WO2013047861A1 - Mold-releasing film and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide a mold-releasing film which has excellent antistatic properties and excellent mold releasability at the same time without being provided with an antistatic layer and a mold-releasing layer separately. The present invention is a mold-releasing film, which has a mold-releasing layer on at least one surface of a base film, and wherein the mold-releasing layer contains, as constituents, (i) a crosslinked silicone resin that is formed from an emulsion silicone resin composition and (ii) a conductive polymer that contains a polyanion and a cationic polythiophene which contains a repeating unit represented by formula (I) as a main component. (In formula (I), each of R¹ and R² independently represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, or alternatively, R¹ and R² combine together and represent an optionally substituted alkylene group having 1-12 carbon atoms.)

Description

Release film and manufacturing method thereof

The present invention relates to a release film and a manufacturing method thereof.

In recent years, the use of silicone release films as process materials has shown significant growth. In particular, silicone release films using polyester film as the base material have a very flat surface compared to those using paper and are less likely to generate dust. It is very useful as a process material in the field. In particular, by utilizing its releasability, it is used for a wide range of applications such as pressure sensitive adhesive release and carrier sheets for molding resin films or ceramic sheets.
As silicone used for such a silicone release film, polydimethylsiloxane having an OH group at the terminal and polydimethylsiloxane having an H group at the terminal (hydrogen polydimethylsiloxane) are prepared using an organotin catalyst. Addition reaction using a platinum catalyst with a type that creates a three-dimensional cross-linked structure by condensation reaction (condensation reaction type), or polydimethylsiloxane with a vinyl group introduced in the molecule such as a terminal and hydrogen polydimethylsiloxane. The mainstream is the type that makes a three-dimensional cross-linked structure (addition reaction type).
However, as can be seen from the silicone main chain bond and the side chain structure, such a silicone release layer has the disadvantages that it does not leak charges and is easily charged. As a result, various problems occur. For example, when coating resin on the surface of the release layer, uneven coating may occur, or the release characteristics when peeling the resin layer from the release film may deteriorate due to release discharge of the release film. is there. Particularly in recent years, since the film surface tends to be flattened, the demand for charging during peeling and rubbing has become more severe.
In order to obtain a satisfactory antistatic property in the conventional method of incorporating an antistatic agent in the release layer in order to solve such a problem of charging, particularly in an addition reaction type using a platinum catalyst, silicone is used. Since the release layer is not sufficiently cured, an antistatic layer and a release layer are separately formed on the film to exhibit antistatic properties and release properties (Patent Documents 1 and 2). However, in such a configuration, since the number of processing steps increases, the cost increases, and the market is not sufficiently competitive.
On the other hand, in recent years, polythiophene-based and polyaniline-based conductive polymers have been commercialized, but due to their low solubility, most practical polymers were dispersed in water. It is treated as a thing. Therefore, when it is intended to be added to a commonly used solvent-based silicone coating solution, it will be separated and cannot be applied. Even in the case of conductive polymers dispersed in a solvent, polythiophene and polyaniline contain sulfur and nitrogen, which are catalyst poisons, against platinum catalysts used in general addition reaction type silicone crosslinking reactions. Cause sclerosis.
JP-A-5-25302 Japanese Patent Laid-Open No. 10-315373

（上記式（Ｉ）中、Ｒ^１およびＲ^２は、相互に独立して、水素原子または炭素数１以上４以下のアルキル基を表す。あるいは、Ｒ^１およびＲ^２は、一緒になって、任意に置換されていてもよい炭素数１以上１２以下のアルキレン基を表す。）
２．離型層中の導電性高分子の含有量が、エマルジョン系シリコーン樹脂組成物１００質量％に対して、０．２質量％以上、２０質量％以下である、上記１に記載の離型フィルム。
　また、本発明は、以下の製造方法を包含する。
３．上記１または２に記載の離型フィルムを製造するに際して、エマルジョン系シリコーン樹脂組成物を含有するシリコーン樹脂組成物エマルジョンと、上記式（Ｉ）で表される繰り返し単位を主成分として含有するカチオン性のポリチオフェンとポリアニオンとを含む導電性高分子の水分散体とを混合して得られた塗液を、基材フィルムの少なくとも片面に塗布して、硬化する、離型フィルムの製造方法。
　また、本発明は、以下の態様を包含する。
４．エマルジョン系シリコーン樹脂組成物が、ジメチルシロキサンを主たる構成成分とする、上記１に記載の離型フィルム。
　また、本発明は、帯電防止層と離型層とを別々に設けることなく、帯電防止性と離型性とを同時に有する離型フィルムにおいて、中剥離力領域ないし重剥離力領域の離型性を有する離型フィルムを提供することを望ましい課題とする。
　本発明者らは、上記望ましい課題を解決するために鋭意検討した。その結果、エマルジョン系シリコーン樹脂組成物、エマルジョン系シリコーンレジンおよび特定の導電性高分子から主になる塗液を用いて形成された離型層によって、上記課題が解決できることを見出し、本発明に到達した。
　すなわち本発明は、望ましい課題を解決するための第２の態様として以下の構成を採用するものである。
５．架橋シリコーン樹脂が、エマルジョン系シリコーン樹脂組成物と、離型層の質量を基準として８５質量％以下の、三官能単位シロキサンおよび四官能単位シロキサンからなる群より選ばれる少なくとも１の構造を主たる構成成分とするエマルジョン系シリコーンレジンと、から形成されてなる、上記４に記載の離型フィルム。
６．基材フィルムの少なくとも片面に離型層を有する離型フィルムであって、該離型層が、
（ｉ）（ｉ−１）ジメチルシロキサンを主たる構成成分とするエマルジョン系シリコーン樹脂組成物と、
　（ｉ−２）離型層の質量を基準として６５質量％以上、８５質量％以下の、三官能単位シロキサンおよび四官能単位シロキサンからなる群より選ばれる少なくとも１の構造を主たる構成成分とするエマルジョン系シリコーンレジンと、
から形成されてなる架橋シリコーン樹脂、および
（ｉｉ）上記式（Ｉ）で表される繰り返し単位を主成分として含有するカチオン性のポリチオフェンとポリアニオンとを含む導電性高分子
を構成成分として含む、上記４に記載の離型フィルム。
７．離型層中の導電性高分子の含有量が、エマルジョン系シリコーン樹脂組成物１００質量％に対して、０．２質量％以上、２０質量％以下である、上記５または６に記載の離型フィルム。
　また、本発明は、以下の製造方法を包含する。
８．上記５または６に記載の離型フィルムを製造するに際して、ジメチルシロキサンを主たる構成成分とするエマルジョン系シリコーン樹脂組成物を含有するシリコーン樹脂組成物エマルジョンと、三官能単位シロキサンおよび四官能単位シロキサンからなる群より選ばれる少なくとも１の構造を主たる構成成分とするエマルジョン系シリコーンレジンを含有するシリコーンレジンエマルジョンと、上記式（Ｉ）で表される繰り返し単位を主成分として含有するカチオン性のポリチオフェンとポリアニオンとを含む導電性高分子の水分散体とを混合して得られた塗液を、基材フィルムの少なくとも片面に塗布して、硬化する、離型フィルムの製造方法。 The present invention was made in order to solve the above-described problems of the conventional release film, and is excellent in antistatic properties and release properties at the same time without separately providing an antistatic layer and a release layer. It is an object to provide a release film.
The present inventors diligently studied to solve the above problems. As a result, the present inventors have found that the above problem can be solved by a release layer formed using a coating liquid mainly composed of an emulsion-based silicone resin composition and a specific conductive polymer, and have reached the present invention.
That is, the present invention employs the following configuration as the first aspect.
1. A release film having a release layer on at least one side of a base film, the release layer comprising:
(I) a crosslinked silicone resin formed from an emulsion-based silicone resin composition, and (ii) a cationic polythiophene containing a repeating unit represented by the following formula (I) as a main component, and a polyanion. Release film having a release layer containing a functional polymer as a constituent component.

(In the above formula (I), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Alternatively, R ¹ and R ² are Represents an optionally substituted alkylene group having 1 to 12 carbon atoms.)
2. 2. The release film according to 1 above, wherein the content of the conductive polymer in the release layer is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition.
Moreover, this invention includes the following manufacturing methods.
3. In producing the release film according to 1 or 2 above, a cationic resin containing a silicone resin composition emulsion containing an emulsion silicone resin composition and a repeating unit represented by the formula (I) as a main component A method for producing a release film, wherein a coating liquid obtained by mixing an aqueous dispersion of a conductive polymer containing polythiophene and polyanion is applied to at least one surface of a base film and cured.
Moreover, this invention includes the following aspects.
4). 2. The release film as described in 1 above, wherein the emulsion silicone resin composition comprises dimethylsiloxane as a main constituent.
Further, the present invention provides a release film having an antistatic property and a release property at the same time without providing an antistatic layer and a release layer separately. It is desirable to provide a release film having
The present inventors have intensively studied to solve the above-mentioned desirable problem. As a result, the present inventors have found that the above problems can be solved by a release layer formed by using a coating liquid mainly composed of an emulsion-based silicone resin composition, an emulsion-based silicone resin, and a specific conductive polymer. did.
That is, the present invention employs the following configuration as a second aspect for solving a desirable problem.
5. The cross-linked silicone resin has at least one structure selected from the group consisting of an emulsion-based silicone resin composition and a trifunctional unit siloxane and a tetrafunctional unit siloxane of 85% by mass or less based on the mass of the release layer. 5. The release film according to 4 above, which is formed from an emulsion-based silicone resin.
6). A release film having a release layer on at least one side of a base film, the release layer comprising:
(I) (i-1) an emulsion-based silicone resin composition containing dimethylsiloxane as a main constituent;
(I-2) Emulsions mainly comprising at least one structure selected from the group consisting of trifunctional unit siloxanes and tetrafunctional unit siloxanes in an amount of 65% by mass or more and 85% by mass or less based on the mass of the release layer. A silicone resin,
And (ii) a conductive polymer containing a cationic polythiophene containing a repeating unit represented by the above formula (I) as a main component and a polyanion as a constituent component, 4. A release film according to 4.
7). The mold release according to 5 or 6 above, wherein the content of the conductive polymer in the mold release layer is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition. the film.
Moreover, this invention includes the following manufacturing methods.
8). When producing the release film as described in 5 or 6 above, it comprises a silicone resin composition emulsion containing an emulsion type silicone resin composition containing dimethylsiloxane as a main constituent, and a trifunctional unit siloxane and a tetrafunctional unit siloxane. A silicone resin emulsion containing an emulsion-based silicone resin whose main component is at least one structure selected from the group, and a cationic polythiophene and a polyanion containing as a main component a repeating unit represented by the above formula (I) A method for producing a release film, in which a coating liquid obtained by mixing an aqueous dispersion of a conductive polymer containing is applied to at least one surface of a base film and cured.

