which a large number of islands of a thermoplastic resin formed from a silica-polyurethane hybrid composite are dispersed in a sea of a silicone resin continuous phase. Have Therefore, this release layer 3 has an improved affinity with the adhesive film as compared to the release layer in which islands formed by the silica-polyurethane hybrid composite are not dispersed.

本発明の場合、離型層３の厚さは特に限定されることはないが、離型性及び経済性を両立させる観点からは、０．０５μｍ以上０．５μｍ以下であることが好ましい。   In the present invention, the thickness of the release layer 3 is not particularly limited, but is preferably 0.05 μm or more and 0.5 μm or less from the viewpoint of achieving both release properties and economic efficiency.

本発明の接着フィルムは、本発明の離型フィルムの離型層に接着剤層を設けたものであり、図２は、本発明に係る接着フィルムの一例を示す断面図である。
図２に示すように、本例の接着フィルム１０は、上述した離型フィルム１の離型層３上に、接着剤層４が設けられて構成される。 The adhesive film of the present invention is obtained by providing an adhesive layer on the release layer of the release film of the present invention, and FIG. 2 is a cross-sectional view showing an example of the adhesive film according to the present invention.
As shown in FIG. 2, the adhesive film 10 of this example is configured by providing an adhesive layer 4 on the release layer 3 of the release film 1 described above.

接着剤層４としては、公知の接着フィルムと同様に、粘着性、熱可塑性、熱硬化性、光硬化性の樹脂層を設けることができ、この樹脂成分として、エポキシ樹脂、フェノキシ樹脂、アクリル樹脂等を含有することができる。接着剤層４を形成するための樹脂組成物には、適宜、重合開始剤、溶剤等を含有させることができる。   As the adhesive layer 4, an adhesive, thermoplastic, thermosetting, and photocurable resin layer can be provided in the same manner as a known adhesive film. As the resin component, epoxy resin, phenoxy resin, acrylic resin can be used. Etc. can be contained. The resin composition for forming the adhesive layer 4 can appropriately contain a polymerization initiator, a solvent, and the like.

また、接着剤層４に導電性粒子を含有させることにより接着剤層４を異方性導電膜に形成し、接着フィルム１０を異方導電性接着フィルム（ＡＣＦ）としてもよい。   Alternatively, the adhesive layer 4 may be formed into an anisotropic conductive film by containing conductive particles in the adhesive layer 4 and the adhesive film 10 may be an anisotropic conductive adhesive film (ACF).

接着フィルム１０の製造方法としては、上述した離型フィルム１の離型層３上に、接着剤層形成用樹脂組成物を塗布し、これを乾燥、硬化させる。
接着剤層４の厚さは特に限定されることはないが、接着性及び経済性を両立させる観点からは、０．００５ｍｍ以上０．０５ｍｍ以下であることが好ましい。 As a manufacturing method of the adhesive film 10, the resin composition for forming an adhesive layer is applied on the release layer 3 of the release film 1 described above, and this is dried and cured.
The thickness of the adhesive layer 4 is not particularly limited, but is preferably 0.005 mm or more and 0.05 mm or less from the viewpoint of achieving both adhesiveness and economy.

以下、本発明を実施例によって具体的に説明するが、本発明は、これらの実施例によって限定されるものではない。
実施例１
アルコキシ基含有シラン変性ポリウレタン樹脂溶液（固形分２５％）（ユリアーノ Ｕ３０２ 荒川化学工業社製）１０重量部、３０％付加反応型シリコーン溶液（ＫＳ−８４７ 信越化学工業社製）２７重量部、白金硬化触媒（ＰＬ−５０Ｔ 信越化学工業社製）０．８重量部、トルエン３０重量部及びＭＥＫ３３重量部を、均一に混合して離型剤組成物を調製した。
なお、本実施例の場合、離型剤組成物の固形分比率（触媒を除く）は、アルコキシ基含有シラン変性ポリウレタン樹脂が２０重量％、シリコーン樹脂が８０％である。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Example 1
10 parts by weight of an alkoxy group-containing silane-modified polyurethane resin solution (solid content 25%) (Yuliano U302 Arakawa Chemical Industries), 27 parts by weight of 30% addition reaction type silicone solution (KS-847 Shin-Etsu Chemical Co., Ltd.), platinum curing A release agent composition was prepared by uniformly mixing 0.8 parts by weight of a catalyst (PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.), 30 parts by weight of toluene and 33 parts by weight of MEK.
In the case of this example, the solid content ratio (excluding the catalyst) of the release agent composition is 20% by weight for the alkoxy group-containing silane-modified polyurethane resin and 80% for the silicone resin.

