JP6201937B2 - Release paper or silicone composition for release film, release paper and release film - Google Patents

Description

  The present invention relates to a silicone composition suitable for producing a release paper and a release film excellent in an effect of suppressing heavy peeling due to exposure to the atmosphere (hereinafter referred to as exposure resistance). A silicone composition capable of maintaining good release characteristics even when the coated surface of the silicone release paper and release film produced by applying the product is exposed to the atmosphere, and a cured film of the composition is formed. The present invention relates to a release paper and release film.

  Release films and release papers are widely used as release films for adhesive or adhesive substances by applying a silicone release agent to the surface of a substrate such as plastic film or paper and forming a cured film by a crosslinking reaction. ing.

  As such a curable organopolysiloxane composition, an addition reaction curing in which a vinyl group-containing organopolysiloxane and an organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom as main components are cured by a hydrosilylation reaction. Mold release compositions are well known, and are widely used as release compositions because of their advantages such as fast curing speed and various changes in release characteristics. However, it has been pointed out that the addition reaction curable peeling composition has a phenomenon that when the film obtained by curing is exposed to the outside air, the peeling force becomes abnormally heavy, and in some cases, it cannot be peeled off. Therefore, in the process of manufacturing labels and adhesive tapes using release paper and release film with release agent film formed using addition reaction curable release composition, silicone coating film is exposed to the atmosphere. If this is done, the releasability required for these products cannot be maintained, resulting in poor peel and a significant degradation in quality.

  In order to solve this problem, a method of blending an alcohol-modified organopolysiloxane or a polyether-modified organopolysiloxane with an addition reaction curable release composition (Japanese Patent Laid-Open No. 55-3460: Patent Document 1), In addition, as a part of the organohydrogenpolysiloxane, a method (JP-A-1-217068: Patent Document 2) in which a compound having a hydrosilyl group only at one terminal silicon atom has been reported. However, although these methods have an effect of suppressing the phenomenon of heavy peeling due to exposure to the atmosphere, they are not sufficient. There was also a disadvantage of reducing the residual adhesive strength of the adhesive layer.

  In Japanese Patent No. 2934118 (Patent Document 3), a method for specifying the structure of a crosslinking agent is shown. Although the decrease in the residual adhesive force is improved, the effect on other peeling characteristics such as a heavy peeling force is exhibited. Was a big one.

Japanese Patent Laid-Open No. 55-3460 Japanese Laid-Open Patent Application No. 1-217068 Japanese Patent No. 2934118

  The present invention has been made in view of the above circumstances, and is an addition-reaction curing type peeling that suppresses the transferability of the release agent and gives a release agent film having an exposure resistance without adversely affecting the residual adhesive force and release force. An object is to provide a silicone composition for paper or a release film, and a release paper and a release film on which a cured film of the composition is formed.

  As a result of intensive studies to achieve the above object, the present inventor has added an alkene and alkadiene having an unsaturated bond at the terminal and an alkenyl group having an unsaturated bond at the terminal to the addition reaction curable silicone composition. By incorporating a specific amount of one or more compounds selected from silane and disiloxane, the release agent has a resistance to exposure without inhibiting the migration of the release agent and adversely affecting the residual adhesive force and release force. A release paper or release film silicone composition that gives a film is obtained, and the release paper and release film on which a cured film of the composition is formed are excellent in exposure resistance and peelability, and on the release paper and release film. It has been found that even if the formed cured film is exposed to air for a long time, the peelability before the exposure can be substantially maintained, and the present invention has been made.

（式中、Ｒ¹は独立にアルケニル基であり、Ｒ²は独立に脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｘ¹は独立に下記一般式（２−１）、Ｘ²は独立に下記一般式（２−２）、Ｘ³は独立に下記一般式（２−３）

で示される基であり、Ｘ⁴はそれぞれ独立に下記一般式（３−１）、Ｘ⁵はそれぞれ独立に下記一般式（３−２）、Ｘ⁶はそれぞれ独立に下記一般式（３−３）

で示される基である。Ｒ¹、Ｒ²は上記の通りであり、ａ１、ａ２、ａ１１、ａ２１、ａ３１、ａ４１、ａ５１、ａ６１はそれぞれ独立に０〜３の整数である。ａ３は正数、ａ４〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２、ａ６３は０又は正数で、これらはオルガノポリシロキサンの２５℃での粘度を０．０５Ｐａ・ｓ以上３０質量％トルエン希釈粘度で７０Ｐａ・ｓ以下の範囲とするように選ばれる。）
（Ｂ）下記一般式（５）で示される両末端に不飽和結合を有する炭素数１０〜３２のアルカジエン、下記一般式（６）で示される末端に不飽和結合を有する炭素数８〜３０のアルケニル基を１〜４個有するシラン、及び下記一般式（７）で示される末端に不飽和結合を有する炭素数８〜３０のアルケニル基を２〜６個有するジシロキサンから選ばれる１種以上の化合物：５〜２０質量部、
ＣＨ₂＝ＣＨ−Ｒ³−ＣＨ＝ＣＨ₂ （５）
(ＣＨ₂＝ＣＨ−Ｒ³）_b1ＳｉＲ⁴ _4-b1 （６）

（式中、Ｒ³はそれぞれ独立に炭素数６〜２８の二価炭化水素基であり、Ｒ⁴は独立に炭素数１〜１０の一価炭化水素基又は炭化水素オキシ基であり、ｂ１は１〜４の整数、ｂ２は独立に１〜３の整数である。）
（Ｃ）下記平均組成式（８）
Ｒ² _c1Ｈ_c2ＳｉＯ_(4-c1-c2)/2 （８）
（式中、Ｒ²は独立に脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、ｃ１は０．１〜２の正数、ｃ２は０．０１〜２の正数で、ｃ１＋ｃ２は３以下の正数であり、１分子中に２個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。）
で示され、１分子中に少なくとも２個のケイ素原子に結合した水素原子を有するオルガノハイドロジェンポリシロキサンであって、Ｒ ² ₂ ＨＳｉＯ _1/2 単位（Ｒ ² は脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基である）を１分子中に２個以上有するオルガノハイドロジェンポリシロキサンであるか、又は該オルガノハイドロジェンポリシロキサンを一部含む混合物：（Ｃ）成分中のケイ素原子に結合した水素原子のモル数が、（Ａ）及び（Ｂ）成分中のアルケニル基及び不飽和基の合計モル数の１〜２０倍に相当する量、
（Ｄ）触媒量の白金族金属系触媒、
（Ｅ）有機溶剤：０〜１００，０００質量部
を含む付加反応硬化型の剥離紙又は剥離フィルム用シリコーン組成物。
〔２〕
（Ｃ）成分が、下記一般式（９）及び／又は下記一般式（１０）で示されるオルガノハイドロジェンポリシロキサンであることを特徴とする〔１〕記載の剥離紙又は剥離フィルム用シリコーン組成物。

（式中、Ｍｅはメチル基であり、Ｒ²は独立に脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｒ⁵はそれぞれ独立に水素原子又は脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｒ⁶及びＲ⁷はそれぞれ独立に脂肪族不飽和結合を含有しないＭｅ以外の非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｙ³はそれぞれ独立に下記一般式（１１−１）、Ｙ⁴はそれぞれ独立に下記一般式（１１−２）、Ｙ⁵はそれぞれ独立に下記一般式（１１−３）