　ここで、上記式（Ｉ）中、Ｒ^１およびＲ^２は、相互に独立して、水素原子または炭素数１以上４以下のアルキル基を表す。あるいは、Ｒ^１およびＲ^２は、一緒になって、任意に置換されていてもよい炭素数１以上１２以下のアルキレン基を表す。Ｒ^１およびＲ^２が、相互に独立して、水素原子または炭素数１以上４以下のアルキル基である場合には、Ｒ^１およびＲ^２としては、メチル基、エチル基、プロピル基、ブチル基が好ましく、メチル基、エチル基が特に好ましい。Ｒ^１およびＲ^２が、一緒になって、任意に置換されていてもよい炭素数１以上１２以下のアルキレン基である場合には、かかる炭素数１以上１２以下のアルキレン基としては、例えばメチレン基、１，２−エチレン基、１，２−プロピレン基、１，３−プロピレン基、１，４−ブチレン基、２，３−ブチレン基、１，２−シクロヘキシレン基等のアルキレン基が挙げられる。中でも特に、メチレン基、１，２−エチレン基、１，２−プロピレン基、２，３−ブチレン基等のα，β−アルキレン基が好ましい。このようなα，β−アルキレン基としては、例えばエテン、プロペン、ヘキセン、オクテン、デセン、ドデセン、およびスチレン等のα−オレフィン類を臭素化して得られる１，２−ジブロモアルカン類から誘導することができる。また、上記アルキレン基における置換基としては、炭素数１以上１２以下のアルキル基およびフェニル基が好ましく、特にメチル基、エチル基、プロピル基が好ましい。
　本発明におけるカチオン性のポリチオフェンは、上記式（Ｉ）で表される３，４−ジ置換チオフェンのみを繰り返し単位としていてもよいし、あるいは、３，４−ジ置換チオフェンを繰り返し単位の主成分として含有し、これと重合可能な他のモノマーを従成分として含有するものであってもよい。ここで「主成分」とは、カチオン性のポリチオフェンを構成する繰返し単位全体に対して、上記式（Ｉ）で表される３，４−ジ置換チオフェンを繰り返し単位とする部分が５０モル％より大きく１００モル％以下の範囲であることを意味する。
　以上のようなポリチオフェンは、カチオン性を示すものである。このようなカチオン性を示すポリチオフェンは、例えば、特開平１−３１３５２１号公報に記載の方法により、モノマーである３，４−ジ置換チオフェンを酸化重合することにより得ることができる。
　（ポリアニオン）
　本発明におけるポリアニオンは、特に限定されるものではない。例えば、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸等の高分子状カルボン酸類、ポリスチレンスルホン酸、ポリビニルスルホン酸等の高分子状スルホン酸類等が挙げられる。
　かかる高分子状カルボン酸類および高分子状スルホン酸類等のポリアニオンは、１種類のアニオン性モノマーのみからなる単独重合体であってもよいし、あるいは、複数種のアニオン性モノマーからなる共重合体であってもよいし、さらには、アニオン性モノマーと当該モノマーと共重合可能な他のモノマー類との共重合体であってもよい。アニオン性モノマーと共重合可能な他のモノマー類としては、例えば、アクリレート類、スチレン類等を挙げることができる。ポリアニオンが共重合体である場合には、少なくとも１種類のアニオン性モノマーが共重合成分として含まれていればよい。
　本発明におけるポリアニオンとしては、これらの中でも、ポリスチレンスルホン酸、および少なくとも一部が金属塩となっているポリスチレンスルホン酸が特に好ましく、導電性の向上効果に優れる。
　なお、ポリアニオンの数平均分子量Ｍｎは、導電性の向上効果を高くするという観点から、１，０００以上２，０００，０００以下の範囲が好ましく、２，０００以上５００，０００以下の範囲がより好ましい。
　カチオン性のポリチオフェンとポリアニオンの量比（質量比）については、カチオン性のポリチオフェン：ポリアニオンの比が、好ましくは１：１．１~１：５．０、さらに好ましくは１：１．２~１：２．０である。
　離型層中の導電性高分子の含有量は、エマルジョン系シリコーン樹脂組成物１００質量％に対して０．２質量％以上、２０質量％以下であることが好ましい。含有量が上記数値範囲であると離型性と帯電防止性の向上効果に優れる。含有量が少なすぎる場合は、帯電防止性の向上効果が低くなる傾向にある。このような観点から、より好ましくは０．３質量％以上、さらに好ましくは０．５質量％以上、特に好ましくは０．７質量％以上である。他方、含有量が多すぎる場合は、離型性の向上効果が低くなり、剥離力が重くなる傾向にある。また、導電性高分子の添加量が多くなるとコストが高くなる傾向がある。さらに、経時保管後の離型層の強度が低くなる傾向にある。このような観点から、より好ましくは１０質量％以下、さらに好ましくは７質量％以下、特に好ましくは５質量％以下である。なお、ここでいう「エマルジョン系シリコーン樹脂組成物１００質量％に対して」とは、「エマルジョン系シリコーン樹脂組成物の固形分１００質量％に対して」という意味である。
　＜シリコーンレジン＞
　本発明の第２の態様におけるシリコーンレジンは、下記式（ＩＩ）で表される三官能単位シロキサン、および下記式（ＩＩＩ）で表される四官能単位シロキサンからなる群より選ばれる少なくとも１の構造を主たる構成成分とするポリオルガノシロキサンである。なお、ここで「主たる構成成分とする」とは、三官能単位シロキサンとしてはＳｉＲ^３Ｏ_３／２単位、四官能単位シロキサンとしてはＳｉＯ_２単位を、合計で、分子中に５０モル％を超える量で含有する態様を示し、好ましくは７０モル％以上、より好ましくは９０モル％以上である。