得られた離型剤組成物を、離型ベース基材である５０μｍ厚のＰＥＴフィルムの一方の面に乾燥厚で０．１μｍとなるようにコイルバーで塗工し、これをオーブン内に入れ、温度１６０℃に１分間保持した後、オーブンから取り出した。こうして、離型ベース基材の一方の面に離型層が設けられた離型フィルムを得た。   The obtained release agent composition was applied to one surface of a 50 μm-thick PET film as a release base substrate with a coil bar so that the dry thickness was 0.1 μm, and this was put in an oven. After maintaining at a temperature of 160 ° C. for 1 minute, it was removed from the oven. Thus, a release film in which a release layer was provided on one surface of the release base substrate was obtained.

＜ａ．粘着フィルムに対する初期剥離強度＞
実施例１で得られた離型フィルムの離型層上に、テスト用アクリル系粘着フィルム（Ｔ４０９０、ソニーケミカル＆インフォメーションデバイス社製）を貼り合わせ、長さ２００ｍｍで幅５０ｍｍの短冊状にカットし、得られた短冊状サンプルに２ｋｇの荷重を載せたまま７０℃で２０時間エージングした。エージング終了後、２５℃でＴ型剥離試験を行い、初期剥離強度（Ｎ／５ｃｍ）を剥離強度試験機（テンシロン オリエンテック社製）を用いて測定した。 <A. Initial peel strength for adhesive film>
On the release layer of the release film obtained in Example 1, an acrylic adhesive film for test (T4090, manufactured by Sony Chemical & Information Device Co., Ltd.) was bonded and cut into a strip shape having a length of 200 mm and a width of 50 mm. The obtained strip-shaped sample was aged at 70 ° C. for 20 hours while a 2 kg load was placed thereon. After the aging was completed, a T-type peel test was performed at 25 ° C., and the initial peel strength (N / 5 cm) was measured using a peel strength tester (manufactured by Tensilon Orientec).

＜ｂ．接着フィルムＡＤＨに対する初期剥離強度＞
実施例１で得られた離型フィルムの一方の面に、接着フィルムＡＤＨ（エポキシ系硬化剤を含む反応性の粘着液）を塗工し、８０℃のオーブン内で１分間保持し、溶媒を除去した。その後、離型フィルム上の接着フィルムＡＤＨ塗膜に対し、アクリル系粘着フィルム（ＰＰテープ、日東電工社製）を貼り合わせ、長さ２００ｍｍで幅５０ｍｍの短冊状にカットし、２５℃でＴ型剥離試験を行い、初期剥離強度（Ｎ／５ｃｍ）を剥離強度試験機（テンシロン オリエンテック社製）を用いて測定した。その結果を表１に示す。 <B. Initial peel strength for adhesive film ADH>
One side of the release film obtained in Example 1 was coated with an adhesive film ADH (reactive adhesive liquid containing an epoxy curing agent), held in an oven at 80 ° C. for 1 minute, and the solvent was removed. Removed. Then, an acrylic adhesive film (PP tape, manufactured by Nitto Denko Corporation) is bonded to the adhesive film ADH coating on the release film, cut into a strip shape of 200 mm in length and 50 mm in width, and T-shaped at 25 ° C. A peel test was performed, and the initial peel strength (N / 5 cm) was measured using a peel strength tester (manufactured by Tensilon Orientec Co., Ltd.). The results are shown in Table 1.