で示される基であり、Ｙ⁶はそれぞれ独立に下記一般式（１２−１）、Ｙ⁷はそれぞれ独立に下記一般式（１２−２）、Ｙ⁸はそれぞれ独立に下記一般式（１２−３）

で示される基であり、Ｒ⁵、Ｒ⁶、Ｒ⁷は上記の通りであり、ｃ１１、ｃ１２、ｃ３１、ｃ４１、ｃ５１、ｃ６１、ｃ７１、ｃ８１はそれぞれ独立に０〜３の整数、ｃ２３は２以上の整数、ｃ１３〜ｃ１９、ｃ２４〜ｃ２９、ｃ３２〜ｃ３８、ｃ４２〜ｃ４８、ｃ５２〜ｃ５８、ｃ６２〜ｃ６６、ｃ７２〜ｃ７６、ｃ８２〜ｃ８６は０以上の整数、ｃ２３＋ｃ２４＋ｃ２５＋ｃ２６＋ｃ２７＋ｃ２８＋ｃ２９は３以上の整数であって、１分子中に２個以上のケイ素原子に結合した水素原子を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。）
〔３〕
（Ｃ）成分が、（Ｃ１）芳香族置換基を含有しないオルガノハイドロジェンポリシロキサンと、（Ｃ２）芳香族置換基を含有するオルガノハイドロジェンポリシロキサンとの混合物であり、これら（Ｃ１）及び（Ｃ２）成分の質量比（Ｃ１）／（Ｃ２）が１／９〜９／１であることを特徴とする〔１〕又は〔２〕記載の剥離紙又は剥離フィルム用シリコーン組成物。
〔４〕
更に、（Ｆ）成分として、下記一般式（１３）で示されるオルガノポリシロキサンを（Ａ）成分１００質量部に対して０．１〜３０質量部含有する〔１〕〜〔３〕のいずれかに記載の剥離紙又は剥離フィルム用シリコーン組成物。

（式中、Ｍｅはメチル基であり、Ｒ⁸は独立に水酸基、アルコキシ基又はアルコキシアルキル基であり、Ｒ⁹は独立に水酸基、アルコキシ基、アルコキシアルキル基及び脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｒ¹⁰は独立に水酸基、アルコキシ基、アルコキシアルキル基及び脂肪族不飽和結合を含有しないＭｅ以外の非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、ｆ１、ｆ２は１〜３の整数であり、ｆ３〜ｆ５はオルガノポリシロキサンの２５℃での粘度を１Ｐａ・ｓ以上３０質量％トルエン希釈粘度で１００Ｐａ・ｓ以下の範囲に入るように選ばれる整数である。）
〔５〕
更に、（Ｇ）成分として、少なくとも２個のアルケニル基を有し、Ｒ² _(3-g1)Ｒ¹ _g1ＳｉＯ_1/2シロキサン単位（Ｍ^R1R2単位）、Ｒ²ＳｉＯ_3/2シロキサン単位（Ｔ^R2単位）（式中、Ｒ¹は独立にアルケニル基であり、Ｒ²は独立に脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、ｇ１は１〜３の整数である。）を必須単位とし、Ｍ^R1R2単位／Ｔ^R2単位のモル比が２／８〜８／２を満たし、２５℃での粘度が０．００１〜１Ｐａ・ｓの範囲を有する、分子末端がＭ^R1R2単位、又はＭ^R1R2単位と一部がシラノール基もしくはアルコキシ基であるオルガノポリシロキサンを（Ａ）成分１００質量部に対して１０〜１００質量部含有する〔１〕〜〔４〕のいずれかに記載の剥離紙又は剥離フィルム用シリコーン組成物。
〔６〕
更に、（Ｈ）成分として、１分子中に少なくともエポキシ基とアルコキシシリル基を有する下記一般式（１４）で示されるオルガノシラン及び／又は下記平均組成式（１５）で示されるその部分加水分解（共）縮合シロキサンを（Ａ）成分１００質量部に対して０．１〜１０質量部含有する〔１〕〜〔５〕のいずれかに記載の剥離紙又は剥離フィルム用シリコーン組成物。
Ｒ¹¹ _h1（ＯＲ¹²）_h2Ｓｉ（Ｒ¹³）_(4-h1-h2) （１４）
Ｒ¹¹ _h3（ＯＲ¹²）_h4（Ｒ¹³）_h5ＳｉＯ_{(4-h3-h4-h5)/2} （１５）
（式中、Ｒ¹¹はエポキシ基を含有する一価有機基であり、Ｒ¹²は炭素数１〜６のアルキル基で、エーテル結合を含んでもよく、一部は加水分解されて水酸基となっていてもよい。Ｒ¹³は非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基である。ｈ１、ｈ２は整数で１≦ｈ１、１≦ｈ２、２≦ｈ１＋ｈ２≦４を満たし、ｈ３〜ｈ５は正数で０＜ｈ３、０＜ｈ４、０≦ｈ５、１＜ｈ３＋ｈ４＋ｈ５≦３を満たし、部分加水分解（共）縮合シロキサンの２５℃での粘度を０．００１〜１Ｐａ・ｓの範囲とする正の数から選ばれる。）
〔７〕
更に、（Ｉ）成分として、下記一般式（１６）で示されるシロキサン単位（Ｍ単位）と下記式（１７）で示されるシロキサン単位（Ｑ単位）とをモル比（Ｍ単位／Ｑ単位）で２／８〜８／２としたＭＱレジンを（Ａ）成分１００質量部に対して１〜１００質量部含有する〔１〕〜〔６〕のいずれかに記載の剥離紙又は剥離フィルム用シリコーン組成物。
Ｒ² _(3-i1)Ｒ¹ _i1ＳｉＯ_1/2 （１６）
ＳｉＯ_4/2 （１７）
（式中、Ｒ¹は独立にアルケニル基であり、Ｒ²は独立に脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、ｉ１は０〜３の整数である。）
〔８〕
更に、（Ｊ）成分として、ノニオン性界面活性剤を（Ａ）成分１００質量部に対して０．１〜５質量部含有する〔１〕〜〔７〕のいずれかに記載の剥離紙又は剥離フィルム用シリコーン組成物。
〔９〕
〔１〕〜〔８〕のいずれかに記載の剥離紙又は剥離フィルム用シリコーン組成物の硬化皮膜が形成された剥離紙又は剥離フィルム。 Accordingly, the present invention provides the following release paper or release film silicone composition, release paper and release film.
[1]
(A) Organopolysiloxane represented by the following general formula (1) and having at least two alkenyl groups in one molecule: 100 parts by mass

Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X ¹ is independently The following general formula (2-1), X ² is independently the following general formula (2-2), X ³ is independently the following general formula (2-3)

X ⁴ is each independently the following general formula (3-1), X ⁵ is each independently the following general formula (3-2), and X ⁶ is each independently the following general formula (3-3). )

It is group shown by these. R ¹ and R ² are as described above, and a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3. a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, a63 is 0 or a positive number, and these are the viscosity of the organopolysiloxane at 25 ° C. In the range of 0.05 Pa · s or more and 30% by mass toluene diluted viscosity of 70 Pa · s or less. )
Carbon atoms having (B) under following general formula (5) alkadienes 10 to 32 carbon atoms and having an unsaturated bond at both terminals represented, the unsaturated bond at the terminal represented by the following general formula (6) 8-30 One or more selected from silanes having 1 to 4 alkenyl groups and disiloxanes having 2 to 6 alkenyl groups having 8 to 30 carbon atoms having an unsaturated bond at the terminal represented by the following general formula (7) Compound: 5-20 parts by mass,
^{_{C H 2 = CH-R 3}} -CH = CH 2 (5)
^{_{(CH 2 = CH-R 3}} ) b1 SiR 4 4-b1 (6)

(Wherein R ³ is each independently a divalent hydrocarbon group having 6 to 28 carbon atoms, R ⁴ is independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 10 carbon atoms, b1 is An integer of 1 to 4, b2 is an integer of 1 to 3 independently.)
(C) The following average composition formula (8)
R ² _c1 H _c2 SiO _{(4-c1-c2) / 2} (8)
(In the formula, R ² independently represents a monovalent hydrocarbon group which is unsubstituted or does not contain an aliphatic unsaturated bond, or is substituted with a halogen atom or a cyano group, c1 is a positive number of 0.1 to 2, and c2 is 0.8. It is a positive number of 01 to 2, c1 + c2 is a positive number of 3 or less, has 2 or more SiH groups in one molecule, and has a viscosity at 25 ° C. in the range of 0.005 to 10 Pa · s. To be elected.)
An organohydrogenpolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule , wherein R ² ₂ HSiO _1/2 units (R ² does not contain an aliphatic unsaturated bond) (A non-substituted or halogen atom or cyano group-substituted monovalent hydrocarbon group) having two or more per molecule, or a mixture partially containing the organohydrogen polysiloxane : C) An amount corresponding to 1 to 20 times the total number of moles of alkenyl groups and unsaturated groups in the components (A) and (B), wherein the number of moles of hydrogen atoms bonded to silicon atoms in the component;
(D) a catalytic amount of a platinum group metal catalyst,
(E) Organic solvent: addition reaction curable type release paper or release film silicone composition containing 0 to 100,000 parts by mass.
[2]
The silicone composition for release paper or release film according to [1], wherein the component (C) is an organohydrogenpolysiloxane represented by the following general formula (9) and / or the following general formula (10): .