　ここで、上記式（ＩＩ）中、Ｒ^３は、炭素数１~１２の鎖状または環状のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ノニル基、デシル基、ドデシル基、オクタデシル基、シクロヘキシル基等）、芳香族基（例えばフェニル基等）、アルケニル基（例えばビニル基等）のいずれかを表す。これらは、１分子中に複数種類を有していても良い。
　本発明の第２の態様においては、離型層を構成する架橋シリコーン樹脂が、上記エマルジョン系シリコーン樹脂組成物と、離型層の質量を基準として８５質量％以下の上記シリコーンレジンとから形成されてなる。これにより、目的とする中剥離力領域ないし重剥離力領域の剥離力を得ることができる。含有量が多すぎる場合は、シリコーン成分が移行しやすくなる傾向にあり、剥離力が重くなりすぎる傾向にあり、そもそも離型性が得られない等の問題が生じる。また、経時保管後の離型層の強度が低くなる傾向にある。かかる観点から、シリコーンレジンの含有量は、８３質量％以下が好ましく、８２質量％以下がより好ましく、８０質量％以下がさらに好ましい。この範囲内において、含有量は目的とする剥離力に応じて適宜設定すればよい。例えば中剥離力領域（軽剥離力領域と重剥離領域との間の剥離力領域をこのように言う場合がある。例えば後述の測定方法によって求められる常温剥離力で６０~２００ｍＮ／２５ｍｍ、好ましくは６０~１００ｍＮ／２５ｍｍの領域。）の剥離力とするには、シリコーンレジンの含有量は３８質量％以上、６５質量％未満とすることが好ましく、３８質量％以上、５５質量％未満とすることがより好ましい。また、中剥離力領域よりも軽い軽剥離力領域（例えば後述の測定方法によって求められる常温剥離力で６０ｍＮ／２５ｍｍ未満の領域。）においては、より軽剥離とするのであればシリコーンレジンを用いないことが好ましいが、含有量が３８質量％未満の範囲で剥離力を微調整することができる。好ましくは３０質量％以上であり、かかる下限未満の範囲においては、剥離力を重くする効果が小さい。
　一方で、含有量が比較的少ない領域においては、シリコーンレジンの含有量を増やしても剥離力が緩やかにしか重くならない傾向がみられる。よって、本発明における好ましい重剥離力領域の剥離力を得るためには、シリコーンレジンの含有量は、６５質量％以上とすることが好ましく、７０質量％以上がより好ましく、７５質量％以上がさらに好ましい。
　本発明の第２の態様においては、かかるシリコーンレジンを、水を主体とする（ここで「主体とする」とは５０質量％を超える割合をいう。）分散媒に分散させてエマルジョン化した、シリコーンレジンエマルジョンを用い、これを含む塗液を塗布し、塗膜を形成し、かかる塗膜を硬化させて離型層を形成する。シリコーンレジンは、かかる硬化により、上述のシリコーン樹脂組成物と反応し、架橋シリコーン樹脂中に取り込まれて離型層を形成し、かかる離型層において剥離力を重くする効果を発現する。
　本発明の第２の態様においては、このようにシリコーンレジンエマルジョンを用いることにより、シリコーン樹脂組成物の項で述べたのと同様に、硫黄、窒素、リン等を含有する導電性高分子を添加しても、シリコーンレジンの反応が阻害されず、剥離力を重くする効果を効率的に奏することができる。また、得られる離型層の硬化性に係る問題を生じ難い。かかるメカニズムは、シリコーン樹脂組成物の項で述べたメカニズムと同様であると考えられる。なお、本発明においては、かかるシリコーンレジンエマルジョンに含有されるシリコーンレジンを、とりわけエマルジョン系シリコーンレジンと呼称することとする。
　シリコーンレジンは、水系でなくともエマルジョンを形成可能なものであればよいが、水系のシリコーンレジンであることが好ましい。水系のシリコーンレジンは、エマルジョンとした際の安定性に優れるため、結果として塗液の安定性を高くすることができる。また、水系の塗液とすることは、環境の面からも好ましい。
　シリコーンレジンのエマルジョン化（乳化）は、シリコーン樹脂組成物の項で述べた公知の方法を用いることができる。
　シリコーンレジンを上述のシリコーン樹脂組成物と共に硬化させる方法として、熱硬化を好ましく例示することができ、すなわちシリコーンレジンとしては、熱硬化性シリコーンレジンが好ましい。本発明におけるシリコーンレジンとしては、水系の熱硬化性シリコーンレジンが特に好ましい。
　上記のようなシリコーンレジンとしては、本発明の要件を満たすものであれば、従来公知の方法により製造したものを用いることもできるし、既製品をそのまま用いることもできる。既製品としては、例えば旭化成ワッカー社製　商品名：ＣＲＡ９２、東レ・ダウコーニング社製　商品名：ＢＹ２２−７３６ＥＸ、ＢＹ２２−７４９ＳＲ、ＳＭ７００１ＥＸ、ＳＭ７００２ＥＸ等を挙げることができる。
　＜離型層に含有することができるその他の成分＞
　本発明の第１の態様および第２の態様においては、さらに導電性を向上させるという観点から、塗液に、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール等のアルキレングリコールを含有させて離型層を形成することができる。また、分子内にアミド結合を有する、室温で液体の水溶性化合物を用いることもできる。また、分子内にアミド結合を有する、室温で液体の水溶性化合物を含有することができる。
　これらの化合物の含有量は、導電性高分子１００質量部に対して、１０質量部以上、１０００質量部以下が好ましい。含有量が少なすぎる場合は、導電性能の向上効果が低くなる傾向にある。かかる観点から、３０質量部以上がさらに好ましい。他方、含有量が多すぎる場合は、透明性、密着性、耐ブロッキング性に劣る傾向にある。また、離型層の耐湿熱性の向上効果が低くなる傾向にある。かかる観点から、６００質量部以下がさらに好ましい。なお、ここでいう「導電性高分子１００質量部に対して」とは、「導電性高分子の固形分１００質量部に対して」という意味である。
　また、本発明における離型層には、本発明の効果が損なわれない範囲内で、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の微粒子、充填剤、上記導電性高分子以外の透明導電剤、核剤等を配合してもよい。
　＜離型フィルムの製造方法＞
　本発明の第１の態様においては、上述したエマルジョン系シリコーン樹脂組成物と、導電性高分子と、任意に添加してもよい白金系触媒と、任意に添加してもよいその他の成分とを構成成分として含む塗液を、基材フィルムに塗布し、得られた塗膜を硬化することによって離型層を形成する。
　また、本発明の第２の態様においては、上述したエマルジョン系シリコーン樹脂組成物と、エマルジョン系シリコーンレジンと、導電性高分子と、任意に添加してもよい白金系触媒と、任意に添加してもよいその他の成分とを構成成分として含む塗液を、基材フィルムに塗布し、得られた塗膜を硬化することによって離型層を形成する。
　塗液は、上記の各成分を、攪拌羽根等を用いて均一に混合することにより製造できる。この際、本発明の第１の態様においては、エマルジョン系シリコーン樹脂組成物は、それを含有するシリコーン樹脂組成物エマルジョンとして用い、また導電性高分子は、その水分散体として用いることが重要である。また、本発明の第２の態様においては、上記に加えて、エマルジョン系シリコーンレジンは、それを含有するシリコーンレジンエマルジョンとして用いることが重要である。これにより各成分を均一に混合することができ、均一な離型層を得ることができる。また、各成分がその機能を相殺せず、離型性と帯電防止性とに同時に優れる離型層を得ることができる。各成分をより均一に混合するために、本発明の目的を損なわない限りにおいて、適当な溶媒を用いて希釈することができる。また、任意成分については、適当な溶媒を用いて溶解したり、分散したりしたものを用いてもよい。
　塗布する際の塗液としては、混合により得られた塗液をそのまま用いても良いが、本発明の目的を損なわない限りにおいて、適当な溶媒で希釈し、適度な粘度となるように調整した塗液を用いることが、均一で、外観が良好な離型層が得られるという観点から好ましい。溶媒としては、水が好ましい。多少のアルコール等を含んでもよい。その場合は、水が５０質量％を超える量であることが好ましい。このようにすることによって、シリコーン樹脂組成物エマルジョンがエマルジョンとして保持されやすくなり、また、シリコーンレジンエマルジョンがエマルジョンとして保持されやすくなり、離型性と帯電防止性の向上効果を高くすることができる。
　塗液を基材フィルムに塗布するための塗布方法としては、公知の任意の塗布方法が適用でき、例えばグラビアロールコート法、リバースロールコート法、ダイコート法、キスコート法、リバースキスコート法、オフセットグラビアコート法、マイヤーバーコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法、カーテンコート法、ドクターブレード法等を単独または組み合わせて適用することができる。また、ハジキなど塗布外観の安定性を向上させる目的で、塗液には若干量の界面活性剤を含有させることができる。
　また、基材フィルムは、塗液を塗布する前に、密着性、塗工性等を向上させることを目的として、必要に応じて表面に予備的処理を施すことも可能である。かかる予備的処理としては、例えば、コロナ放電処理、プラズマ放電処理等の物理的表面処理、あるいは、基材フィルムの製膜中または製膜後に有機樹脂系または無機樹脂系の塗料を塗布して、塗膜密着層を形成する化学的表面処理を挙げることができる。
　塗液を基材フィルムに塗布後、乾燥、および硬化する条件としては、１００℃以上、１８０℃以下の温度で１０秒以上、１２０秒以下の時間加熱することが好ましく、１２０℃以上、１６０℃以下の温度で２０秒以上、９０秒以下の時間加熱することがさらに好ましく、１３０℃以上、１５０℃以下の温度で３０秒以上、６０秒以下の時間加熱することが特に好ましい。上記のごとく乾燥条件を採用することによって、離型層の強度をより高くすることができる。また、基材フィルムと離型層との密着性をより高くすることができる。また、繰り出し帯電をより好適に抑制することができる。
　かくして本発明の離型フィルムを得ることができる。
　＜離型フィルムの特性＞
　（離型層の厚み）
　本発明の第１の態様および第２の態様において、離型層の厚みは、好ましくは１０ｎｍ以上、３μｍ以下である。厚みが薄すぎると均一な塗膜形成が難しくなり、剥離力が重くなる傾向にある。また、剥離力の均一性に劣る傾向にあり、離型性の向上効果が低下するばかりでなく、離型層中の導電高分子の量が少ない為に、表面抵抗値が高くなる傾向にあり、帯電防止性の向上効果が低くなる傾向にある。さらに、経時保管後の離型層の強度が低くなる傾向にある。かかる観点から、５０ｎｍ以上がより好ましく、０．３μｍ以上がさらに好ましく、０．５μｍ以上が特に好ましい。他方、厚すぎると、帯電防止性能を発揮するのに必要以上の材料を消費し、経済的でないばかりか、巻き取ったロールの状態で表裏が貼り付くブロッキングと呼ばれる異常を生じ、使用することができなくなる。かかる観点から、２μｍ以下がより好ましく、１．５μｍ以下がさらに好ましく、０．８μｍ以下が特に好ましく、０．７μｍ以下が最も好ましい。
　（剥離力）
　本発明においては、第１の態様を採用することで、離型性を発現するための架橋シリコーン樹脂の態様（例えばシリコーン樹脂組成物における主剤や架橋剤の置換基）や添加剤（例えば粒子の添加）、厚み等を適宜調整することによって、所望する幅広い剥離力に対応することができる。特には、導電性高分子による硬化阻害が抑制されているため、軽剥離力領域の剥離力とすることも可能である。そしてかかる離型性と同時に帯電防止性を具備するため、例えば粘着層を有する製品の製造用やシート形成用のキャリアシートとして好適に用いることができる。特に、製造する製品が脆い場合においてキャリアシートの剥離時に製品の破壊を抑制したり、また剥離を容易にすることによって生産性を向上したりする際において、軽剥離力とすることが有用である。
　また、本発明の第２の態様を採用することで、中剥離力領域ないし重剥離力領域の剥離力とすることが可能である。そしてかかる離型性と同時に帯電防止性を具備するため、例えば粘着層を有する製品の製造用やシート形成用のキャリアシートであって、特に使用工程中において製品が誤ってキャリアシートから剥離してしまうエラーを高度に抑制したい場合等において、好適に用いることができる。また、異方性導電性接着フィルムやノンキャリアフィルム等の電子材料接着テープの重剥離側の離型フィルム（キャリアフィルム）として好適に用いることができる。
　本発明の第１の態様の離型フィルムの剥離力は、後述の測定方法によって求められる常温剥離力において、好ましくは２０~３００ｍＮ／２５ｍｍであり、より好ましくは、２０~２００ｍＮ／２５ｍｍ、さらに好ましくは２０~１００ｍＮ／２５ｍｍ、特に好ましくは３０~６０ｍＮ／２５ｍｍである。常温剥離力が上記数値範囲にあると、離型性に優れ、例えば電子部材用粘着テープに対して適度な剥離力となり、剥離の際に粘着剤が変形して不均一になってしまう等の問題を抑制することができる。また、離型層上に粘着樹脂等を塗布乾燥した後の工程において、粘着樹脂等がめくれ易くなることを抑制できる。
　また、後述の測定方法によって求められる加熱剥離力においては、好ましくは２０~５００ｍＮ／２５ｍｍ、より好ましくは２０~３００ｍＮ／２５ｍｍ、さらに好ましくは２０~２００ｍＮ／２５ｍｍ、特に好ましくは４０~１００ｍＮ／２５ｍｍである。加熱剥離力が上記数値範囲にあると、剥離が軽すぎることによる取扱い時に意図しない時に粘着剤の剥離や、剥離が重すぎる事による剥離時の粘着剤の変形を抑止することができる。
　本発明の第１の態様の離型フィルムは、後述の測定方法によって求められる常温経時剥離力が、好ましくは２０~５００ｍＮ／２５ｍｍ、より好ましくは２０~３００ｍＮ／２５ｍｍ、さらに好ましくは２０~１００ｍＮ／２５ｍｍ、特に好ましくは３０~６０ｍＮ／２５ｍｍである。２０ｍＮ／２５ｍｍより軽いと、経時保管後の使用において、粘着樹脂等の離型フィルムへキャスト成型した製品がめくれ易くなり、歩留りの低下を引き起こす。また、５００ｍＮ／２５ｍｍよりも重いと、生産工程等で粘着樹脂等の製品が離型フィルムから容易に剥離する事ができなくなる。
　本発明の第１の態様としての離型フィルムは、後述の測定方法によって求められる加熱経時剥離力が、好ましくは２０~５００ｍＮ／２５ｍｍ、より好ましくは２０~３００ｍＮ／２５ｍｍ、さらに好ましくは２０~２００ｍＮ／２５ｍｍ、特に好ましくは４０~１００ｍＮ／２５ｍｍである。２０ｍＮ／２５ｍｍより軽いと、経時保管後の使用において、粘着樹脂等の離型フィルムへキャスト成型した製品がめくれ易くなり、歩留りの低下を引き起こす。また、５００ｍＮ／２５ｍｍよりも重いと、生産工程等で粘着樹脂等の製品が離型フィルムから容易に剥離する事ができなくなる。
　このような剥離力とするためには、離型塗膜が適切な状態である必要があり、塗膜が著しく薄い場合は、塗膜のはじきが生じ、はじき部分で剥離が重くなってしまい、また、塗膜が著しく厚い場合にも、ロールで巻き取った時に、離型層が、上に巻かれ積層されたフィルムに貼りついてしまい、ロールからフィルムを繰り出した時に、離型層が凝集破壊等してしまい、適切な離型性が損なわれるといったことから、前述したような適切な塗膜厚み範囲とすることが重要となる。また、経時剥離力を達成するためには、余剰の架橋剤のハイドロジェンシランを低減する事も効果がある。また、離型層形成後に、例えば４０~６０℃で１~７日間程度の加温処理を施すことによっても良化する傾向にある。
　本発明の第２の態様の離型フィルムの剥離力は、後述の測定方法によって求められる常温剥離力において、好ましくは２００~８００ｍＮ／２５ｍｍであり、より好ましくは２５０ｍＮ／２５ｍｍ以上、さらに好ましくは２７０ｍＮ／２５ｍｍ以上であり、また、より好ましくは６００ｍＮ／２５ｍｍ以下、さらに好ましくは５００ｍＮ／２５ｍｍ以下、特に好ましくは４５０ｍＮ／２５ｍｍ以下である。常温剥離力が上記数値範囲にあると、離型性に優れ、例えば電子材料接着テープに適した剥離力とすることができる。特に、異方性導電性接着フィルムにおいて、異方性導電性接着フィルムの基盤への接続の際、特に仮接続の工程において、適度な剥離力となり、離型フィルムの浮き無く、また加熱工程において基盤からの接着剤の剥がれ（ナキワカレ）等の問題を抑制することができる。
　また、後述の測定方法によって求められる加熱剥離力においては、好ましくは４００~９００ｍＮ／２５ｍｍであり、より好ましくは４５０ｍＮ／２５ｍｍ以上であり、また、より好ましくは８００ｍＮ／２５ｍｍ以下であり、さらに好ましくは７００ｍＮ／２５ｍｍ以下である。加熱剥離力が上記数値範囲にあると、剥離が軽すぎることによる取り扱い時における意図しない粘着剤の剥離や、剥離が重過ぎることによる剥離時の粘着剤の変形を抑制することができる。また、例えば電子材料接着テープ、特に異方導電性接着フィルムの離型フィルムとして使用する場合においては、上記の剥離力範囲にあると、異方性導電性フィルムの基盤への接続の際、特に仮接続の工程において、適度な剥離力となり、離型フィルムの浮き無く、また加熱工程において基盤からの接着剤の剥がれ（ナキワカレ）等の問題を抑制することができる。
　本発明の第２の態様の離型フィルムは、後述の測定方法によって求められる常温経時剥離力が、好ましくは２００~７００ｍＮ／２５ｍｍ、より好ましくは３００~６００ｍＮ／２５ｍｍである。また、本発明の離型フィルムは、後述の測定方法によって求められる加熱経時剥離力が、好ましくは５５０~１１００ｍＮ／２５ｍｍ、より好ましくは６００~１０００ｍＮ／２５ｍｍである。経時剥離力が上記範囲にあると、経時保管後の使用において、離型フィルムの剥離力の安定性を得ることができる。
　このような剥離力とするためには、エマルジョン系シリコーン樹脂組成物を用いることが効果的である。また、エマルジョン系シリコーンレジンを用いることが効果的である。また、離型塗膜が適切な状態である必要があり、塗膜が著しく薄い場合は、塗膜のはじきが生じ、はじき部分で剥離が重くなりすぎてしまい、また、塗膜が著しく厚い場合にも、ロールで巻き取った時に、離型層が、上に巻かれ積層されたフィルムに貼りついてしまい、ロールからフィルムを繰り出した時に、離型層が凝集破壊等してしまい、適切な離型性が損なわれるといったことから、前述したような適切な塗膜厚み範囲とすることが重要となる。また、経時剥離力を達成するためには、余剰の架橋剤のハイドロジェンシランを低減する事も効果がある。また、離型層形成後に、例えば４０~６０℃で１~７日間程度の加温処理を施すことによっても良化する傾向にある。
　（残留接着率）
　本発明の第１の態様および第２の態様の離型フィルムの常温残留接着率は８０％以上であることが好ましく、さらに好ましくは９０％以上、特に好ましくは９５％以上である。常温残留接着率が上記数値範囲にあると、例えば電子部材用粘着テープにおいて、経時しても剥離力が安定になる。８０％より低いと、製品へのシリコーン成分の転写が多くなり、粘着力の低下やシリコーン成分による汚染が発生しやすくなり、歩留り低下を引き起こす。離型層の形成において、導電性高分子と同時に用いるシリコーン樹脂組成物として、溶剤系のシリコーン樹脂組成物を用いると、常温残留接着率を高くすることができない。上記のような常温残留接着率を達成するためには、用いるシリコーン樹脂組成物はエマルジョン系シリコーン樹脂組成物である必要がある。
　また、加熱残留接着率は７０％以上が好ましく、さらに好ましくは８０％以上、特に好ましくは８５％以上である。加熱残留接着率が上記数値範囲にあると、被着体へのシリコーン移行が低い為、粘着剤等の性能低下を防ぐことができる。７０％より低いと、長期保管によって製品へのシリコーン成分の転写が多くなり、粘着力の低下やシリコーン成分による汚染が発生しやすくなり、歩留り低下を引き起こす。
　このような残留接着率とするためには、エマルジョン系シリコーン樹脂組成物を用いることが効果的である。また、エマルジョン系シリコーンレジンを用いることが効果的である。また、シリコーンの未反応成分等の低分子成分も、残留接着率を低下させるため、塗膜の架橋を十分にすることも重要である。架橋を十分にするには、主には公知の文献等に記載されているが、適切な量の架橋剤及び触媒の添加と、十分な加熱が重要であり、これらを調整すればよい。
　（表面抵抗値）
　本発明の第１の態様および第２の態様における離型層の表面抵抗値は、１×１０^５~１×１０^１３Ω／□であることが好ましい。表面抵抗値が上記数値範囲にあると、例えば電子部材用粘着テープの保護フィルムとして用いた場合等において、ゴミなどの付着を抑制でき、電子部材の品質が高くなり、歩留も高くなる。また、優れた離型性とすることが容易となる。表面抵抗値が低いと、ゴミなどの付着の抑制効果は向上する傾向にあるが、低くしすぎると離型性の向上効果が低くなる傾向にある。他方、表面抵抗値が高いと、優れた離型性は得やすくなるが、高くしすぎるとゴミ付着の抑制効果が低くなる傾向にある。このような観点から、表面抵抗値は、さらに好ましくは１×１０^９~１×１０^１２Ω／□である。
　このようは表面抵抗値とするには、導電性高分子の添加量を調整したり、上述のアルキレングリコールの添加を調整したりすればよい。例えば、導電性高分子の添加量を増やすと、表面抵抗値は低くなる傾向にある。また、エマルジョン系のシリコーン樹脂組成物を用いないと、塗膜が上手く形成できず、表面抵抗値も低くなる傾向にある。また、エマルジョン系シリコーンレジンを用いることも好ましい。 <Release film>
The release film as the first aspect of the present invention has a release layer on at least one side of the base film, and the release layer has a crosslinked silicone resin as a release component and an antistatic component. Is a release film having both excellent antistatic properties and release properties at the same time.
The release film as the second aspect of the present invention has a release layer on at least one surface of the base film, and the release layer has a silicone resin composition and silicone as release components. The cross-linked silicone resin formed from the resin and the conductive polymer as an antistatic component are present in the same layer. Excellent antistatic properties and releasability in the medium or heavy peel force region Is a mold release film.
Hereafter, each structural component which comprises the release film of this invention is demonstrated.
<Base film>
In the present invention, the base film used in the first and second embodiments is not particularly limited. For example, polyester, polystyrene, polyimide, polyamide, polysulfone, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, and blends thereof And a sheet, a film, or a nonwoven fabric made of a phenol resin, an epoxy resin, an ABS resin, or the like.
Among them, a biaxially oriented polyester film can be preferably used from the viewpoint of excellent mechanical properties, dimensional stability, heat resistance, electrical properties, etc., and in particular, mechanical properties, heat resistance, dimensional stability. Since it is excellent, a polyethylene terephthalate film or a polyethylene-2,6-naphthalate film is particularly preferable. These may contain some copolymerization components.
The thickness of the base film is not particularly limited, but is preferably 500 μm or less. If it is thicker than 500 μm, the rigidity of the base film is too high, and the handling property tends to be poor when the conductive film is attached to a display or the like. From such a viewpoint, it is more preferably 100 μm or less, particularly preferably 50 μm or less. Moreover, it is preferable that it is 1 micrometer or more, and can have moderate intensity | strength. From such a viewpoint, it is more preferably 10 μm or more, particularly preferably 20 μm or more.
<Release layer>
The release layer in the first aspect of the present invention comprises a crosslinked silicone resin comprising an emulsion silicone resin composition, a cationic polythiophene containing as a main component a repeating unit represented by the above formula (I), and a polyanion Is contained as a constituent component.
The release layer in the second aspect of the present invention has at least one structure selected from the group consisting of an emulsion-based silicone resin composition containing dimethylsiloxane as a main constituent, and a trifunctional unit siloxane and a tetrafunctional unit siloxane. A cross-linked silicone resin formed from an emulsion-based silicone resin containing as a main component, and a cationic polythiophene containing a repeating unit represented by the above formula (I) as a main component and a polyanion. A molecule is included as a constituent component.
The release layer in the present invention contains a cross-linked silicone resin and a conductive polymer as essential components, but when adding the conductive polymer and optional components described later, they are desired. The amount to be added may be added so that the remaining part of the release layer is a crosslinked silicone resin.
Hereafter, each structural component which comprises the mold release layer in this invention is demonstrated.
<Silicone resin composition>
In the present invention, the silicone resin composition used in the first and second embodiments comprises a polysiloxane having at least two unsaturated groups or hydroxyl groups in one molecule, or preferably a polydimethylsiloxane. The main component and a crosslinking agent made of hydrogen polysiloxane having at least two hydrogen atoms directly bonded to silicon atoms in one molecule or preferably hydrogen polydimethylsiloxane are contained as constituents. In the present invention, the silicone resin composition is preferably composed mainly of dimethylsiloxane. Here, “with dimethylsiloxane as the main constituent” means —Si (CH ₃ ) ₂ An embodiment in which the O-unit is contained in the molecule in an amount exceeding 50 mol% in each of the main agent and the crosslinking agent is shown, preferably 70 mol% or more, more preferably 90 mol% or more.
Here, when the main agent has a vinyl group as an unsaturated group, the ratio of the amount of dimethylsilyl group to the amount of vinyl group in the polysiloxane (-Si (CH ₃ ) ₂ H / -CH = CH ₂ ) (Molar ratio) is usually preferably 0.5 or more and 3 or less. If this ratio is too low, unreacted vinyl groups are likely to remain, and crosslinking will be weakened, and transfer of unreacted components to the adherend will increase, leading to a reduction in the quality of the adherend such as an adhesive. . On the other hand, if the ratio is too large, that is, if the amount of residual dimethylsilyl groups increases, it may react with the material applied on the release layer, which tends to cause heavy peeling.
Further, when the main agent has a hydroxyl group, the ratio of the amount of dimethylsilyl group to the amount of silanol group in the polysiloxane (-Si (CH ₃ ) ₂ H / -Si (CH ₃ ) ₂ OH) (molar ratio) is usually preferably 0.5 or more and 3 or less. If the ratio is too low, unreacted silanol groups are likely to remain, and crosslinking is weakened, and transfer of unreacted components to the adherend increases, resulting in a decrease in the quality of the adherend such as an adhesive. . On the other hand, if the ratio is too large, that is, if the amount of residual dimethylsilyl groups increases, it may react with the material applied on the release layer, which tends to cause heavy peeling.
In the present invention, a silicone resin composition obtained by dispersing such a silicone resin composition in a dispersion medium mainly containing water (herein, “mainly” means a proportion exceeding 50% by mass) is emulsified. Using a product emulsion, a coating liquid containing the product emulsion is applied to form a coating film, and the coating film is cured to form a release layer. The silicone resin composition becomes a crosslinked silicone resin by such curing and exhibits releasability. In the second embodiment, the silicone resin described later is also involved in the curing to become a crosslinked silicone resin, and exhibits the releasability in the middle peel force region or heavy peel force region. In addition, there is an effect of increasing the strength of the release layer by curing.
In general, for example, in the case of an addition reaction type silicone, sulfur, nitrogen, phosphorus and the like are catalyst poisons for the catalyst, but when a silicone resin composition emulsion is used, sulfur, nitrogen and the like are contained. Addition of the conductive polymer does not cause a problem in the curability of the obtained release layer. This is different from the conventional case where the silicone resin composition is dissolved in a solvent (for example, the one dissolved in an organic solvent), and the inside of the emulsion where the silicone resin composition exists and the conductive polymer exist. It is speculated that the separation from the outside of the emulsion is greatly affected. That is, when the silicone resin composition is dissolved in a solvent, the curing reaction occurs in the solvent. Similarly, the conductive polymer present in the solvent can participate in the curing reaction and inhibits the curing. In contrast, when the silicone resin composition is in the form of an emulsion, the curing reaction takes place inside the emulsion, so that the conductive polymer existing outside the emulsion is different in the system inside and outside the emulsion. Therefore, it is presumed that it cannot participate in the curing reaction and hardly causes inhibition of curing. Thus, when the silicone resin composition is an emulsion, the curing reaction in the presence of the conductive polymer is completely different from the conventional one, and the obtained release layer is also completely different from the conventional one. It becomes. In the present invention, the emulsion means a dispersion medium in which fine particles not mixed with the emulsion are dispersed. Such fine particles have, for example, a size ranging from about 1 μm to about 1 nm. In the present invention, the silicone resin composition contained in the silicone resin composition emulsion is particularly referred to as “emulsion-based silicone resin composition”.
The silicone resin composition in the present invention is not limited to an aqueous type, but may be any type capable of forming an emulsion, but is preferably an aqueous type silicone resin composition. Since the water-based silicone resin composition is excellent in stability when formed into an emulsion, the stability of the coating material can be increased as a result. Moreover, it is preferable from an environmental viewpoint to set it as a water-based coating agent.
In the present invention, a known method can be used for emulsification (emulsification) of the silicone resin composition. For example, a silicone resin composition prepared in advance and an emulsifier (if necessary, other components) are mixed with a homogenizer, an azide. It can be mechanically emulsified in an aqueous medium using a homomixer, an ultra planetary mixer or the like.
In the present invention, thermosetting can be preferably exemplified as a method for curing the silicone resin composition, that is, a thermosetting silicone resin composition is preferable as the silicone resin composition. As the silicone resin composition in the present invention, an aqueous thermosetting silicone resin composition is particularly preferable.
The silicone resin composition includes an addition reaction type and a condensation reaction type. From the viewpoint of excellent peeling property improvement effect, the silicone resin composition is an addition reaction type (the main agent is a polysiloxane having at least two unsaturated groups in one molecule). Siloxane, preferably polydimethylsiloxane) is preferred. As the crosslinking agent, a conventionally known crosslinking agent or one recommended by the manufacturer may be preferably used as the main crosslinking agent used at the same time.
As the main agent and the crosslinking agent as described above, those produced by a conventionally known method can be used as long as they satisfy the requirements of the present invention, and ready-made products can be used as they are. Moreover, what mixed the main ingredient and the crosslinking agent beforehand can also be used. Examples of the ready-made products include: Wacker Silicone product name: 400E, Dow Corning product name: X2-7720, Asahi Kasei Wacker product name: D480, Shin-Etsu Chemical product name: X52-6015, Momentive product name: SM3300E, manufactured by Arakawa Chemical Industries, Ltd. Product name: Silico Lease 902 and the like can be mentioned.
<Platinum catalyst>
In the first and second aspects of the present invention, the release layer preferably contains a platinum-based catalyst. The platinum-based catalyst is a catalyst for promoting the addition reaction between the main agent and the crosslinking agent, and a known catalyst can be used as the catalyst used in the addition reaction. Examples of such platinum-based catalysts include chloroplatinic acid, chloroplatinic acid alcohol solutions and aldehyde solutions, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like. The amount of the platinum-based catalyst added may be any amount that is usually used, but the amount of platinum metal added is preferably 1 to 1000 ppm, more preferably 10 to 300 ppm, relative to 100 parts by mass of the main agent. When the amount is high, the strength of the release layer is increased and the cost is excellent.
<Conductive polymer>
The conductive polymer that is an essential component of the release layer in the first and second aspects of the present invention contains cationic polythiophene and a polyanion as essential components. The method for producing the conductive polymer used in the present invention is not particularly limited. For example, it can be obtained by oxidative polymerization of a substance that becomes a cationic polythiophene monomer in an aqueous polyanion solution. .
(Cationic polythiophene)
The cationic polythiophene in the present invention contains 3,4-disubstituted thiophene represented by the following formula (I) as a main component of the repeating unit.