＜ｃ．ブロッキング＞
上記ｂ．接着フィルムADHに対する初期剥離強度の試験において、ブロッキングの発生状況をカバーフィルム（接着フィルムＡＤＨとアクリル系粘着フィルムの積層物）への転着の発生率によって調べ、次の評価基準で評価した。
［評価基準］
Ａ：カバーフィルムへの転着の発生率 １％以下
Ｂ：カバーフィルムへの転着の発生率 １％以上１０％未満
Ｃ：カバーフィルムへの転着の発生率 １０％以上
結果を表１に示す。 <C. Blocking>
B. In the initial peel strength test for the adhesive film ADH, the occurrence of blocking was examined by the rate of occurrence of transfer to the cover film (a laminate of the adhesive film ADH and the acrylic adhesive film) and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: Rate of occurrence of transfer to cover film 1% or less B: Rate of occurrence of transfer to cover film 1% to less than 10% C: Rate of occurrence of transfer to cover film 10% or more The results are shown in Table 1. Show.

＜ｄ．ジャーキー＞
上記ｂ．接着フィルムADHに対する初期剥離強度の試験において、ジャーキーの発生状況を、剥離力チャートにおける最大値（Ｍａｘ）と最小値（Ｍｉｎ）の差の平均の剥離力（Ａｖｅ）に対する割合Ｒ（Ｒ＝１００×（Ｍａｘ―Ｍｉｎ）/Ａｖｅ）によって調べ、次の評価基準で評価した。
［評価基準］
Ａ：Ｒの値が２０％以下（実使用上問題のないレベル）
Ｂ：Ｒの値が２０％以上５０％未満
Ｃ：Ｒの値が５０％以上
結果を表１に示す。 <D. Jerky>
B. In the test of the initial peel strength for the adhesive film ADH, the jerky generation state is determined by the ratio R (R = 100 ×) to the average peel force (Ave) of the difference between the maximum value (Max) and the minimum value (Min) in the peel force chart. (Max-Min) / Ave) and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: The value of R is 20% or less (a level where there is no problem in actual use)
B: The value of R is 20% or more and less than 50%. C: The value of R is 50% or more.

＜ｅ．初期残留接着率＞
上記ａ．粘着フィルムに対する初期剥離強度の試験において引き剥がしたテスト用アクリル系粘着フィルムを、平滑なステンレス板にハンドローラで貼り付け、剥離強度を上述した方法で測定した（残留剥離強度）。
これとは別に未使用のテスト用アクリル系粘着フィルムを平滑なステンレス板にハンドローラで貼り付け、剥離強度を上述した方法で測定した（基準剥離強度）。そして基準剥離強度に対する残留剥離強度の割合として初期残留接着率（％）を算出した。その結果を表１に示す。 <E. Initial residual adhesion rate>
A. The acrylic adhesive film for test peeled off in the initial peel strength test for the adhesive film was attached to a smooth stainless steel plate with a hand roller, and the peel strength was measured by the method described above (residual peel strength).
Separately, an unused acrylic test film for test was attached to a smooth stainless steel plate with a hand roller, and the peel strength was measured by the method described above (reference peel strength). The initial residual adhesion rate (%) was calculated as the ratio of the residual peel strength to the reference peel strength. The results are shown in Table 1.

＜実施例２＞
実施例１のアルコキシ基含有シラン変性ポリウレタン樹脂溶液（ユリアーノ Ｕ３０２ 荒川化学工業社製）１０重量部に代えて、他のアルコキシ基含有シラン変性ポリウレタン樹脂溶液（ユリアーノ Ｕ３０１ 荒川化学工業社製）１０重量部を配合した以外は、実施例１と同一の方法によってサンプルを作成し、同一の実験を行った。その結果を表１に示す。 <Example 2>
Instead of 10 parts by weight of the alkoxy group-containing silane-modified polyurethane resin solution (Yuliano U302 manufactured by Arakawa Chemical Industries) of Example 1, 10 parts by weight of another alkoxy group-containing silane-modified polyurethane resin solution (Yuliano U301 manufactured by Arakawa Chemical Industries) A sample was prepared by the same method as in Example 1 except that the same experiment was performed. The results are shown in Table 1.