(In the formula, Me is a methyl group, R ² is an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group independently containing no aliphatic unsaturated bond, and R ⁵ is independently a hydrogen atom. Or an unsubstituted or unsubstituted monovalent hydrocarbon group substituted with a halogen atom or a cyano group, wherein R ⁶ and R ⁷ are each independently an unsubstituted group other than Me that does not contain an aliphatic unsaturated bond, or A monovalent hydrocarbon group substituted with a halogen atom or a cyano group, Y ³ is each independently the following general formula (11-1), Y ⁴ is each independently the following general formula (11-2), and Y ⁵ is each independently The following general formula (11-3)

Y ⁶ is each independently the following general formula (12-1), Y ⁷ is each independently the following general formula (12-2), and Y ⁸ is each independently the following general formula (12-3) )

R ⁵ , R ⁶ and R ⁷ are as described above, c11, c12, c31, c41, c51, c61, c71 and c81 are each independently an integer of 0 to 3, c23 is 2 C13-c19, c24-c29, c32-c38, c42-c48, c52-c58, c62-c66, c72-c76, c82-c86 are integers greater than or equal to 0, c23 + c24 + c25 + c26 + c27 + c28 + c29 is an integer greater than or equal to 3. One molecule has hydrogen atoms bonded to two or more silicon atoms, and the viscosity at 25 ° C. is selected in the range of 0.005 to 10 Pa · s. )
[3]
Component (C) is a mixture of (C1) an organohydrogenpolysiloxane containing no aromatic substituent and (C2) an organohydrogenpolysiloxane containing an aromatic substituent, and these (C1) and (C The silicone composition for release paper or release film according to [1] or [2] , wherein the mass ratio (C1) / (C2) of component C2) is from 1/9 to 9/1.
[4]
Furthermore, as component (F), any one of [1] to [ 3 ] containing 0.1 to 30 parts by mass of organopolysiloxane represented by the following general formula (13) with respect to 100 parts by mass of component (A) The silicone composition for release paper or release film described in 1.

(In the formula, Me is a methyl group, R ⁸ is independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group, and R ⁹ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and a non-aliphatic unsaturated bond. A substituted or halogen atom or a cyano group-substituted monovalent hydrocarbon group, and R ¹⁰ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an unsubstituted or halogen atom or cyano group other than Me containing no aliphatic unsaturated bond It is a substituted monovalent hydrocarbon group, f1 and f2 are integers of 1 to 3, and f3 to f5 are the viscosity of organopolysiloxane at 25 ° C. of 1 Pa · s or more and 30% by mass in toluene diluted viscosity of 100 Pa · s. (An integer chosen to fall within the following range.)
[5]
Furthermore, as component (G), it has at least two alkenyl groups, and R ² _(3-g1) R ¹ _g1 SiO _1/2 siloxane unit (M ^R1R2 unit), R ² SiO _3/2 siloxane unit (T ^R2 unit) (wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, and g1 is Is an integer of 1 to 3)), the molar ratio of M ^R1R2 units / TR ² units satisfies 2/8 to 8/2, and the viscosity at 25 ° C. is in the range of 0.001 to 1 Pa · s. 10 to 100 parts by mass of an organopolysiloxane having a molecular end of M ^R1R2 unit, or M ^R1R2 unit and a part of which is a silanol group or an alkoxy group is contained in 100 parts by mass of component (A). [4] for release paper or a release film according to any one of Recone composition.
[6]
Furthermore, as the component (H), organosilane represented by the following general formula (14) having at least an epoxy group and an alkoxysilyl group in one molecule and / or partial hydrolysis thereof represented by the following average composition formula (15) ( The silicone composition for release paper or release film according to any one of [1] to [ 5 ], comprising 0.1 to 10 parts by mass of (co) condensed siloxane with respect to 100 parts by mass of component (A).
R ¹¹ _{h 1} (OR ¹² ) _{h 2} Si (R ¹³ ) _{(4-h 1 -h 2)} (14)
_{^{R 11 h3 (OR 12) h4}} (R 13) h5 SiO (4-h3-h4-h5) / 2 (15)
(In the formula, R ¹¹ is a monovalent organic group containing an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms and may contain an ether bond, and some of them are hydrolyzed to become a hydroxyl group. R ¹³ is an unsubstituted or monovalent hydrocarbon group substituted with a halogen atom or a cyano group, h1 and h2 are integers satisfying 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, and h3 to h5 Is a positive number satisfying 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, and the partially hydrolyzed (co) condensed siloxane has a viscosity at 25 ° C. in the range of 0.001 to 1 Pa · s. (Selected from positive numbers.)
[7]
Furthermore, as a component (I), a siloxane unit (M unit) represented by the following general formula (16) and a siloxane unit (Q unit) represented by the following formula (17) are used in a molar ratio (M unit / Q unit). The silicone composition for release paper or release film according to any one of [1] to [ 6 ], comprising 1 to 100 parts by weight of MQ resin having 2/8 to 8/2 per 100 parts by weight of component (A). object.
R ² _(3-i1) R ¹ _i1 SiO _1/2 (16)
SiO _4/2 (17)
Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and i1 is 0 to 3 Is an integer.)
[8]
The release paper or release according to any one of [1] to [ 7 ], further comprising 0.1 to 5 parts by mass of a nonionic surfactant as component (J) with respect to 100 parts by mass of component (A). Silicone composition for film.
[9]
A release paper or release film on which a cured film of the silicone composition for release paper or release film according to any one of [1] to [ 8 ] is formed.

  The release agent and release film of the present invention are excellent in exposure resistance and peelability. The release paper and release film obtained by applying and curing the release paper or release film silicone composition of the present invention can substantially maintain the peelability before exposure even when the silicone coated surface is exposed to air for a long time.

  The present invention is described in detail below. In the present invention, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, and Vi is a vinyl group.

[Silicone composition for release paper or release film]
The silicone composition for release paper or release film of the present invention is an addition reaction curable type silicone composition containing the following components (A) to (D) and optionally (E) to (J), and an addition reaction. It is hardened by.

Component (A) The organopolysiloxane of component (A) constituting the addition reaction curable silicone composition of the present invention has a structure represented by the following general formula (1), and has at least two in one molecule. It has an alkenyl group.

（式中、Ｒ¹は独立にアルケニル基であり、Ｒ²は独立に脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｘ¹は独立に下記一般式（２−１）、Ｘ²は独立に下記一般式（２−２）、Ｘ³は独立に下記一般式（２−３）

で示される基であり、Ｘ⁴はそれぞれ独立に下記一般式（３−１）、Ｘ⁵はそれぞれ独立に下記一般式（３−２）、Ｘ⁶はそれぞれ独立に下記一般式（３−３）

で示される基である。Ｒ¹、Ｒ²は上記の通りであり、ａ１、ａ２、ａ１１、ａ２１、ａ３１、ａ４１、ａ５１、ａ６１はそれぞれ独立に０〜３の整数である。ａ３は正数、ａ４〜ａ６、ａ１２〜ａ１５、ａ２２〜ａ２５、ａ３２〜ａ３５、ａ４２、ａ４３、ａ５２、ａ５３、ａ６２、ａ６３は０又は正数で、これらはオルガノポリシロキサンの２５℃での粘度を０．０５Ｐａ・ｓ以上３０質量％トルエン希釈粘度で７０Ｐａ・ｓ以下の範囲とするように選ばれる。）

Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X ¹ is independently The following general formula (2-1), X ² is independently the following general formula (2-2), X ³ is independently the following general formula (2-3)

X ⁴ is each independently the following general formula (3-1), X ⁵ is each independently the following general formula (3-2), and X ⁶ is each independently the following general formula (3-3). )

It is group shown by these. R ¹ and R ² are as described above, and a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3. a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, a63 is 0 or a positive number, and these are the viscosity of the organopolysiloxane at 25 ° C. In the range of 0.05 Pa · s or more and 30% by mass toluene diluted viscosity of 70 Pa · s or less. )

In the above formula (1), R ¹ is an alkenyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, such as the same or different vinyl group, allyl group, propenyl group, etc., and R ¹ is a vinyl group. It is industrially preferable.