Here, in the above formula (I), R ¹ And R ² Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Or R ¹ And R ² Together represent an optionally substituted alkylene group having 1 to 12 carbon atoms. R ¹ And R ² Are independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ¹ And R ² As a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group and an ethyl group are particularly preferable. R ¹ And R ² Together are optionally substituted alkylene groups having 1 to 12 carbon atoms, examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, -An alkylene group such as an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,4-butylene group, a 2,3-butylene group, and a 1,2-cyclohexylene group. Of these, α, β-alkylene groups such as a methylene group, 1,2-ethylene group, 1,2-propylene group, and 2,3-butylene group are particularly preferable. Examples of such α, β-alkylene groups are derived from 1,2-dibromoalkanes obtained by bromination of α-olefins such as ethene, propene, hexene, octene, decene, dodecene, and styrene. Can do. Moreover, as a substituent in the said alkylene group, a C1-C12 alkyl group and a phenyl group are preferable, and especially a methyl group, an ethyl group, and a propyl group are preferable.
The cationic polythiophene in the present invention may contain only 3,4-disubstituted thiophene represented by the above formula (I) as a repeating unit, or 3,4-disubstituted thiophene as a main component of the repeating unit. And other monomers that can be polymerized therewith as secondary components. Here, the “main component” means that the proportion of the repeating unit of the 3,4-disubstituted thiophene represented by the above formula (I) is 50 mol% with respect to the entire repeating unit constituting the cationic polythiophene. It means that it is in the range of 100 mol% or less.
The polythiophene as described above exhibits a cationic property. Such cationic polythiophene can be obtained, for example, by oxidative polymerization of 3,4-disubstituted thiophene, which is a monomer, by the method described in JP-A-1-313521.
(Polyanion)
The polyanion in the present invention is not particularly limited. Examples thereof include polymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid, and polymaleic acid, and polymeric sulfonic acids such as polystyrene sulfonic acid and polyvinyl sulfonic acid.
Such polyanions such as polymeric carboxylic acids and polymeric sulfonic acids may be homopolymers composed of only one type of anionic monomer, or may be copolymers composed of a plurality of types of anionic monomers. Further, it may be a copolymer of an anionic monomer and other monomers copolymerizable with the monomer. Examples of other monomers copolymerizable with an anionic monomer include acrylates and styrenes. When the polyanion is a copolymer, it is sufficient that at least one anionic monomer is contained as a copolymerization component.
Among these, as the polyanion in the present invention, polystyrene sulfonic acid and polystyrene sulfonic acid at least part of which is a metal salt are particularly preferable and are excellent in the effect of improving conductivity.
The number average molecular weight Mn of the polyanion is preferably in the range of 1,000 or more and 2,000,000 or less, and more preferably in the range of 2,000 or more and 500,000 or less, from the viewpoint of enhancing the conductivity improving effect. .
Regarding the quantitative ratio (mass ratio) between the cationic polythiophene and the polyanion, the ratio of cationic polythiophene: polyanion is preferably 1: 1.1 to 1: 5.0, more preferably 1: 1.2 to 1. : 2.0.
The content of the conductive polymer in the release layer is preferably 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition. When the content is in the above numerical range, the effect of improving the releasability and antistatic property is excellent. When the content is too small, the effect of improving the antistatic property tends to be low. From such a viewpoint, it is more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 0.7% by mass or more. On the other hand, when there is too much content, the improvement effect of mold release property becomes low and it exists in the tendency for peeling force to become heavy. Moreover, when the addition amount of the conductive polymer increases, the cost tends to increase. Furthermore, the strength of the release layer after storage over time tends to be low. From such a viewpoint, it is more preferably 10% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less. Here, “with respect to 100% by mass of the emulsion type silicone resin composition” means “with respect to 100% by mass of the solid content of the emulsion type silicone resin composition”.
<Silicone resin>
The silicone resin in the second aspect of the present invention has at least one structure selected from the group consisting of a trifunctional unit siloxane represented by the following formula (II) and a tetrafunctional unit siloxane represented by the following formula (III). Is a polyorganosiloxane having as a main component. Here, “main component” means that the trifunctional unit siloxane is SiR. ³ O _3/2 The unit, tetrafunctional unit siloxane is SiO ₂ The aspect which contains a unit in the quantity exceeding 50 mol% in a molecule | numerator in total is shown, Preferably it is 70 mol% or more, More preferably, it is 90 mol% or more.