＜比較例１＞
上記アルコキシ基含有シラン変性ポリウレタン樹脂（ユリアーノ Ｕ３０２ 荒川化学工業社製）１０重量部に代えて、１０％エチルセルロース溶液（Ｎ１００、ハーキュレス社製）２０重量部を配合した以外は、実施例１と同一の方法によってサンプルを作成し、同一の実験を行った。その結果を表１に示す。
なお、比較例１の場合、セルロースの配合比は、離型剤組成物の樹脂固形分全体に対して２０重量％であり、離型剤組成物の樹脂固形分比率はセルロースが２０重量％、シリコーン樹脂が約８０％である。 <Comparative Example 1>
The same as in Example 1 except that 20 parts by weight of a 10% ethylcellulose solution (N100, manufactured by Hercules Co., Ltd.) was blended in place of 10 parts by weight of the alkoxy group-containing silane-modified polyurethane resin (Juliano U302 Arakawa Chemical Industries). Samples were prepared by the method and the same experiment was conducted. The results are shown in Table 1.
In the case of Comparative Example 1, the blending ratio of cellulose is 20% by weight with respect to the entire resin solid content of the release agent composition, and the resin solid content ratio of the release agent composition is 20% by weight of cellulose, Silicone resin is about 80%.

＜比較例２＞
上記アルコキシ基含有シラン変性ポリウレタン樹脂（ユリアーノ Ｕ３０２ 荒川化学工業社製）を添加せず、実施例１と同一の方法によってサンプルを作成し、同一の実験を行った。その結果を表１に示す。 <Comparative example 2>
A sample was prepared by the same method as in Example 1 and the same experiment was performed without adding the alkoxy group-containing silane-modified polyurethane resin (Yuriano U302, manufactured by Arakawa Chemical Industries, Ltd.). The results are shown in Table 1.

＜比較例３＞
上記アルコキシ基含有シラン変性ポリウレタン樹脂（ユリアーノ Ｕ３０２ 荒川化学工業社製）１０重量部に代えて、ポリエステル樹脂（エリーテル ＶＥ３２００ ユニチカ社製）の１０重量％（トルエン/ＭＥＫ＝１：１）溶液２０重量部を配合した以外は、実施例１と同一の方法によってサンプルを作成し、同一の実験を行った。なお、比較例３の場合、離型剤組成物の固形分比率（触媒を除く）は、ポリエステル樹脂が２０重量％、シリコーン樹脂が８０％である。その結果を表１に示す。 <Comparative Example 3>
Instead of 10 parts by weight of the above alkoxy group-containing silane-modified polyurethane resin (Yuliano U302 Arakawa Chemical Industries), 20 parts by weight of a 10% by weight (toluene / MEK = 1: 1) solution of a polyester resin (Eritel VE3200 manufactured by Unitika) A sample was prepared by the same method as in Example 1 except that the same experiment was performed. In the case of Comparative Example 3, the solid content ratio (excluding the catalyst) of the release agent composition is 20% by weight for the polyester resin and 80% for the silicone resin. The results are shown in Table 1.

＜比較例４＞
上記アルコキシ基含有シラン変性ポリウレタン樹脂（ユリアーノ Ｕ３０２ 荒川化学工業社製）１０重量部に代えて、シリカ（ＤＦ-5ＶＬＤ，龍森社製）の１０重量％ゾル(トルエン）２０重量部を配合した以外は、実施例１と同一の方法によってサンプルを作成し、同一の実験を行った。なお、比較例４の場合、離型剤組成物の固形分比率（触媒を除く）は、２０重量％、シリコーン樹脂が８０％である。その結果を表１に示す。 <Comparative Example 4>
In place of 10 parts by weight of the above alkoxy group-containing silane-modified polyurethane resin (Juliano U302 Arakawa Chemical Industries), 20 parts by weight of sol (toluene) 10% by weight of silica (DF-5VLD, manufactured by Tatsumori) Sample was prepared by the same method as in Example 1 and the same experiment was conducted. In the case of Comparative Example 4, the solid content ratio (excluding the catalyst) of the release agent composition is 20% by weight, and the silicone resin is 80%. The results are shown in Table 1.