R ² is an unsubstituted or substituted monovalent hydrocarbon group that does not contain the same or different aliphatic unsaturated bonds, and is an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a cycloalkyl group such as a cyclohexyl group. Group, phenyl group, aryl group such as tolyl group or the like, or chloromethyl in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, bromine or cyano groups An unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond having preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a group, trifluoropropyl group, cyanoethyl group, etc. it can. From the viewpoint of production and characteristics, it is preferable that R ² is 80 mol% or more of a methyl group or a phenyl group, and more preferably 40 mol% or more, particularly 50 mol% or more of R ² is a methyl group, and 40 mol% or less. Is preferably a phenyl group.

  There are two or more alkenyl groups in one molecule of the organopolysiloxane of the component (A), and if it is less than two, there is a high possibility that uncrosslinked molecules remain after curing, and the curing property is lowered, which is not desirable. Desirably, the alkenyl group content per 100 g of organopolysiloxane is 0.001 to 0.5 mol, and more desirably 0.002 to 0.45 mol. If this content is less than 0.001 mol, the curability may be lowered, and if it exceeds 0.5 mol, the pot life may be shortened and handling may be difficult.

  In the above formula (1), the number of alkenyl groups in one molecule is preferably 2 to 300, particularly 3 to 280. In this case, the number of alkenyl groups is calculated from [a1 + a2 + a4 + a5 × {a11 + a13 + a14 × (a41 + a43) + a15 × (a51 + a53 + a61 + a63)} + a6 × {a21 + a23 + a31 + a33 + (a24 + a34) × (a41 + a43) + (a25 + a51) × (+ 25 + a51) ×

In the above formula (1), a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3.
Further, in the above formula (1), a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, a63 are 0 or a positive number. It is a positive number that satisfies the viscosity described later.

  The viscosity of the organopolysiloxane (A) at 25 ° C. is in the range of 0.05 Pa · s to 30% by mass toluene diluted viscosity, preferably 70 Pa · s or less, preferably 0.1 Pa · s to 30% by mass in toluene. The viscosity is in the range of 60 Pa · s or less. If the viscosity is less than 0.05 Pa · s, the releasability is not sufficient, and if it exceeds 70 Pa · s with a 30% by weight toluene diluted viscosity, the workability is lowered. Here, the viscosity can be measured with a rotational viscometer (hereinafter the same).

  In the above formula (1), the degree of polymerization is preferably selected to be in the range of 50 to 20,000, particularly 55 to 19,000. In this case, the degree of polymerization is [2 + a3 + a4 + a5 × {2 + a12 + a13 + a14 × (2 + a42 + a43) + a15 × (3 + a52 + a53 + a62 + a63)} + a6 × {3 + a22 + a23 + a32 + a33 + (a24 + a34) × (2 + a42 + 63 +) + (3 × 25 + 63 ++)

  The main skeleton structure of the (A) component organopolysiloxane is a linear structure as shown in the formula (1) when a5 and a6 are 0, or in the formula (1), a5 and / or a6 is It is a branched chain structure as shown in the case where it is not 0.

Specific examples of the component (A) include the following.
Me ₂ ViSiO- (Me ₂ SiO) ₁₀₀₀ -SiViMe ₂
MeVi ₂ SiO— (Me ₂ SiO) ₅₀₀ —SiVi ₂ Me
Vi ₃ SiO— (Me ₂ SiO) ₂₀₀₀ —SiVi ₃
Me ₂ ViSiO- (Me ₂ SiO) ₉₉₀₀ (MeViSiO) ₁₀₀ -SiViMe ₂

(B) Component The (B) component of the present invention is blended as one of the components for improving the exposure resistance, and has 8 carbon atoms having an unsaturated bond at the terminal represented by the following general formula (4). -30 alkenes, alkadienes having 10 to 32 carbon atoms having unsaturated bonds at both ends represented by the following general formula (5), and 8 to 8 carbon atoms having unsaturated bonds at the terminals represented by the following general formula (6) Silane having 1 to 4 alkenyl groups, particularly 1 to 3 alkenyl groups, and 2 to 6 alkenyl groups having 8 to 30 carbon atoms having an unsaturated bond at the terminal represented by the following general formula (7), One or more compounds selected from 2 to 4 disiloxanes are used.

（式中、Ｒ³はそれぞれ独立に炭素数６〜２８の二価炭化水素基であり、Ｒ⁴は独立に炭素数１〜１０の一価炭化水素基又は炭化水素オキシ基であり、ｂ１は１〜４の整数、ｂ２は独立に１〜３の整数である。） ^{_{CH 2 = CH-R 3 -H}} (4)
^{_{CH 2 = CH-R 3 -CH}} = CH 2 (5)
^{_{(CH 2 = CH-R 3}} ) b1 SiR 4 4-b1 (6)

(Wherein R ³ is each independently a divalent hydrocarbon group having 6 to 28 carbon atoms, R ⁴ is independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 10 carbon atoms, b1 is An integer of 1 to 4, b2 is an integer of 1 to 3 independently.)

In the above formulas (4) to (7), R ³ is a divalent hydrocarbon group having 6 to 28 carbon atoms, preferably 6 to 24 carbon atoms. Hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene Group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group, eicosamethylene group, docosamethylene group, Alkylene group such as tetracosamethylene group, hexacosamethylene group, octacosamethylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cyclododecylene group, cyclotetradecylene group, cyclohexadecylene group , Cyclooctadecylene group, cycloeicosile Cycloalkylene group such as a phenylene group, tolylene group, xylylene group, trimethyl phenylene group, a naphthylene group, an arylene group such as biphenylene, methylene phenylene group, an aralkylene group such as methylene-phenylene-methylene group.

R ⁴ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms or a hydrocarbon oxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Preferred are those which do not contain a group unsaturated bond, for example, methyl groups, ethyl groups, propyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups, octyl groups and other alkyl groups, cyclohexyl Cycloalkyl group such as a group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, etc., and as hydrocarbon oxy group For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy Group, pentyloxy group, hexyloxy group, Sepuchiruokishi group, octyloxy group, methoxyethyl group, methoxybutyl group, ethoxyethyl group, an ethoxy butyl group, ethoxyhexyl group, propoxybutyl group, butoxybutyl group.

  b1 is an integer of 1 to 4, preferably 1 to 3, and b2 is an integer of 1 to 3, preferably 1 or 2.

  Specific examples of the alkene represented by the formula (4) include 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene and 1-octadecene. 1-eicosene, 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene and the like.

  Specific examples of the alkadiene represented by the formula (5) include 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,15-hexadecadiene, 1 , 17-octadecadien, 1,19-eicosadiene, 1,21-docosadiene, 1,3-tetracosadien, 1,25-hexacosadiene, 1,27-octacosadiene, 1,29-triacontadiene, and the like.

As the silane represented by the formula (6), specifically,
_{CH 2 = CH- (CH 2)} 6 -Si (CH 3) 3,
_{CH 2 = CH- (CH 2)} 8 -Si (CH 3) 3,
_{CH 2 = CH- (CH 2)} 6 -Si (C 3 H 7) 3,
_{CH 2 = CH- (CH 2)} 6 -Si (CH 3) 2 OCH 3,
_{CH 2 = CH- (CH 2)} 6 -Si (CH 3) (OCH 3) 2,
_{[CH 2 = CH- (CH 2} ) 6] 2 Si (CH 3) 2,
_{CH 2 = CH- (CH 2)} 12 -Si (CH 3) 3
Etc.