Here, in the above formula (II), R ³ Is a linear or cyclic alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, nonyl group, decyl group, dodecyl group, octadecyl group, cyclohexyl group, etc.), aromatic It represents either a group (for example, a phenyl group) or an alkenyl group (for example, a vinyl group). These may have multiple types in one molecule.
In the second aspect of the present invention, the crosslinked silicone resin constituting the release layer is formed from the emulsion-based silicone resin composition and 85% by mass or less of the silicone resin based on the mass of the release layer. It becomes. Thereby, the peeling force of the target middle peeling force area | region thru | or heavy peeling force area | region can be obtained. When there is too much content, it exists in the tendency for a silicone component to transfer easily, and there exists a tendency for peeling force to become heavy too much, and the problem that releasability cannot be obtained in the first place arises. In addition, the strength of the release layer after storage over time tends to be low. From this viewpoint, the content of the silicone resin is preferably 83% by mass or less, more preferably 82% by mass or less, and further preferably 80% by mass or less. Within this range, the content may be appropriately set according to the target peeling force. For example, a medium peel force region (a peel force region between a light peel force region and a heavy peel region may be referred to in this way. For example, a normal temperature peel force obtained by a measurement method described later is 60 to 200 mN / 25 mm, preferably In order to obtain a peeling force of 60 to 100 mN / 25 mm.), The content of the silicone resin is preferably 38% by mass or more and less than 65% by mass, and 38% by mass or more and less than 55% by mass. Is more preferable. Further, in a light peeling force region that is lighter than the medium peeling force region (for example, a region having a normal temperature peeling force that is less than 60 mN / 25 mm obtained by a measurement method described later), a silicone resin is not used if light peeling is achieved. Although it is preferable, the peeling force can be finely adjusted within a range of less than 38% by mass. The content is preferably 30% by mass or more, and in the range below the lower limit, the effect of increasing the peeling force is small.
On the other hand, in the region where the content is relatively low, there is a tendency that the peeling force becomes only moderately heavy even if the content of the silicone resin is increased. Therefore, in order to obtain a peeling force in a preferable heavy peeling force region in the present invention, the content of the silicone resin is preferably 65% by mass or more, more preferably 70% by mass or more, and further 75% by mass or more. preferable.
In the second aspect of the present invention, the silicone resin is emulsified by being dispersed in a dispersion medium mainly composed of water (here, “mainly” means a ratio exceeding 50% by mass). A silicone resin emulsion is used, a coating liquid containing the same is applied to form a coating film, and the coating film is cured to form a release layer. The silicone resin reacts with the above-described silicone resin composition by such curing, takes in the crosslinked silicone resin to form a release layer, and exhibits an effect of increasing the peeling force in the release layer.
In the second aspect of the present invention, by using the silicone resin emulsion as described above, a conductive polymer containing sulfur, nitrogen, phosphorus, etc. is added in the same manner as described in the section of the silicone resin composition. Even so, the reaction of the silicone resin is not inhibited, and the effect of increasing the peeling force can be efficiently achieved. Moreover, it is hard to produce the problem regarding the sclerosis | hardenability of the mold release layer obtained. Such a mechanism is considered to be the same as the mechanism described in the section of the silicone resin composition. In the present invention, the silicone resin contained in the silicone resin emulsion is particularly referred to as an emulsion-based silicone resin.
The silicone resin may be any silicone resin that can form an emulsion without being aqueous, but is preferably an aqueous silicone resin. A water-based silicone resin is excellent in stability when formed into an emulsion, and as a result, the stability of the coating liquid can be increased. Moreover, it is preferable from an environmental viewpoint to set it as a water-based coating liquid.
For emulsification (emulsification) of the silicone resin, a known method described in the section of the silicone resin composition can be used.
As a method of curing the silicone resin together with the above-described silicone resin composition, thermosetting can be preferably exemplified. That is, as the silicone resin, a thermosetting silicone resin is preferable. As the silicone resin in the present invention, an aqueous thermosetting silicone resin is particularly preferable.
As the silicone resin as described above, a silicone resin produced by a conventionally known method can be used as long as it satisfies the requirements of the present invention, or a ready-made product can be used as it is. Examples of the ready-made products include Asahi Kasei Wacker's trade name: CRA92, Toray Dow Corning Inc. trade names: BY22-736EX, BY22-749SR, SM7001EX, SM7002EX, and the like.
<Other components that can be contained in the release layer>
In the first and second aspects of the present invention, from the viewpoint of further improving the conductivity, the coating liquid is allowed to contain an alkylene glycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, or polyethylene glycol. A mold layer can be formed. A water-soluble compound having an amide bond in the molecule and liquid at room temperature can also be used. In addition, it can contain a water-soluble compound having an amide bond in the molecule and liquid at room temperature.
The content of these compounds is preferably 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive polymer. When the content is too small, the effect of improving the conductive performance tends to be low. From this viewpoint, 30 parts by mass or more is more preferable. On the other hand, when there is too much content, it exists in the tendency which is inferior to transparency, adhesiveness, and blocking resistance. Moreover, the improvement effect of the heat-and-moisture resistance of a mold release layer tends to become low. From this viewpoint, 600 parts by mass or less is more preferable. Here, “with respect to 100 parts by mass of the conductive polymer” means “with respect to 100 parts by mass of the solid content of the conductive polymer”.
In the release layer of the present invention, an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, a dye, an organic, You may mix | blend inorganic microparticles | fine-particles, a filler, transparent conductive agents other than the said conductive polymer, a nucleating agent, etc.
<Method for producing release film>
In the first aspect of the present invention, the emulsion-based silicone resin composition described above, a conductive polymer, a platinum-based catalyst that may be optionally added, and other components that may optionally be added. A release liquid is formed by applying a coating liquid containing as a constituent component to a substrate film and curing the obtained coating film.
In the second aspect of the present invention, the emulsion-based silicone resin composition, the emulsion-based silicone resin, the conductive polymer, the platinum catalyst that may be optionally added, and the optional addition. The release layer is formed by applying a coating liquid containing other components as optional components to the base film and curing the obtained coating film.
The coating liquid can be produced by uniformly mixing the above components using a stirring blade or the like. At this time, in the first aspect of the present invention, it is important that the emulsion-based silicone resin composition is used as a silicone resin composition emulsion containing the emulsion-based silicone resin composition, and the conductive polymer is used as an aqueous dispersion thereof. is there. In the second aspect of the present invention, in addition to the above, it is important to use the emulsion-based silicone resin as a silicone resin emulsion containing the emulsion-based silicone resin. Thereby, each component can be mixed uniformly and a uniform release layer can be obtained. Moreover, each component does not cancel its function, and a release layer having excellent release properties and antistatic properties can be obtained. In order to mix each component more uniformly, as long as the objective of this invention is not impaired, it can dilute using a suitable solvent. Moreover, about arbitrary components, you may use what was melt | dissolved or disperse | distributed using the suitable solvent.
As a coating liquid at the time of coating, the coating liquid obtained by mixing may be used as it is, but as long as the object of the present invention is not impaired, it is diluted with an appropriate solvent and adjusted to have an appropriate viscosity. It is preferable to use a coating liquid from the viewpoint of obtaining a release layer that is uniform and has a good appearance. As the solvent, water is preferable. It may contain some alcohol. In that case, it is preferable that the amount of water exceeds 50% by mass. By doing in this way, it becomes easy to hold | maintain a silicone resin composition emulsion as an emulsion, and it becomes easy to hold | maintain a silicone resin emulsion as an emulsion, and it can make the improvement effect of a mold release property and antistatic property high.
As a coating method for coating the coating liquid on the base film, any known coating method can be applied. For example, gravure roll coating method, reverse roll coating method, die coating method, kiss coating method, reverse kiss coating method, offset gravure method A coating method, a Mayer bar coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, a doctor blade method, and the like can be applied alone or in combination. Further, for the purpose of improving the stability of the coating appearance such as repelling, the coating liquid can contain a slight amount of a surfactant.
In addition, the base film can be subjected to a preliminary treatment on the surface as needed for the purpose of improving adhesion, coating property and the like before applying the coating liquid. As such preliminary treatment, for example, physical surface treatment such as corona discharge treatment, plasma discharge treatment, or coating of an organic resin or inorganic resin during or after the formation of the base film, Examples thereof include a chemical surface treatment for forming a coating adhesion layer.
The conditions for drying and curing after applying the coating liquid to the base film are preferably heated at a temperature of 100 ° C. or higher and 180 ° C. or lower for 10 seconds or longer and 120 seconds or shorter, 120 ° C. or higher and 160 ° C. It is more preferable to heat at a temperature of 20 seconds or more and 90 seconds or less at the following temperature, and heating at a temperature of 130 ° C. or more and 150 ° C. or less for 30 seconds to 60 seconds is particularly preferable. By adopting the drying conditions as described above, the strength of the release layer can be further increased. Moreover, the adhesiveness of a base film and a mold release layer can be made higher. In addition, it is possible to more appropriately suppress the feeding charging.
Thus, the release film of the present invention can be obtained.
<Characteristics of release film>
(Thickness of release layer)
In the first and second aspects of the present invention, the thickness of the release layer is preferably 10 nm or more and 3 μm or less. When the thickness is too thin, it is difficult to form a uniform coating film, and the peeling force tends to increase. In addition, the uniformity of the peeling force tends to be inferior, and not only the effect of improving the releasability is lowered, but also the surface resistance value tends to be increased because the amount of the conductive polymer in the release layer is small. The antistatic property improving effect tends to be low. Furthermore, the strength of the release layer after storage over time tends to be low. In this respect, 50 nm or more is more preferable, 0.3 μm or more is further preferable, and 0.5 μm or more is particularly preferable. On the other hand, if it is too thick, it consumes more material than necessary to exhibit antistatic performance, and it is not economical, and it causes an abnormality called blocking where the front and back stick in the state of the wound roll, and it can be used. become unable. From this viewpoint, 2 μm or less is more preferable, 1.5 μm or less is more preferable, 0.8 μm or less is particularly preferable, and 0.7 μm or less is most preferable.
(Peeling power)
In the present invention, by adopting the first aspect, a cross-linked silicone resin aspect (for example, a main agent or a substituent of a cross-linking agent in a silicone resin composition) and an additive (for example, particles) for exhibiting releasability are adopted. Addition), thickness, etc., can be adjusted as appropriate to accommodate a wide range of desired peeling forces. In particular, since the inhibition of curing by the conductive polymer is suppressed, it is possible to obtain a peeling force in a light peeling force region. And since it has antistatic property simultaneously with this mold release property, it can use suitably as a carrier sheet for manufacture of the product which has an adhesion layer, or a sheet | seat formation, for example. In particular, when the product to be manufactured is brittle, it is useful to use a light release force when suppressing the breakage of the product at the time of peeling the carrier sheet or improving the productivity by facilitating the peeling. .
Further, by adopting the second aspect of the present invention, it is possible to obtain a peeling force in a medium peel force region or a heavy peel force region. And in order to have anti-static properties at the same time as such mold release properties, for example, it is a carrier sheet for manufacturing a product having a pressure-sensitive adhesive layer or a sheet forming, and the product is erroneously peeled off from the carrier sheet especially during the use process. This can be suitably used in the case where it is desired to highly suppress the error that occurs. Moreover, it can use suitably as a release film (carrier film) on the heavy release side of an electronic material adhesive tape such as an anisotropic conductive adhesive film or a non-carrier film.
The peel strength of the release film of the first aspect of the present invention is preferably 20 to 300 mN / 25 mm, more preferably 20 to 200 mN / 25 mm, and even more preferably, at room temperature peel force determined by the measurement method described later. Is 20 to 100 mN / 25 mm, particularly preferably 30 to 60 mN / 25 mm. When the room temperature peel force is in the above numerical range, it is excellent in releasability, for example, an appropriate peel force for an adhesive tape for electronic members, and the adhesive is deformed and becomes non-uniform when peeled. The problem can be suppressed. Moreover, it can suppress that an adhesive resin etc. turns easily in the process after apply | coating and drying adhesive resin etc. on a mold release layer.
Further, in the heat peeling force required by the measurement method described later, it is preferably 20 to 500 mN / 25 mm, more preferably 20 to 300 mN / 25 mm, still more preferably 20 to 200 mN / 25 mm, and particularly preferably 40 to 100 mN / 25 mm. is there. When the heat peeling force is in the above numerical range, it is possible to suppress the peeling of the adhesive when not intended during handling due to too light peeling, and the deformation of the adhesive during peeling due to too heavy peeling.
The release film of the first aspect of the present invention has a room temperature aging force determined by a measurement method described later, preferably 20 to 500 mN / 25 mm, more preferably 20 to 300 mN / 25 mm, and still more preferably 20 to 100 mN / 25 mm, particularly preferably 30 to 60 mN / 25 mm. If it is lighter than 20 mN / 25 mm, the product cast into a release film such as an adhesive resin is likely to be turned over after use with storage over time, resulting in a decrease in yield. On the other hand, if it is heavier than 500 mN / 25 mm, a product such as an adhesive resin cannot be easily peeled off from the release film in the production process.
The release film as the first aspect of the present invention has a heating aging peel force determined by a measurement method described later, preferably 20 to 500 mN / 25 mm, more preferably 20 to 300 mN / 25 mm, and still more preferably 20 to 200 mN. / 25 mm, particularly preferably 40 to 100 mN / 25 mm. If it is lighter than 20 mN / 25 mm, the product cast into a release film such as an adhesive resin is likely to be turned over after use with storage over time, resulting in a decrease in yield. On the other hand, if it is heavier than 500 mN / 25 mm, a product such as an adhesive resin cannot be easily peeled off from the release film in the production process.
In order to have such a peeling force, the release coating film needs to be in an appropriate state.If the coating film is extremely thin, the coating film will repel, and the peeling will be heavy at the repelling part, In addition, even when the coating film is extremely thick, when it is wound up with a roll, the release layer sticks to the film wound up and laminated, and when the film is unwound from the roll, the release layer is cohesive failure Therefore, it is important to set the appropriate coating thickness range as described above. Moreover, in order to achieve the peeling force with time, it is also effective to reduce the excess hydrogen silane as a crosslinking agent. In addition, after the release layer is formed, it tends to be improved by performing a heating treatment at 40 to 60 ° C. for about 1 to 7 days.
The peel strength of the release film of the second aspect of the present invention is preferably 200 to 800 mN / 25 mm, more preferably 250 mN / 25 mm or more, and even more preferably 270 mN in the room temperature peel force determined by the measurement method described later. / 25 mm or more, more preferably 600 mN / 25 mm or less, further preferably 500 mN / 25 mm or less, and particularly preferably 450 mN / 25 mm or less. When the room temperature peel force is in the above numerical range, the release property is excellent, and for example, a peel force suitable for an electronic material adhesive tape can be obtained. In particular, in the anisotropic conductive adhesive film, when connecting the anisotropic conductive adhesive film to the substrate, in particular in the temporary connection process, it becomes an appropriate peeling force, the release film does not float, and in the heating process Problems such as peeling of the adhesive from the substrate (Nakiwakare) can be suppressed.
Moreover, in the heat peeling force calculated | required by the below-mentioned measuring method, Preferably it is 400-900mN / 25mm, More preferably, it is 450mN / 25mm or more, More preferably, it is 800mN / 25mm or less, More preferably 700 mN / 25 mm or less. When the heat peeling force is in the above numerical range, it is possible to suppress unintentional peeling of the adhesive during handling due to too light peeling, and deformation of the adhesive during peeling due to excessive peeling. Further, for example, when used as an electronic material adhesive tape, particularly as a release film for an anisotropic conductive adhesive film, when it is in the above-mentioned peeling force range, especially when connecting to the base of the anisotropic conductive film, In the temporary connection step, an appropriate peeling force is obtained, the release film does not float, and problems such as peeling of the adhesive from the substrate (sparkling) in the heating step can be suppressed.
In the release film of the second aspect of the present invention, the room temperature aging peel force determined by the measurement method described later is preferably 200 to 700 mN / 25 mm, more preferably 300 to 600 mN / 25 mm. In addition, the release film of the present invention has a heat aging peeling force determined by a measurement method described later, preferably 550 to 1100 mN / 25 mm, more preferably 600 to 1000 mN / 25 mm. When the peel strength with time is in the above range, the stability of the peel strength of the release film can be obtained in use after storage over time.
In order to obtain such a peeling force, it is effective to use an emulsion-based silicone resin composition. It is also effective to use an emulsion type silicone resin. Also, the release coating must be in an appropriate state. If the coating is extremely thin, the coating will be repelled, the peeling will be too heavy at the repelling area, and the coating will be extremely thick. In addition, when the film is wound with a roll, the release layer adheres to the film wound and laminated thereon, and when the film is unwound from the roll, the release layer coagulates and breaks. Since the moldability is impaired, it is important to set the appropriate coating thickness range as described above. Moreover, in order to achieve the peeling force with time, it is also effective to reduce the excess hydrogen silane as a crosslinking agent. In addition, after the release layer is formed, it tends to be improved by performing a heating treatment at 40 to 60 ° C. for about 1 to 7 days.
(Residual adhesion rate)
The room temperature residual adhesion rate of the release films of the first and second aspects of the present invention is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. When the room temperature residual adhesion rate is in the above numerical range, for example, in an adhesive tape for electronic members, the peeling force becomes stable over time. If it is lower than 80%, the transfer of the silicone component to the product increases, the adhesive strength is reduced and contamination with the silicone component is likely to occur, resulting in a decrease in yield. In forming the release layer, if a solvent-based silicone resin composition is used as the silicone resin composition used simultaneously with the conductive polymer, the room temperature residual adhesion rate cannot be increased. In order to achieve the above room temperature residual adhesion rate, the silicone resin composition to be used needs to be an emulsion type silicone resin composition.
Further, the heat residual adhesion rate is preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more. When the heating residual adhesion rate is in the above numerical range, the silicone transfer to the adherend is low, so that it is possible to prevent the performance degradation of the pressure-sensitive adhesive or the like. If it is lower than 70%, the transfer of the silicone component to the product will increase due to long-term storage, and the adhesive strength and contamination by the silicone component will easily occur, resulting in a decrease in yield.
In order to obtain such a residual adhesion rate, it is effective to use an emulsion type silicone resin composition. It is also effective to use an emulsion type silicone resin. Further, since low molecular components such as unreacted components of silicone also reduce the residual adhesion rate, it is important to sufficiently crosslink the coating film. In order to achieve sufficient crosslinking, it is mainly described in known literatures and the like. However, addition of an appropriate amount of a crosslinking agent and a catalyst and sufficient heating are important, and these may be adjusted.
(Surface resistance value)
The surface resistance value of the release layer in the first and second embodiments of the present invention is 1 × 10 ⁵ ~ 1 × 10 ¹³ It is preferable that it is Ω / □. When the surface resistance value is in the above numerical range, for example, when used as a protective film for an adhesive tape for electronic members, adhesion of dust and the like can be suppressed, the quality of the electronic members is increased, and the yield is also increased. Moreover, it becomes easy to set it as the outstanding mold release property. When the surface resistance value is low, the effect of suppressing the adhesion of dust and the like tends to be improved, but when it is too low, the effect of improving the releasability tends to be low. On the other hand, when the surface resistance value is high, excellent release properties are easily obtained, but when it is too high, the effect of suppressing dust adhesion tends to be low. From such a viewpoint, the surface resistance value is more preferably 1 × 10. ⁹ ~ 1 × 10 ¹² Ω / □.
In order to obtain such a surface resistance value, the addition amount of the conductive polymer may be adjusted, or the addition of the above-described alkylene glycol may be adjusted. For example, when the addition amount of the conductive polymer is increased, the surface resistance value tends to decrease. If an emulsion-based silicone resin composition is not used, a coating film cannot be formed well and the surface resistance value tends to be low. It is also preferable to use an emulsion type silicone resin.