Figure 0005671923
Figure 0005671923

＜ｆ．ＡＣＦ剥離強度のアルコキシ基含有シラン変性ポリウレタン樹脂の添加量依存性＞
ＡＣＦとして、以下のものを用いた。
まず、フェノキシ樹脂（ＹＰ５０ 東都化成社製）５０重量部、エポキシ樹脂（８２８ 油化シェル社製）５０重量部、イミダゾール系硬化剤（ＨＸ３９４１ＨＰ 旭化成社製）１００重量部、シランカップリング剤（Ａ１８７ モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）３．２重量部、平均粒径１００ｎｍのポリブタジエン粒子０．５重量部を、溶剤トルエンに溶解して絶縁性接着剤樹脂、すなわち、バインダー溶液を調製した。 <F. Dependence of ACF peel strength on addition amount of alkoxy group-containing silane-modified polyurethane resin>
The following were used as ACF.
First, 50 parts by weight of a phenoxy resin (YP50, manufactured by Tohto Kasei Co., Ltd.), 50 parts by weight of an epoxy resin (made by 828 Yuka Shell Co., Ltd.), 100 parts by weight of an imidazole curing agent (HX3941HP, manufactured by Asahi Kasei Co., Ltd.), a silane coupling agent (A187 Momentive) (Performance Materials Japan G.K.) 3.2 parts by weight, 0.5 parts by weight of polybutadiene particles having an average particle diameter of 100 nm were dissolved in a solvent toluene to prepare an insulating adhesive resin, that is, a binder solution. .

そして、このバインダー溶液１００重量部に、導電粒子として、平均粒径５μｍのベンゾグアナミン粒子にニッケル−金めっきを施したものを３．５重量部加えてバインダーとした。
さらに、このバインダーを剥離用のＰＥＴフィルム上に乾燥後の厚さが２５μｍになるようにコーティングし、異方導電性接着フィルムを得た。この異方導電性接着フィルムを幅２ｍｍのスリット状に切断し、ＡＣＦのサンプルとした。 Then, 3.5 parts by weight of benzoguanamine particles having an average particle diameter of 5 μm applied to the binder solution was added to 100 parts by weight of the binder solution to obtain a binder.
Furthermore, this binder was coated on a PET film for peeling so that the thickness after drying was 25 μm to obtain an anisotropic conductive adhesive film. This anisotropic conductive adhesive film was cut into a slit shape having a width of 2 mm to obtain an ACF sample.

上記実施例１の離型フィルムにおいて、アルコキシ基含有シラン変性ポリウレタン樹脂溶液（ユリアーノ Ｕ３０２ 荒川化学工業社製）の配合量を２０重量％、４０重量％、６０重量％、８０重量％とし、上述した「ｂ．接着フィルムＡＤＨに対する初期剥離強度」の方法によってＡＣＦ剥離強度）を測定した。その結果を図３に示す。   In the release film of Example 1, the compounding amount of the alkoxy group-containing silane-modified polyurethane resin solution (Yuriano U302 Arakawa Chemical Industries, Ltd.) was 20% by weight, 40% by weight, 60% by weight, and 80% by weight. ACF peel strength) was measured by the method of “b. Initial peel strength for adhesive film ADH”. The result is shown in FIG.