などが挙げられる。 Specifically, as the disiloxane represented by the formula (7),

Etc.

  The structure of the alkenyl compound of component (B), which has a low or no Si content, suppresses volatility by using a relatively high molecular weight compound, most of which forms chemical bonds in the cured film. As well as forming a bias in the dispersion state of component (B) in the cured film formed by crosslinking of component (A), which is the main component, for example, a tendency to separate light and shade near the surface and inside the film It is presumed to have an effect as shown. Probably, the effect of improving the exposure resistance appears by forming a portion having a high hydrocarbon group concentration. In addition, the blending of these alkenyl compounds hardly affects the peeling characteristics, and is also suitable as a technique for preventing heavy peeling, residual adhesive strength reduction, transferability, and the like.

  (B) The compounding quantity of a component is 5-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 7-18 mass parts. If it is less than 5 parts by mass, the effect of improving the exposure resistance of the cured film of the composition is insufficient, and if it exceeds 20 parts by mass, the curing property is lowered.

Component (C) The organohydrogenpolysiloxane which is the component (C) of the present invention has at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and is represented by the following average composition formula (8): It is shown.
R ² _c1 H _c2 SiO _{(4-c1-c2) / 2} (8)
(Wherein R ² is the same as above, c1 is a positive number of 0.1 to 2, c2 is a positive number of 0.01 to 2, c1 + c2 is a positive number of 3 or less, and It has two or more SiH groups and is selected so that the viscosity at 25 ° C. falls within the range of 0.005 to 10 Pa · s.)

In the above formula (8), R ² can be exemplified monovalent hydrocarbon group not containing a similar aliphatic unsaturated bonds and R ² in the formula (1), a methyl group. Among these, an ethyl group, a propyl group, An alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group are preferred.
C1 is a positive number of 0.1 to 2, preferably 0.2 to 2, c2 is 0.01 to 2, preferably 0.04 to 1.5, and more preferably 0.1 to 1. And c1 + c2 is a positive number of 3 or less, preferably 0.5 to 3, more preferably 1 to 3, having 2 or more SiH groups in one molecule, and a viscosity at 25 ° C. of 0.005 to 0.005. It is selected to be in the range of 10 Pa · s, preferably in the range of 0.01 to 10 Pa · s. When the viscosity is out of the range, curability is lowered.

  In the organohydrogenpolysiloxane of component (C), the number of hydrogen atoms bonded to silicon atoms in one molecule is 2 or more, preferably 3 to 1,000. If it is less than 2, the curability is insufficient. Desirably, the SiH group content per 100 g of organohydrogenpolysiloxane is 0.1 to 1.7 mol, preferably 0.2 to 1.7 mol, and more preferably 0.3 to 1.7 mol. Is a mole. If the content is too small, the curability may be insufficient, and if the content is too large, the storage stability may decrease.

  The viscosity at 25 ° C. of the organohydrogenpolysiloxane of component (C) is preferably in the range of 0.005 to 10 Pa · s, more preferably in the range of 0.005 to 5 Pa · s. If the viscosity is too small, the curability may be insufficient, and if it is too high, the storage stability may be insufficient.

  Further, the molecular structure of the component (C) may be any of linear, branched or cyclic, and may be a combination of these, or a mixture of them may be used.

As the compound represented by the formula (8), specifically, a linear methylhydrogensiloxane which is a polymer composed of Me ₃ SiO _1/2 and Me (H) SiO _2/2 siloxane units; Me ₂ (H ) Linear methyl hydrogen siloxane which is a polymer composed of SiO _1/2 , Me (H) SiO _2/2 and Me ₂ SiO _2/2 siloxane units; Me ₃ SiO _1/2 , Me (H) SiO _{2 / 2} and MePhSiO _2/2 polymer consisting of linear methylphenylhydrogensiloxane; from Me ₂ (H) SiO _1/2 , Me (H) SiO _2/2 and Ph ₂ SiO _2/2 siloxane units comprising polymer a is straight-chain methyl phenyl _{siloxane; Me 3 SiO 1/2, Me (} H) of the branch is a polymer consisting of SiO _2/2 and MeSiO _3/2 siloxane units methylhydrogensiloxane white San _{siloxane; Me 2 (H) SiO 1/2} , Me (H) SiO 2/2, Ph 2 SiO 2/2 and PhSi [theta] _3/2 branch a polymer consisting of siloxane units of methyl phenyl siloxane; Me (H) Cyclic methyl hydrogen siloxane which is a polymer composed only of SiO _2/2 siloxane units; Cyclic methyl hydro siloxane which is a polymer composed of Me ₂ SiO _2/2 and Me (H) SiO _2/2 siloxane units Gensiloxane; cyclic methylphenylhydrogensiloxane which is a polymer composed of MePhSiO _2/2 and Me (H) SiO _2/2 siloxane units.

  More preferably, the component (C) is an organohydrogenpolysiloxane having a linear or branched structure represented by the following general formula (9) and / or an organohydrogen having a cyclic structure represented by the following general formula (10). It may be a polysiloxane, or an organohydrogenpolysiloxane in which a linear structure and a cyclic structure are simultaneously contained in one molecule.

（式中、Ｒ²は上記と同じであり、Ｒ⁵はそれぞれ独立に水素原子又は脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｒ⁶及びＲ⁷はそれぞれ独立に脂肪族不飽和結合を含有しないＭｅ以外の非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｙ³はそれぞれ独立に下記一般式（１１−１）、Ｙ⁴はそれぞれ独立に下記一般式（１１−２）、Ｙ⁵はそれぞれ独立に下記一般式（１１−３）

で示される基であり、Ｙ⁶はそれぞれ独立に下記一般式（１２−１）、Ｙ⁷はそれぞれ独立に下記一般式（１２−２）、Ｙ⁸はそれぞれ独立に下記一般式（１２−３）

で示される基であり、Ｒ⁵、Ｒ⁶、Ｒ⁷は上記の通りであり、ｃ１１、ｃ１２、ｃ３１、ｃ４１、ｃ５１、ｃ６１、ｃ７１、ｃ８１はそれぞれ独立に０〜３の整数、ｃ２３は２以上の整数、ｃ１３〜ｃ１９、ｃ２４〜ｃ２９、ｃ３２〜ｃ３８、ｃ４２〜ｃ４８、ｃ５２〜ｃ５８、ｃ６２〜ｃ６６、ｃ７２〜ｃ７６、ｃ８２〜ｃ８６は０以上の整数、ｃ２３＋ｃ２４＋ｃ２５＋ｃ２６＋ｃ２７＋ｃ２８＋ｃ２９は３以上の整数であって、１分子中に２個以上、特に３個以上のＳｉＨ基を有し、２５℃の粘度が０．００５〜１０Ｐａ・ｓの範囲に入るように選ばれる。）

(Wherein, R ² is as defined above, R ⁵ are each independently no hydrogen atom or an aliphatic unsaturated bond unsubstituted or halogen atom or cyano group-substituted monovalent hydrocarbon group, R ⁶ And R ⁷ are each independently a monovalent hydrocarbon group that is unsubstituted or substituted with a halogen atom or a cyano group other than Me and does not contain an aliphatic unsaturated bond, and Y ³ independently represents the following general formula (11-1) , Y ⁴ are each independently the following general formula (11-2), Y ⁵ are each independently the following general formula (11-3)

Y ⁶ is each independently the following general formula (12-1), Y ⁷ is each independently the following general formula (12-2), and Y ⁸ is each independently the following general formula (12-3) )

R ⁵ , R ⁶ and R ⁷ are as described above, c11, c12, c31, c41, c51, c61, c71 and c81 are each independently an integer of 0 to 3, c23 is 2 C13-c19, c24-c29, c32-c38, c42-c48, c52-c58, c62-c66, c72-c76, c82-c86 are integers greater than or equal to 0, c23 + c24 + c25 + c26 + c27 + c28 + c29 is an integer greater than or equal to 3. One molecule has two or more, particularly three or more SiH groups, and is selected so that the viscosity at 25 ° C. falls within the range of 0.005 to 10 Pa · s. )

The formula (9), in (10), R ² can monovalent exemplified hydrocarbon groups containing no similar aliphatic unsaturated bonds and R ² in the formula (1), a methyl group. Among these, an ethyl group An alkyl group such as propyl group and butyl group, a cycloalkyl group such as cyclohexyl group, and an aryl group such as phenyl group are preferable.
R ⁵ is each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, cyclohexyl A cycloalkyl group such as a group, an aryl group such as a phenyl group or a tolyl group, or a halogen atom such as fluorine, chlorine or bromine, a cyano group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups as a substituent An unsubstituted or substituted monovalent carbon such as a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc., preferably not containing an aliphatic unsaturated bond having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms Examples thereof include hydrogen groups, and among these, hydrogen atoms, methyl groups, ethyl groups, propyl groups, alkyl groups such as butyl groups, cycloalkyl groups such as cyclohexyl groups, etc. Group, an aryl group such as a phenyl group is preferable.