　［実施例２−１］
　＜基材フィルム＞
　酢酸マンガンをエステル交換触媒、亜燐酸を安定剤、三酸化アンチモンを重合触媒とし、滑剤として酸化ケイ素粒子（平均粒径１．８μｍ）を０．０６質量％含有する、固有粘度が０．５６（２３℃、ｏ−クロロフェノール溶媒）のポリエチレンテレフタレートペレットを乾燥後、溶融温度２８０~３００℃で溶融し、ついで表面温度２０℃の回転冷却ドラム上に押出して厚み５２０μｍの未延伸フィルムを得た。
　得られた未延伸フィルムを温度７５℃に予熱し、次いで低速、高速のロール間で１５ｍｍ上方より８００℃の表面温度のＩＲヒーターにて加熱して縦方向に３．６倍に延伸し、急冷し、続いて横延伸機に供給し、温度１２０℃にて横方向に３．９倍に延伸した。得られた二軸配向フィルムを２３０℃の温度で５秒間熱固定し、厚み３８μｍの熱固定二軸配向ポリエステルフィルムを得た。得られたポリエステルフィルムは、片面にコロナ処理を施した。
　＜離型層＞
　水に対し、付加反応型のシリコーン樹脂組成物のエマルジョン（信越化学工業株式会社製：Ｘ５２−６０１５、固形分４０質量％、このシリコーン樹脂組成物は、主剤および架橋剤からなり、かかる主剤および架橋剤は、それぞれ−Ｓｉ（ＣＨ_３）_２Ｏ−単位を分子中に５０モル％を超える量で含有する。）、触媒（信越化学工業株式会社製：ＣＡＴ−ＰＭ−１０Ａ）、ジエチレングリコール、及びバイトロンＰ（ポリエチレンジオキシチオフェン０．５質量％、ポリスチレンスルホン酸がドーパントとして０．８質量％添加された導電性高分子の水分散体、アグファマテリアルズ社製、固形分１．３質量％）、シリコーンレジンのエマルジョン（旭化成ワッカー社製：ＣＲＡ９２、固形分５０質量％、このシリコーンレジンは、三官能単位シロキサンおよび／または四官能単位シロキサンを含有し、ＳｉＲ^３Ｏ_３／２単位および／またはＳｉＯ_２単位を分子中に合計５０モル％を超える量で含有する。）を以下に示す混合比で添加・攪拌して塗液とした後、かかる塗液を、上記で得られたポリエステルフィルムのコロナ処理が施された方の表面に、常法のロールコートにより塗布し、１４０℃の乾燥温度にて６０秒乾燥し、乾燥後の膜厚みが０．８μｍの離型層を形成し、離型フィルムを得た。得られた離型フィルムの特性を表２に示す。なお、下記におけるかっこ内は、シリコーン樹脂組成物の固形分１００質量％に対する各成分の固形分の質量比を示す。
　水　　　　　　　　　：１８．６質量部
　Ｘ５２−６０１５　　：　２．２質量部　（１００質量％）
　ＣＡＴ−ＰＭ−１０Ａ：　０．１１質量部（１２．５質量％）
　ジエチレングリコール：　０．５質量部
　バイトロンＰ　　　　：　３．０質量部　（４．４質量％）
　ＣＲＡ９２　　　　　：　６．６質量部　（３７５質量％）
　なお、離型層中におけるシリコーンレジンの質量割合は、７６．２質量％である。
　［実施例２−２］
　離型層を形成するための塗液における各成分の混合比を次の通りとした以外は、実施例２−１と同様の方法にて離型層を形成し、離型フィルムを得た。得られた離型フィルムの特性を表２に示す。
　水　　　　　　　　　：１８．７質量部
　Ｘ５２−６０１５　　：　２．０質量部（１００質量％）
　ＣＡＴ−ＰＭ−１０Ａ：　０．１質量部（１２．５質量％）
　ジエチレングリコール：　０．５質量部
　バイトロンＰ　　　　：　３．０質量部（４．９質量％）
　ＣＲＡ９２　　　　　：　６．８質量部（４２５質量％）
　なお、離型層中におけるシリコーンレジンの質量割合は、７８．４質量％である。
　［実施例２−３］
　離型層を形成するための塗液における各成分の混合比を次の通りとし、乾燥後の塗布厚みを１．３μｍとした以外は、実施例２−１と同様の方法にて離型層を形成し、離型フィルムを得た。得られた離型フィルムの特性を表２に示す。
　水　　　　　　　　　：１１．３質量部
　Ｘ５２−６０１５　　：　７．３質量部（１００質量％）
　ＣＡＴ−ＰＭ−１０Ａ：　０．４質量部（１３．７質量％）
　ジエチレングリコール：　０．５質量部
　バイトロンＰ　　　　：　３．０質量部（１．３質量％）
　ＣＲＡ９２　　　　　：　７．５質量部（１２８．４質量％）
　なお、離型層中におけるシリコーンレジンの質量割合は、５２．８質量％である。
　［実施例２−４］
　離型層を形成するための塗液における各成分の混合比を次の通りとし、乾燥後の塗布厚みを０．４μｍとした以外は、実施例２−１と同様の方法にて離型層を形成し、離型フィルムを得た。得られた離型フィルムの特性を表２に示す。
　水　　　　　　　　　：２２．３質量部
　Ｘ５２−６０１５　　：　０．５質量部　（１００質量％）
　ＣＡＴ−ＰＭ−１０Ａ：　０．０２質量部（１０質量％）
　ジエチレングリコール：　０．５質量部
　バイトロンＰ　　　　：　３．０質量部　（１９．５質量％）
　ＦＺ−７７　　　　　：　０．１質量部
　ＣＲＡ９２　　　　　：　３．６質量部　（９００質量％）
　なお、離型層中におけるシリコーンレジンの質量割合は、８７．４質量％である。
　また、ＦＺ−７７は界面活性剤（東レダウコーニング社製）である。
　［比較例２−１］
　メチルエチルケトン（ＭＥＫ）７０質量部とトルエン３０質量部とからなる溶剤に、主剤としてのポリジメチルシロキサンを主成分とするシリコーン（信越化学工業株式会社製：ＴＰＲ６７００、トルエン溶液、固形分３０質量％）を１０質量部溶解し、触媒（信越化学工業株式会社製：ＣＭ６７０）を０．２質量部混合し、バイトロンＰを１０質量部及びＣＲＡ９２を１０質量部添加したところ、塗液の分離が発生したが、塗布を行いサンプルを作成した。
　ＭＥＫ　　　　　　　：　７０質量部
　トルエン　　　　　　：　３０質量部
　ＴＰＲ６７００　　　：　１０質量部（１００質量％）
　ＣＭ６７０　　　　　：０．２質量部（６．７質量％）
　バイトロンＰ　　　　：　１０質量部（４．３質量％）
　ＣＲＡ９２　　　　　：　１０質量部（１６６．７質量％）
　なお、離型層中におけるシリコーンレジンの質量割合は、６０．０質量％である。
　［実施例２−５~２−１４］
　離型層を形成するための塗液における各成分の混合比を表３に示すとおりとし、乾燥後の塗布厚みを表２に示すとおりとした以外は、実施例２−１と同様の方法にて離型層を形成し、離型フィルムを得た。得られた離型フィルムの特性を表２に示す。
　なお、表中、ａＥ＋ｂは、ａ×１０^ｂを示す。