＜ｇ．ＡＣＦ剥離強度のセルロースの添加量依存性＞
上記比較例１の離型フィルムにおいて１０％エチルセルロース溶液（Ｎ１００、ハーキュレス社製）の配合量が２０重量％、４０重量％、６０重量％、８０重量％となる離型フィルムのサンプルを作成し、上記ｆと同様のＡＣＦを用い、上述した方法によってＡＣＦ剥離強度を測定した。その結果を図４に示す。 <G. Dependence of ACF peel strength on cellulose addition amount>
In the release film of Comparative Example 1, a release film sample in which the blending amount of a 10% ethylcellulose solution (N100, manufactured by Hercules Co., Ltd.) is 20% by weight, 40% by weight, 60% by weight, and 80% by weight is prepared. ACF peel strength was measured by the method described above using the same ACF as in f above. The result is shown in FIG.

＜ｈ．残留接着率のアルコキシ基含有シラン変性ポリウレタン樹脂の添加量依存性＞
上記実施例１においてアルコキシ基含有シラン変性ポリウレタン樹脂溶液（ユリアーノ Ｕ３０２ 荒川化学工業社製）の配合量を２０重量％、４０重量％、６０重量％、８０重量％とし、上記ｆと同様のＡＣＦを用い、上述したｅの方法と同様にして残留接着率を測定した。その結果を図５に示す。 <H. Dependence of residual adhesive rate on addition amount of alkoxy group-containing silane-modified polyurethane resin>
In Example 1 above, the compounding amount of the alkoxy group-containing silane-modified polyurethane resin solution (Yuliano U302 Arakawa Chemical Industries) was 20% by weight, 40% by weight, 60% by weight, and 80% by weight. The residual adhesion rate was measured in the same manner as in the above method e. The result is shown in FIG.

＜ｉ．ＡＣＦ残留接着率のセルロースの添加量依存性＞
１０％エチルセルロース溶液（Ｎ１００、ハーキュレス社製）の配合量が２０重量％である比較例１と同様にして、１０％エチルセルロース溶液が４０重量％、６０重量％、８０重量％となる離型フィルムを作成し、上記ｆと同様のＡＣＦを用い、上述したｅの方法と同様にして残留接着率を測定した。その結果を図６に示す。 <I. Dependence of ACF Residual Adhesion on Addition of Cellulose>
In the same manner as in Comparative Example 1 in which the blending amount of 10% ethylcellulose solution (N100, manufactured by Hercules) is 20% by weight, a release film in which the 10% ethylcellulose solution becomes 40%, 60%, and 80% by weight is obtained. The residual adhesion rate was measured in the same manner as in the method e described above, using the same ACF as in the above f. The result is shown in FIG.

＜評価＞
図３から明らかなように、シリコーン樹脂中にアルコキシ基含有シラン変性ポリウレタン樹脂を含有させた実施例においては、アルコキシ基含有シラン変性ポリウレタン樹脂の含有量を増加させると、接着フィルムに対する剥離強度を上昇させて所望の値にすることができる。 <Evaluation>
As is apparent from FIG. 3, in the example in which the alkoxy group-containing silane-modified polyurethane resin is contained in the silicone resin, the increase in the content of the alkoxy group-containing silane-modified polyurethane resin increases the peel strength against the adhesive film. To achieve a desired value.

また、本実施例では、図５から明らかなように、アルコキシ基含有シラン変性ポリウレタン樹脂の含有量を６０重量％まで増加させた場合であっても、残留接着率は９０％より大きく、その低下は見られない。
一方、図４から明らかなように、シリコーン樹脂中にエチルセルロースを含有させた比較例１では、エチルセルロースの含有量を増加させた場合であっても、接着フィルムに対する剥離強度は上昇せず、むしろ低下する傾向が見られる。 Further, in this example, as is apparent from FIG. 5, even when the content of the alkoxy group-containing silane-modified polyurethane resin is increased to 60% by weight, the residual adhesion rate is larger than 90%, and the decrease Is not seen.
On the other hand, as is clear from FIG. 4, in Comparative Example 1 in which ethyl cellulose was contained in the silicone resin, even when the content of ethyl cellulose was increased, the peel strength against the adhesive film did not increase, but rather decreased. The tendency to do is seen.