R ⁶ and R ⁷ are each independently an unsubstituted or substituted monovalent hydrocarbon group other than Me that does not contain an aliphatic unsaturated bond, an alkyl group such as an ethyl group, a propyl group, or a butyl group, or a cyclohexyl group. A part or all of the hydrogen atoms bonded to the carbon atoms of these groups as a substituent, such as a fluorine atom, a chlorine atom, a halogen atom such as bromine, or a cyano group. An unsubstituted or substituted monovalent hydrocarbon which does not contain an aliphatic unsaturated bond, preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a substituted chloromethyl group, trifluoropropyl group and cyanoethyl group Examples include groups.
Among these, as R ⁶ , an alkyl group is preferable, and an effect of changing the performance of the cured film can be obtained by using a substituent having a changed carbon number. However, since the curability tends to decrease when the number of carbon atoms becomes too large, those selected from those having 4 or less carbon atoms are preferred, and ethyl and propyl groups are industrially preferred. An ethyl group having 2 carbon atoms is a desirable choice for obtaining releasability. R ⁷ is preferably an alkyl group such as an ethyl group, a propyl group or a butyl group, or a cycloalkyl group such as a cyclohexyl group.

The substituents contained in one molecule of component (C) may be different from each other, but it is economical that the methyl group is preferably 50 mol% or more, more preferably 80 mol% or more of the total substituents. Is advantageous. For release films, there are many uses that require higher transparency of the cured film and adhesion to the substrate. In that case, the substituent of the component (C) is a bulky substitution having more carbon atoms than the methyl group. By changing to a group or an aromatic substituent, an effect of promoting wetting or interaction with the film substrate surface can be obtained. Assuming that the component (C) having no aromatic substituent is the component (C1) and the component (C) having an aromatic substituent is the component (C2), the (C1) / (C2) mass part ratio = 1/9 It is desirable to use an organohydrogenpolysiloxane mixture of ˜9 / 1, particularly 2/8 to 9/1, and it is easy to balance with other properties such as peel strength of the cured film.
Here, as the component (C1), in the general formula (9) and / or the general formula (10), R ² is a monovalent hydrocarbon group other than an aromatic group not containing an aliphatic unsaturated bond, R ⁵ is a monovalent hydrocarbon group other than an aromatic group not containing a hydrogen atom or an aliphatic unsaturated bond, and R ⁶ and R ⁷ are monovalent hydrocarbon groups other than an aromatic group not containing an aliphatic unsaturated bond A structure is preferred.
In addition, as the component (C2), in the general formula (9) and / or the general formula (10), at least one of R ² and R ^{5 to} R ⁷ is a monovalent hydrocarbon group having an aromatic group. Some structures are preferred.

In the above formulas (9) and (10), c11, c12, c31, c41, c51, c61, c71, and c81 are each independently an integer of 0 to 3, preferably 0 or 1.
The organohydrogenpolysiloxane of component (C) is an organohydrogenpolysiloxane having two or more R ² ₂ HSiO _1/2 units (R ² is the same as above) in one molecule, or the organohydropolysiloxane It is preferable that it is a mixture containing a part of genpolysiloxane.

In the above formulas (9) and (10), c23 is an integer of 2 or more, c13 to c19, c24 to c29, c32 to c38, c42 to c48, c52 to c58, c62 to c66, c72 to c76, c82 to c86 is an integer of 0 or more, is a positive number that has 2 or more, particularly 3 or more SiH groups in one molecule, and satisfies the viscosity of the component (C) described above.
In the above formula (10), c23 + c24 + c25 + c26 + c27 + c28 + c29 is an integer of 3 or more.

The number of SiH groups in the organohydrogenpolysiloxane represented by the above formulas (9) and (10) is 2 or more, particularly 3 or more, and if it is less than 2, the time required for curing is long and the production efficiency decreases. There is.
In the above formula (9), the number of SiH groups in one molecule is preferably selected so as to be in the range of 2 to 1,000, particularly 3 to 1,000, especially 3 to 500. . In this case, the number of SiH groups in one molecule is calculated from [c11 + c12 + c13 + c14 + c15 × {c31 + c32 + c33 + c34 × (c61 + c62 + c63)} + c16 × {c41 + c42 + c43 + c51 + c52 + c53 + (c44 + c54) × (c61 + c63 + 81 + 72 + c63 + 82 + c + 82 + c ++).
In the above formula (10), the number of SiH groups in one molecule is preferably selected so as to be in the range of 2 to 100, particularly 3 to 100, especially 4 to 50. In this case, the number of SiH groups in one molecule is calculated from [c23 + c24 + c25 × {c31 + c32 + c33 + c34 × (c61 + c62 + c63)} + c26 × {c41 + c42 + c43 + c51 + c52 + c53 + (c44 + c54) × (c61 + c62 + c63) + (c45 + c55) + 82 × c ++ 83 +

In the above formula (9), the degree of polymerization is preferably 3 to 1,000, particularly 3 to 500. In this case, the polymerization degree blade, [2 + c13 + c14 + c15 × {2 + c32 ++ c33 + c34 × (2 + c62 + c63 + c64 + c65 + c66) + c35 × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86) + c36 + c37 + c38} + c16 × {3 + c42 + c43 + c46 + c47 + c48 + c52 + c53 + c56 + c57 + c58 + (c44 + c54) × (2 + c62 + c63 + c64 + c65 + c66) + (c45 + c55) × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86)} + c17 + c18 + c19] scolded calculated is.
In the above formula (10), the degree of polymerization is preferably selected in the range of 3 to 100, particularly 4 to 50. In this case, the polymerization degree blade, [c23 + c24 + c25 × {2 + c32 ++ c33 + c34 × (2 + c62 + c63 + c64 + c65 + c66) + c35 × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86) + c36 + c37 + c38} + c26 × {3 + c42 + c43 + c46 + c47 + c48 + c52 + c53 + c56 + c57 + c58 + (c44 + c54) × (2 + c62 + c63 + c64 + c65 + c66) + (c45 + c55) × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86)} + c27 + c28 + c29] scolded calculated is.

Specific examples of the organohydrogenpolysiloxane represented by the above formulas (9) and (10) include the following.
Me ₃ SiO— (Me (H) SiO) ₁₀₀ —SiMe ₃
Me ₂ (H) SiO— (Me (H) SiO) ₅₀ — (Me ₂ SiO) ₅₀ —Si (H) Me ₂

Examples of the organohydrogenpolysiloxane in which a linear structure and a cyclic structure are simultaneously contained in one molecule include, for example, an organohydrogenpolysiloxane represented by the above formula (9) and the above formula (10). The organohydrogenpolysiloxane is crosslinked between one of the molecular chain terminal SiH groups of the formula (9) and one of the SiH groups of the formula (10), and the Si atoms are divalent organic groups (—CH ₂ -CH ₂ -, etc.) or an oxygen atom (-O-) organohydrogenpolysiloxane can be exemplified with two structures coupled linear structures and a cyclic structure via a.