発明の効果
　本発明によれば、帯電防止層と離型層とを別々に設けることなく、帯電防止性と離型性とに同時に優れる離型フィルムを提供することができる。
　本発明の第１の態様によれば、帯電防止性とともに、幅広い範囲の剥離力とすることができる。特に、導電性高分子による硬化阻害が抑制されているため、軽剥離力領域の剥離力とすることもできる。これにより、軽剥離が要求される用途、例えば粘着層を有する製品の製造に用いられるキャリアシートや、各種シートの形成に用いられるキャリアシート等として好適に用いることができる。
　また、本発明の第２の態様によれば、帯電防止性とともに、中剥離力領域ないし重剥離力領域の剥離力とすることができる。これにより、重剥離が要求される用途、例えば異方性導電性接着フィルムやノンキャリアフィルム等の電子材料接着テープの重剥離側の離型フィルム（キャリアフィルム）として好適に用いることができる。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each evaluation in an Example followed the following method.
(1) Release Layer Thickness After the release film sample was cut into triangular pieces, a Pt (platinum) layer having a thickness of 2 nm was formed on the release layer surface by coating. The obtained sample was fixed to a multiaxial embedding capsule, embedded using an epoxy resin, sliced in a direction perpendicular to the surface direction of the film using a microtome ULTRACUT-S, and a thickness of 50 nm. An ultra-thin sample was obtained. Next, the obtained ultra-thin sample was placed on a grid and vapor-stained with 2% osmic acid at 60 ° C. for 2 hours. Using the ultra-thin sample after vapor staining, the film cross section was observed with a transmission electron microscope LEM-2000 under the condition of an acceleration voltage of 100 kv, and the thickness of the release layer was measured. The measurement was carried out for 10 arbitrary points, and the average value thereof was defined as the thickness (unit: nm) of the release layer.
(2) Smear The appearance after the surface of the release layer was lightly boiled with the belly of an index finger cleaned with gauze impregnated with ethyl alcohol was confirmed and evaluated according to the following criteria.
○: No change in appearance is confirmed.
X: Change in appearance such as cloudiness is confirmed.
(3) Love-off The surface of the release layer of the sample is rubbed ten times strongly with the thumb belly cleaned with gauze impregnated with ethyl alcohol. A cellophane tape (manufactured by Nichiban Co., Ltd., cello tape (registered trademark)) is pressure-bonded with a rubber roller so as to cross the rubbed portion, and then reciprocated once with a 2 kg metal roller. The bonded cellophane tape was peeled off by hand, and the hook of the cellophane tape was evaluated according to the following criteria in comparison with the surface of the release layer that was not rubbed.
○: There is no catch or is equivalent to the non-rubbed part.
X: The catch is strong compared with the non-rubbed part.
(4) Aging storage lab-off The samples were stored for 7 days in an environment of 60 ° C. and 90% relative humidity, and evaluated in the same manner as the rub-off using samples subjected to the aging treatment.
○: There is no catch or is equivalent to the non-rubbed part.
X: The catch is strong compared with the non-rubbed part.
(5) Room temperature peeling force A 10 cm x 20 cm release film sample was cut out, a 25 mm wide polyester adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) was pasted on the surface of the release layer, and a 2 kg x 45 mm wide pressure roller. 1. Apply a reciprocating load. The sample with the tape attached is cut into 25 mm width x 150 mm length, stored at room temperature (23 ° C) for 2 hours, and then the 31B adhesive tape side is attached and fixed to an aluminum plate with a length of 50 mm width x 125 mm. The release film was peeled off at a peel angle of 180 ° and a peel speed of 300 mm / min, and the peel strength was measured. This measurement was performed three times, and the average value was taken as the room temperature peeling force (unit: N / 25 mm).
(6) Heat peel force The measurement was carried out in the same manner as the room temperature peel force except that the storage conditions were 20 g / cm ^{2 under} a load of 20 g / cm ² for 20 hours, and the heat peel force (unit: N / 25 mm).
(7) Separation force at room temperature over time A 10 cm × 20 cm release film sample was cut out, a 25 mm width polyester adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) was pasted on the surface of the release layer, and a 2 kg × 45 mm width press roller Then, apply one reciprocating load. The sample with the tape attached is cut into 25 mm width × 150 mm length and left in the room (23 ° C.) for 24 hours, and then the 31B adhesive tape side is attached and fixed to an aluminum plate with a length of 50 mm width × 125 mm. . This is fixed to a tensile tester, the release film is peeled off at a peel angle of 180 ° and a peel speed of 300 mm / min, and the peel force is measured. This measurement is performed three times, and the average value is taken as the room temperature aging peel force (unit: N / 25 mm).
(8) Peeling force with heating 10 cm × 20 cm release film sample was cut out, and a 25 mm width polyester adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) was pasted on the surface of the release layer, and a 2 kg × 45 mm width press roller Then, apply one reciprocating load. The sample with the tape attached was cut to 25 mm width x 150 mm length, left in a dryer at 70 ° C for 20 hours, then left in a room at 23 ° C for 1 hour, and the 31B adhesive tape side was 50 mm wide. Affixed to a 125 mm long aluminum plate. This is fixed to a tensile tester, the release film is peeled off at a peel angle of 180 ° and a peel speed of 300 mm / min, and the peel force is measured. This measurement is performed three times, and the average value is taken as the heating aging peel force (unit: N / 25 mm).
(9) Room temperature residual adhesion rate After attaching a polyester adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) to a cold-rolled stainless steel plate (SUS304) specified in JIS G4305, it is peeled off to give a peeling force. Measure and use as basic adhesive strength (f0). Next, a new polyester pressure-sensitive adhesive tape is pressure-bonded to the release layer coating surface of the sample film with a 2 kg pressure roller, left for 30 seconds, and then peeled off. And this peeled polyester adhesive tape is affixed on said stainless steel plate, it is peeled, peeling force is measured, and it is set as residual adhesive force (f). From the obtained basic adhesive force (f0) and residual adhesive force (f), the residual adhesive rate (unit:%) was determined using the following formula.
Residual adhesion rate (%) = (f / f0) × 100
(10) Heating residual adhesion rate The heating residual adhesion rate was determined in the same manner as the room temperature residual adhesion rate except that the standing was performed in a dryer at 70 ° C for 24 hours.
(11) Surface resistance value On the surface of the release layer, the surface resistance value was measured with a measuring instrument (R8340 / R12704) manufactured by Advantest Corporation. The measurement environment was a sample film that had been aged for 24 hours in an atmosphere of a temperature of 23 ° C. and a humidity of 55%.
[Example 1-1]
<Base film>
Manganese acetate is used as a transesterification catalyst, phosphorous acid is used as a stabilizer, antimony trioxide is used as a polymerization catalyst, and 0.06% by mass of silicon oxide particles (average particle size: 1.8 μm) is used as a lubricant. 23 ° C., o-chlorophenol solvent) polyethylene terephthalate pellets were dried, melted at a melting temperature of 280 to 300 ° C., and then extruded onto a rotary cooling drum having a surface temperature of 20 ° C. to obtain an unstretched film having a thickness of 520 μm.
The obtained unstretched film is preheated to a temperature of 75 ° C., then heated by an IR heater with a surface temperature of 800 ° C. from above 15 mm between low-speed and high-speed rolls, stretched 3.6 times in the machine direction, and rapidly cooled. Subsequently, the film was supplied to a transverse stretching machine and stretched 3.9 times in the transverse direction at a temperature of 120 ° C. The obtained biaxially oriented film was heat-set at a temperature of 230 ° C. for 5 seconds to obtain a heat-fixed biaxially oriented polyester film having a thickness of 38 μm. In the film forming step, 3-glycidoxypropyltrimethoxysilane is used as an anchor coat layer of a release layer on one side of the polyester film at a position immediately before the uniaxially stretched film that has been longitudinally stretched enters transverse stretching. A 3% by weight aqueous solution (containing 2.0% by weight of a surfactant in the solid content) was applied in an amount of 5 g / m ² (wet) and dried.
<Release layer>
Emulsion of an addition reaction type silicone resin composition with respect to water (manufactured by Shin-Etsu Chemical Co., Ltd .: X52-6015, solid content 40% by mass, this silicone resin composition comprises a main agent and a crosslinking agent. Each of the agents contains —Si (CH ₃ ) ₂ O— units in the molecule in an amount exceeding 50 mol%.), Catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: CAT-PM-10A), diethylene glycol, and vitron P (Polyethylenedioxythiophene 0.5% by mass, conductive polymer aqueous dispersion added with 0.8% by mass polystyrene sulfonate as a dopant, manufactured by Agfa Materials, solid content 1.3% by mass) After adding and stirring at the mixing ratio shown below to obtain a coating solution, the coating solution is prepared by using the polyester film anchor coat layer obtained above. The formed surface is coated by a conventional roll coat and dried at a drying temperature of 140 ° C. for 60 seconds to form a release layer having a thickness of 0.7 μm after drying. Obtained. The properties of the obtained release film are shown in Table 1. In addition, the inside of the parenthesis in the following shows mass ratio of each component with respect to 100 mass% of solid content of a silicone resin composition.
Water: 190 parts by mass X52-6015: 73 parts by mass (100% by mass)
CAT-PM-10A: 4 parts by mass (13.7% by mass)
Diethylene glycol: 5 parts by weight Vitron P: 30 parts by weight (1.3% by weight)
[Example 1-2]
A release layer was formed in the same manner as in Example 1-1 except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 1.
Water: 190 parts by mass X52-6015: 73 parts by mass (100% by mass)
CAT-PM-10A: 4 parts by mass (13.7% by mass)
Diethylene glycol: 5 parts by weight Vitron P: 15 parts by weight (0.7% by weight)
[Example 1-3]
The release layer was formed in the same manner as in Example 1-1 except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows and the coating thickness after drying was 0.5 μm. And a release film was obtained. The properties of the obtained release film are shown in Table 1.
Water: 220 parts by mass X52-6015: 50 parts by mass (100% by mass)
CAT-PM-10A: 2 parts by mass (10.0% by mass)
Diethylene glycol: 5 parts by weight Vitron P: 20 parts by weight (1.3% by weight)
[Example 1-4]
A release layer was formed in the same manner as in Example 1-3, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows.
Water: 220 parts by mass X52-6015: 50 parts by mass (100% by mass)
CAT-PM-10A: 2 parts by mass (10.0% by mass)
Diethylene glycol: 5 parts by weight Vitron P: 10 parts by weight (0.7% by weight)
[Example 1-5]
A release layer was formed in the same manner as in Example 1-1 except that the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 1.
In deionized water, when stirring, silicone emulsion 400E (manufactured by Wacker Silicones, silicone: methylpolysiloxane having vinyl group, crosslinker) is added as a main ingredient to prevent premature reaction with platinum catalyst Inhibitors in combination, solid content concentration of 50% by mass), crosslinker V72 (made by Wacker Silicones, an emulsion of methylhydrogen polysiloxane, which reacts with double bonds in methylsiloxane, solid content concentration 50 mass%), a silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-403), and polyoxyethylene oleyl ether (trade name: Emulgen 404, produced by Kao Corporation) as a nonionic surfactant, diethylene glycol And Vitron P are shown below Adding and stirred to a coating liquid in the mixing ratio.
Water: 580 parts by mass 400E: 67 parts by mass (90.6% by mass)
V72: 7 parts by mass (9.4% by mass)
KBM-403: 2 parts by mass (5.4% by mass)
Emulgen 404: 1 part by mass (2.7% by mass)
Diethylene glycol: 15 parts by weight Vitron P: 34 parts by weight (1.1% by weight)
[Example 1-6]
A release layer was formed in the same manner as in Example 1-5 except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 1.
Water: 580 parts by mass 400E: 67 parts by mass (90.6% by mass)
V72: 7 parts by mass (9.4% by mass)
KBM-403: 2 parts by mass (5.4% by mass)
Emulgen 404: 1 part by mass (2.7% by mass)
Diethylene glycol: 15 parts by weight Vitron P: 17 parts by weight (0.5% by weight)
[Comparative Example 1-1]
A release layer was formed in the same manner as in Example 1-3, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows.
Water: 220 parts by mass X52-6015: 50 parts by mass (100% by mass)
CAT-PM-10A: 2 parts by mass (10.0% by mass)
Diethylene glycol: 5 parts by weight Vitron P: 0 parts by weight (0.0% by weight)
[Comparative Example 1-2]
Silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: TPR6700, toluene solution, solid content 30% by mass) containing polydimethylsiloxane as a main component in a solvent composed of 70 parts by mass of methyl ethyl ketone (MEK) and 30 parts by mass of toluene 10 parts dissolved, 0.2 parts by weight of catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: CM670) and 10 parts by weight of Vitron P were added. It was created.
MEK: 70 parts by mass Toluene: 30 parts by mass TPR6700: 10 parts by mass (100% by mass)
CM670: 0.2 mass part (6.7 mass%)
Vitron P: 10 parts by mass (4.3% by mass)
[Comparative Example 1-3]
The base film in Example 1-1 was used as it was. Evaluation was performed on the surface on the side not having the anchor coat layer.
In the table, aE + b represents a × 10 ^b .