さらに、この比較例１では、エチルセルロースを含有させることにより、図６に示すように、残留接着率が８０％程度に低下してしまう。
他方、比較例３のようにシリコーン樹脂中にポリエステルを含有させた場合には、ポリエステルの含有量を増加させても、接着フィルムに対する剥離強度は上昇しなかった。
さらに、比較例４のようにシリコーン樹脂中にシリカを含有させた場合には、ＡＣＦに対する剥離強度は実施例と比較してかなり小さく、シリカの含有量を増加させても、接着フィルムに対する剥離強度は上昇しなかった。 Furthermore, in this comparative example 1, by including ethyl cellulose, the residual adhesion rate is reduced to about 80% as shown in FIG.
On the other hand, when the polyester was contained in the silicone resin as in Comparative Example 3, the peel strength against the adhesive film did not increase even when the polyester content was increased.
Further, when silica is contained in the silicone resin as in Comparative Example 4, the peel strength against ACF is considerably smaller than that of the Examples, and the peel strength against the adhesive film is increased even if the silica content is increased. Did not rise.

以上の結果から明らかなように、本発明によれば、剥離強度の安定しないブロッキング現象を防止することができ、接着フィルムとしての性能を大きく損なわずに安定した剥離強度を確保することができる。   As apparent from the above results, according to the present invention, it is possible to prevent a blocking phenomenon in which the peel strength is not stable, and it is possible to ensure a stable peel strength without greatly impairing the performance as an adhesive film.

本発明の離型フィルムは、異方導電性接着フィルム等の接着フィルムの保護に有用であり、本発明の離型剤組成物は、離型フィルムの離型層を形成するのに有用である。   The release film of the present invention is useful for protecting an adhesive film such as an anisotropic conductive adhesive film, and the release agent composition of the present invention is useful for forming a release layer of the release film. .

１…離型フィルム、２…離型ベース基材、３…離型層、４…接着剤層、１０…接着フィルム DESCRIPTION OF SYMBOLS 1 ... Release film, 2 ... Release base substrate, 3 ... Release layer, 4 ... Adhesive layer, 10 ... Adhesive film

Claims (3)

離型ベース基材と、該離型ベース基材の一方の面に設けられた離型層と、該離型層に設けられた接着剤層とを有する接着フィルムであって、
該離型層が、アルケニル基を有するポリジメチルシロキサンと、それを硬化させる白金系硬化触媒と、アルコキシ基含有シラン変性ポリエーテル系ポリウレタン樹脂とを含有する離型剤組成物の硬化膜であり、
該離型剤組成物中のアルコキシ基含有シラン変性ポリエーテル系ポリウレタン樹脂の含有量が、１．２５重量％以上２０重量％以下であることを特徴とする接着フィルム。 An adhesive film having a release base substrate, a release layer provided on one surface of the release base substrate, and an adhesive layer provided on the release layer,
The release layer includes a polydimethylsiloxane having an alkenyl group, and a platinum curing catalyst for curing it, Ri cured film der of the release agent composition containing an alkoxy-containing silane-modified polyether-based polyurethane resin ,
Adhesive film content of the alkoxy group-containing silane-modified polyether-based polyurethane resin of the releasing agent composition is, you characterized in that 1.25 to 20% by weight. 該離型層が、シリコーン樹脂による連続相中にシリカ−ポリウレタンハイブリッド複合体が島状に分散している海島構造を有する請求項１記載の接着フィルム。 The release layer is silica in the continuous phase by the silicone resin - adhesive film of claim 1 having a sea-island structure polyurethane hybrid complex is dispersed in an island shape. 該接着剤層が、結着樹脂中に導電粒子が分散された異方導電性接着剤層である請求項１又は２記載の接着フィルム。 The adhesive film of the adhesive layer is, according to claim 1 or 2, wherein the anisotropic conductive adhesive layer electrically conductive particles dispersed in a binder resin.
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