  In a linear structure, a branched structure, and a cyclic structure, the cross-linked state of the cured film can be different, so that the peeling characteristics can be controlled by using differently. The annular structure is effective for making the cured film harder and reducing the speed dependency of the peeling force. The linear structure is effective in reducing the peel strength of the cured film. The branched structure is effective in improving the curability of the composition in that many terminal SiH functional groups advantageous for the curing reaction can be introduced.

Examples of the branched organohydrogenpolysiloxane having a special structure among the branched organohydrogenpolysiloxanes represented by the above formula (9) include monofunctional R ² ₂ HSiO _1/2 siloxane units (R ² is Same as above (hereinafter the same), hereinafter referred to as ^MH units) and / or R ² ₃ SiO _1/2 siloxane units (hereinafter referred to as M units) and trifunctional R ² SiO _3/2 siloxane units (hereinafter referred to as T units). Siloxane (hereinafter referred to as HMT siloxane), ^MH units or siloxane composed of M units and tetrafunctional SiO _4/2 siloxane units (hereinafter referred to as Q units) (hereinafter referred to as HMQ siloxane). Can be mentioned.
In any siloxane, the group represented by R ² is industrially preferably a Me group or a Ph group.

The molar ratio of ( ^MH unit + M unit) / T unit in HMT siloxane is 2/8 to 8/2, especially 3/7 to 7/3, and the molar ratio of M unit / ^MH unit is 0/10 to 9 /. 1, especially 0/10 to 8/2. Moreover, although it is desirable that the molecular terminal is bonded to an ^MH unit or an M unit, the terminal may be partially formed as a silanol group or an alkoxy group.
Similarly for HMQ siloxane, the molar ratio of ( ^MH units + M units) / Q units is 2/8 to 8/2, especially 3/7 to 7/3, and the molar ratio of M units / ^MH units is 0 / 10-9 / 1, especially 0 / 10-8 / 2, preferably ^MH unit or M unit is bonded to the end of the molecule, but the end is partially formed with a silanol group or alkoxy group You can do it.

Specific examples of these HMT siloxane and HMQ siloxane include the following.

  These HMT siloxane and HMQ siloxane show the effect of improving the exposure resistance, and even if used alone, the effect can be expected to some extent, but the combined use with the component (B) can greatly improve the exposure resistance. it can. It is presumed that the organohydrogenpolysiloxane having a branched structure is likely to gather on the surface of the cured film due to its structural characteristics and forms a surface that is not easily exposed.

In HMQ siloxane, it is preferable to increase the molar ratio of ( ^MH units + M units) / Q units or decrease the degree of polymerization in order to suppress heavy peeling. Conventionally, HMQ siloxane has been known to be used as a heavy release control agent. In particular, if the molar ratio of ( ^MH unit + M unit) / Q unit is increased or the polymerization degree is lowered, heavy release can be achieved. It can be effectively suppressed. A similar effect can be expected by using HMDQ siloxane containing a bifunctional (R ² ) ₂ SiO _2/2 siloxane unit (hereinafter referred to as D unit). HMT siloxane can also be improved by the same method as necessary.

As the component (C), the organohydrogenpolysiloxane may be used alone or in combination of two or more.
The compounding amount of the organohydrogenpolysiloxane of the component (C) is such that the number of moles of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (C) is the components (A) and (B) (or this) The amount corresponds to 1 to 20 times, preferably 1.1 to 15 times the total number of moles of the alkenyl group (unsaturated group) in the optional component described below. (C) If the number of moles of SiH groups in the component is less than 1 times the total number of moles of alkenyl groups (unsaturated groups), the curability will be inadequate. There is no significant increase in the effect, which causes a change over time and is also economically disadvantageous. In addition, as a compounding quantity with general organohydrogenpolysiloxane, it can be set as the range of 0.1-30 mass parts with respect to 100 mass parts of (A) component organopolysiloxane.

(D) Component The platinum group metal catalyst (addition reaction catalyst) which is the component (D) of the present invention comprises (A) and (B) components (or an optional component containing an alkenyl group described later) and ( C) Used to accelerate the crosslinking reaction with the component and form a cured film. Examples of such an addition reaction catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, platinum vinyl group-containing siloxane coordination compound, rhodium, rhodium-olefin complex, and the like. Can be mentioned.

  The amount of the addition reaction catalyst used is a catalytic amount, and can be appropriately increased or decreased depending on the reactivity of the component or the desired curing rate, but platinum is added to the total mass of the components (A) to (C). It is preferable to add 5 to 1,000 ppm (mass ratio) as the amount of rhodium or the amount of rhodium in order to form a sufficient cured film.

(E) component The organic solvent which is (E) component of this invention is mix | blended as needed for the purpose of the improvement of process bath stability, the coating property with respect to various base materials, and adjustment of a coating amount and a viscosity. In particular, the silicone composition for a release film is advantageous because it provides a desirable effect of enabling thin film coating and improving the smoothness of the surface of the cured film. As an organic solvent, what can melt | dissolve compositions, such as toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, hexane, 2-butanone uniformly, can be used, for example.
The component (E) is an optional component, and can be used as a solvent-free release paper or a silicone composition for a release film without blending when danger and safety reduction due to an organic solvent are not preferable. is there.

(E) The organic solvent of a component may be used individually by 1 type, or may use 2 or more types together.
(E) When using a component, the usage-amount is 10-100,000 mass parts with respect to 100 mass parts of said (A) component, Especially the range of 10-10,000 mass parts is preferable. If the blending amount is too large, it may be difficult to control the coating amount. If the blending amount is too small, the effect of blending the solvent, coating properties and pot life may not be seen.

  The silicone composition of the present invention can be easily produced by uniformly mixing the components (A), (B), (C), (D) and, if necessary, the component (E). In order to ensure the pot life, the component (C) or the component (D) is preferably added and mixed immediately before coating. Moreover, when using the organic solvent which is (E) component, after melt | dissolving (A) component uniformly in (E) component, (B), (C) component or (B), (D) component is used. Mixing is advantageous.

  In the silicone composition of the present invention, the following components (F) to (J) can be used as optional additional components as long as the effects of the present invention are not reduced.

（式中、Ｒ⁸は独立に水酸基、アルコキシ基又はアルコキシアルキル基であり、Ｒ⁹は独立に水酸基、アルコキシ基、アルコキシアルキル基及び脂肪族不飽和結合を含有しない非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、Ｒ¹⁰は独立に水酸基、アルコキシ基、アルコキシアルキル基及び脂肪族不飽和結合を含有しないＭｅ以外の非置換又はハロゲン原子もしくはシアノ基置換の一価炭化水素基であり、ｆ１、ｆ２は１〜３の整数であり、ｆ３〜ｆ５はオルガノポリシロキサンの２５℃での粘度を１Ｐａ・ｓ以上３０質量％トルエン希釈粘度で１００Ｐａ・ｓ以下の範囲に入るように選ばれる整数である。） Component (F) The component (F) is an organopolysiloxane represented by the following general formula (13). Component (F) differs from component (A) in that it does not contain an alkenyl group as a functional group.

Wherein R ⁸ is independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group, and R ⁹ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an unsubstituted or halogen atom or cyano group that does not contain an aliphatic unsaturated bond. A substituted monovalent hydrocarbon group, and R ¹⁰ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and a monovalent hydrocarbon group substituted with an unsubstituted or halogen atom or cyano group other than Me, which does not contain an aliphatic unsaturated bond F1 and f2 are integers of 1 to 3, and f3 to f5 so that the viscosity of the organopolysiloxane at 25 ° C. falls within the range of 1 Pa · s to 30% by mass in toluene dilution viscosity of 100 Pa · s or less. (An integer chosen.)

In the above formula (13), R ⁸ is independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and a sec-butoxy group. , Tert-butoxy group and the like having 1 to 6 carbon atoms, and examples of the alkoxyalkyl group include carbon such as methoxyethyl group, ethoxyethyl group, methoxypropyl group, ethoxypropyl group, methoxybutyl group, and ethoxybutyl group. The thing of number 1-6 is mentioned.