[Example 2-1]
<Base film>
Manganese acetate is used as a transesterification catalyst, phosphorous acid is used as a stabilizer, antimony trioxide is used as a polymerization catalyst, and 0.06% by mass of silicon oxide particles (average particle size: 1.8 μm) is used as a lubricant. 23 ° C., o-chlorophenol solvent) polyethylene terephthalate pellets were dried, melted at a melting temperature of 280 to 300 ° C., and then extruded onto a rotary cooling drum having a surface temperature of 20 ° C. to obtain an unstretched film having a thickness of 520 μm.
The obtained unstretched film is preheated to a temperature of 75 ° C., then heated by an IR heater with a surface temperature of 800 ° C. from above 15 mm between low-speed and high-speed rolls, stretched 3.6 times in the machine direction, and rapidly cooled. Subsequently, the film was supplied to a transverse stretching machine and stretched 3.9 times in the transverse direction at a temperature of 120 ° C. The obtained biaxially oriented film was heat-set at a temperature of 230 ° C. for 5 seconds to obtain a heat-fixed biaxially oriented polyester film having a thickness of 38 μm. The obtained polyester film was subjected to corona treatment on one side.
<Release layer>
Emulsion of an addition reaction type silicone resin composition with respect to water (manufactured by Shin-Etsu Chemical Co., Ltd .: X52-6015, solid content 40% by mass, this silicone resin composition comprises a main agent and a crosslinking agent. Each of the agents contains —Si (CH ₃ ) ₂ O— units in the molecule in an amount exceeding 50 mol%.), Catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: CAT-PM-10A), diethylene glycol, and vitron P (polyethylenedioxythiophene 0.5% by mass, conductive polymer aqueous dispersion with 0.8% by mass polystyrene sulfonic acid added as a dopant, manufactured by Agfa Materials, solid content 1.3% by mass), Silicone resin emulsion (manufactured by Asahi Kasei Wacker Co., Ltd .: CRA92, solid content 50 mass%, this silicone resin is trifunctional Containing siloxane and / or tetrafunctional unit siloxane, and containing SiR ³ O _3/2 units and / or SiO ₂ units in a total amount exceeding 50 mol% in the molecule) After stirring to make a coating solution, the coating solution is applied to the surface of the polyester film obtained above subjected to corona treatment by a conventional roll coat, and at a drying temperature of 140 ° C. After drying for 60 seconds, a release layer having a dried film thickness of 0.8 μm was formed to obtain a release film. The properties of the obtained release film are shown in Table 2. In addition, the inside of the parenthesis in the following shows the mass ratio of the solid content of each component with respect to 100 mass% of solid content of a silicone resin composition.
Water: 18.6 parts by mass X52-6015: 2.2 parts by mass (100% by mass)
CAT-PM-10A: 0.11 parts by mass (12.5% by mass)
Diethylene glycol: 0.5 part by weight Vitron P: 3.0 part by weight (4.4% by weight)
CRA92: 6.6 parts by mass (375% by mass)
In addition, the mass ratio of the silicone resin in a release layer is 76.2 mass%.
[Example 2-2]
A release layer was formed in the same manner as in Example 2-1, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows to obtain a release film. The properties of the obtained release film are shown in Table 2.
Water: 18.7 parts by mass X52-6015: 2.0 parts by mass (100% by mass)
CAT-PM-10A: 0.1 part by mass (12.5% by mass)
Diethylene glycol: 0.5 parts by weight Vitron P: 3.0 parts by weight (4.9% by weight)
CRA92: 6.8 parts by mass (425% by mass)
In addition, the mass ratio of the silicone resin in a release layer is 78.4 mass%.
[Example 2-3]
The release layer was formed in the same manner as in Example 2-1, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows and the coating thickness after drying was 1.3 μm. And a release film was obtained. The properties of the obtained release film are shown in Table 2.
Water: 11.3 parts by mass X52-6015: 7.3 parts by mass (100% by mass)
CAT-PM-10A: 0.4 parts by mass (13.7% by mass)
Diethylene glycol: 0.5 parts by weight Vitron P: 3.0 parts by weight (1.3% by weight)
CRA92: 7.5 parts by mass (128.4% by mass)
In addition, the mass ratio of the silicone resin in a release layer is 52.8 mass%.
[Example 2-4]
The release layer was formed in the same manner as in Example 2-1, except that the mixing ratio of each component in the coating liquid for forming the release layer was as follows and the coating thickness after drying was 0.4 μm. And a release film was obtained. The properties of the obtained release film are shown in Table 2.
Water: 22.3 parts by mass X52-6015: 0.5 parts by mass (100% by mass)
CAT-PM-10A: 0.02 parts by mass (10% by mass)
Diethylene glycol: 0.5 parts by weight Vitron P: 3.0 parts by weight (19.5% by weight)
FZ-77: 0.1 parts by mass CRA92: 3.6 parts by mass (900% by mass)
In addition, the mass ratio of the silicone resin in a release layer is 87.4 mass%.
FZ-77 is a surfactant (manufactured by Toray Dow Corning).
[Comparative Example 2-1]
Silicone (manufactured by Shin-Etsu Chemical Co., Ltd .: TPR6700, toluene solution, solid content 30% by mass) containing polydimethylsiloxane as a main component in a solvent composed of 70 parts by mass of methyl ethyl ketone (MEK) and 30 parts by mass of toluene When 10 parts by mass was dissolved, 0.2 parts by mass of catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: CM670) was mixed, and 10 parts by mass of Vitron P and 10 parts by mass of CRA92 were added. The sample was prepared by coating.
MEK: 70 parts by mass Toluene: 30 parts by mass TPR6700: 10 parts by mass (100% by mass)
CM670: 0.2 mass part (6.7 mass%)
Vitron P: 10 parts by mass (4.3% by mass)
CRA92: 10 parts by mass (166.7% by mass)
In addition, the mass ratio of the silicone resin in a release layer is 60.0 mass%.
[Examples 2-5 to 2-14]
The same method as in Example 2-1 except that the mixing ratio of each component in the coating liquid for forming the release layer is as shown in Table 3 and the coating thickness after drying is as shown in Table 2. Thus, a release layer was formed to obtain a release film. The properties of the obtained release film are shown in Table 2.
In the table, aE + b represents a × 10 ^b .

Effect of the Invention According to the present invention, it is possible to provide a release film that is excellent in antistatic properties and release properties at the same time without separately providing an antistatic layer and a release layer.
According to the 1st aspect of this invention, it can be set as the peeling force of the wide range with antistatic property. In particular, since the inhibition of curing by the conductive polymer is suppressed, the peeling force in the light peeling force region can be obtained. Thereby, it can use suitably as a carrier sheet used for the use for the use for which light peeling is requested | required, for example, manufacture of the product which has an adhesion layer, various sheets, etc.
In addition, according to the second aspect of the present invention, it is possible to achieve the peel force in the middle peel force region or heavy peel force region as well as antistatic properties. Thereby, it can be suitably used as a release film (carrier film) on the heavy peeling side of an electronic material adhesive tape such as an anisotropic conductive adhesive film or a non-carrier film, where heavy peeling is required.

According to the present invention, it is possible to produce a release film having excellent release properties and antistatic properties by a single coating. Moreover, since the obtained film can be used suitably for manufacture of the product which has an adhesion layer, a carrier sheet for sheet formation, etc., the industrial applicability is high.

Claims (8)

A release film having a release layer on at least one side of a base film, the release layer comprising:
(I) a crosslinked silicone resin formed from an emulsion-based silicone resin composition, and (ii) a cationic polythiophene containing a repeating unit represented by the following formula (I) as a main component, and a polyanion. Release film containing a functional polymer as a constituent.

(In the above formula (I), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Alternatively, R ¹ and R ² are Represents an optionally substituted alkylene group having 1 to 12 carbon atoms.) The release film according to claim 1, wherein the content of the conductive polymer in the release layer is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition. . 3. A cation containing a silicone resin composition emulsion containing an emulsion-based silicone resin composition and a repeating unit represented by the formula (I) as a main component in producing the release film according to claim 1. A method for producing a release film, wherein a coating liquid obtained by mixing an aqueous dispersion of a conductive polymer containing a conductive polythiophene and a polyanion is applied to at least one surface of a base film and cured. The release film according to claim 1, wherein the emulsion-based silicone resin composition contains dimethylsiloxane as a main constituent. The cross-linked silicone resin has at least one structure selected from the group consisting of an emulsion-based silicone resin composition and a trifunctional unit siloxane and a tetrafunctional unit siloxane of 85% by mass or less based on the mass of the release layer. The release film according to claim 4, which is formed from an emulsion-based silicone resin. A release film having a release layer on at least one side of a base film, the release layer comprising:
(I) (i-1) an emulsion-based silicone resin composition containing dimethylsiloxane as a main constituent;
(I-2) Emulsions mainly comprising at least one structure selected from the group consisting of trifunctional unit siloxanes and tetrafunctional unit siloxanes in an amount of 65% by mass or more and 85% by mass or less based on the mass of the release layer. And (ii) a conductive polymer containing a cationic polythiophene containing a repeating unit represented by the above formula (I) as a main component and a polyanion. The release film according to claim 4, which is contained as a component. The release polymer according to claim 5 or 6, wherein the content of the conductive polymer in the release layer is 0.2% by mass or more and 20% by mass or less with respect to 100% by mass of the emulsion silicone resin composition. Mold film. In producing the release film according to claim 5 or 6, from a silicone resin composition emulsion containing an emulsion silicone resin composition containing dimethylsiloxane as a main constituent, a trifunctional unit siloxane and a tetrafunctional unit siloxane A silicone resin emulsion containing an emulsion-based silicone resin whose main constituent is at least one structure selected from the group consisting of: a cationic polythiophene and a polyanion containing as a main component a repeating unit represented by the above formula (I) A method for producing a release film, in which a coating liquid obtained by mixing an aqueous dispersion of a conductive polymer containing is applied to at least one surface of a base film and cured.