R ⁹ is independently an hydroxyl group, an alkoxy group, an alkoxyalkyl group and an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, specifically, a methyl group, an ethyl group, a propyl group, a butyl group Alkyl groups such as cycloalkyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups and tolyl groups, or some or all of hydrogen atoms bonded to carbon atoms of these groups as substituents are fluorine, chlorine, bromine An unsubstituted or substituted monovalent hydrocarbon having preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a halogen atom such as chloromethyl group substituted with a cyano group, a trifluoropropyl group, or a cyanoethyl group An unsubstituted monovalent hydrocarbon group that does not contain a hydroxyl group, an alkoxy group, or an aliphatic unsaturated bond is preferable, and a methyl group, an ethyl group, a pro Group, an alkyl group such as butyl group, cycloalkyl groups such as cyclohexyl group, a phenyl group, aryl groups such as tolyl group are more preferable.

R ¹⁰ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an unsubstituted or substituted monovalent hydrocarbon group other than Me that does not contain an aliphatic unsaturated bond, specifically, an ethyl group, a propyl group, a butyl group Alkyl groups such as cycloalkyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups and tolyl groups, or some or all of hydrogen atoms bonded to carbon atoms of these groups as substituents are fluorine, chlorine, bromine An unsubstituted or substituted monovalent hydrocarbon having preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a halogen atom such as chloromethyl group substituted with a cyano group, a trifluoropropyl group, or a cyanoethyl group An unsubstituted monovalent hydrocarbon group that does not contain a hydroxyl group, an alkoxy group, and an aliphatic unsaturated bond is preferable, and an ethyl group, a propyl group, a Alkyl groups such as group, cycloalkyl groups such as cyclohexyl group, a phenyl group, aryl groups such as tolyl group are more preferable.
f1 and f2 are integers of 1 to 3, preferably 1 or 2, and f3 to f5 are integers satisfying the viscosity described later.

  The viscosity at 25 ° C. of the organopolysiloxane as component (F) is in the range of 1 Pa · s to 30% by mass with toluene dilution viscosity of 100 Pa · s or less, particularly 10 Pa · s to 30% by mass with toluene dilution viscosity of 50 Pa · s. A range is preferable. If the viscosity is too low, the cured film may be insufficiently slipped. If it is too high, industrial handling may be difficult.

  Siloxanes that are straight-chain polymers and do not have functional groups in the side chains are effective for imparting slipperiness to the cured film, and lightening the peeling force without reducing the residual adhesive force. Can also be expected. The release film also exhibits the effect of preventing falling off due to the effect of sliding.

Specific examples of the component (F) include the following polysiloxanes.
_{(HO) Me 2 SiO- (Me} 2 SiO) 10000 -SiMe 2 (OH)
(MeO) Me ₂ SiO— (Me ₂ SiO) ₂₀₀₀ —SiMe ₂ (OMe)
(EtO) Me ₂ SiO— (Me ₂ SiO) ₅₀₀ — (Ph ₂ SiO) ₃₀ —SiMe ₂ (OEt)
(HO) Me ₂ SiO— (Me ₂ SiO) ₅₀₀ — (Ph ₂ SiO) ₁₀ —SiMe ₂ (OH)

  (F) It is preferable that the compounding quantity in the case of mix | blending a component is 0.1-30 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 0.2-20 mass parts. If the amount is less than 0.1 parts by mass, the effect of imparting slipperiness may not be obtained. If the amount exceeds 30 parts by mass, the residual adhesive force may be reduced.

(G) As a component (G) component, the component which improves base-material adhesiveness can be mix | blended. Component (G) is an organopolysiloxane having at least two alkenyl groups, and is a monofunctional R ² _(3-g1) R ¹ _g1 SiO _1/2 siloxane unit (wherein R ¹ and R ² are Same as above (hereinafter the same), g1 is an integer of 1 to 3, hereinafter referred to as M ^R1R2 unit), and trifunctional R ² SiO _3/2 siloxane unit (hereinafter referred to as T ^R2 unit) as an essential unit. It is preferable that the molar ratio of M ^R1R2 unit / T ^R2 unit is 2/8 to 8/2, and the viscosity at 25 ° C. is in the range of 0.001 to 1 Pa · s. Although it is desirable that the M ^R1R2 unit is bonded to the molecular end, it may be partially formed as a silanol group or an alkoxy group.

In the above formula, R ¹ is the formula can be exemplified the same alkenyl group as R ¹ (1), a vinyl group is preferred industrially among these. Further, R ² is the formula (1) R ² and can monovalent exemplified hydrocarbon groups containing no similar aliphatic unsaturated bond, a methyl group. Among these, a phenyl group is preferred industrially. g1 is an integer of 1 to 3, preferably 1 or 2.

Component (G) is an organopolysiloxane having a molar ratio of M ^R1R2 units / T ^R2 units of 2/8 to 8/2, preferably 3/7 to 7/3. If the molar ratio is less than 2/8, the effect of improving adhesion may be reduced, and if it exceeds 8/2, industrial production becomes difficult.

In addition, the difunctional R ² _(2-g2) R ¹ _g2 SiO _2/2 siloxane unit (wherein g2 is 0, 1 or 2 as long as the effect of the component (G) is not impaired. D ^R1R2 _May contain tetrafunctional SiO _4/2 siloxane units (Q units), but especially in the case of a release film, when stronger adhesion is required, ^{MR 1R2} units not containing them / T molar ratio of ^R2 units are siloxane desirably 2 / 8-8 / 2. In addition, when it includes D ^R1R2 unit or Q unit, it is always used so as to be a small amount with respect to both M ^R1R2 unit and T ^R2 unit.
The component (G) is different from the component (A) in that there are more T ^R2 units than D ^R1R2 units.

  The alkenyl group content of the organopolysiloxane of component (G) is preferably 0.01 to 2.5 mol, more preferably 0.03 to 2.0 mol, as the alkenyl group content per 100 g of organopolysiloxane. More preferably, it is 0.05-1.5 mol. If the content is too small, the effect of improving the adhesion may be reduced, and if the content is too high, the pot life may be shortened.

  The organopolysiloxane (G) has a viscosity at 25 ° C. of 0.001 to 1 Pa · s, particularly preferably 0.005 to 0.5 Pa · s, more preferably 0.01 to 0.1 Pa · s. It is preferable that it is the range of s, More preferably, it is the range of 0.01-0.05 Pa.s, and it is preferable to have a polymerization degree which becomes this viscosity range. If the viscosity is less than 0.001 Pa · s, the effect of improving the adhesion may be reduced, and if it exceeds 1 Pa · s, the solubility or dispersibility in the composition may be reduced.

  Moreover, the (G) component can also be expected to have an effect of further enhancing the effect of improving the exposure resistance when used in combination with the branched organohydrogenpolysiloxane of the (C) component. It is presumed that the characteristics of the branched structure can be drawn more strongly by bonding with the branched organohydrogenpolysiloxane by addition reaction.

Specific examples of the component (G) include the following.

(G) As for the compounding quantity in the case of mix | blending a component, 10-100 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 15-100 mass parts. If it is less than 10 parts by mass, the effect of improving the substrate adhesion may be reduced, and if it exceeds 100 parts by mass, the heavy peeling may be increased.
When the component (G) is blended, the ratio of the number of moles of SiH groups in the component (C) to the number of moles of alkenyl groups in the blended component (G) (SiH group / alkenyl group) is 1 or more, particularly It is desirable from the point which can prevent the fall of sclerosis | hardening to add the (C) component of the quantity used as 1-3.

(H) Component As another component for improving substrate adhesion, (H) organosilane represented by the following general formula (14) having at least an epoxy group and an alkoxysilyl group in one molecule and / or the following average composition formula A partially hydrolyzed (co) condensed siloxane of the organosilane of the formula (14) represented by (15) can be used.
R ¹¹ _{h 1} (OR ¹² ) _{h 2} Si (R ¹³ ) _{(4-h 1 -h 2)} (14)
_{^{R 11 h3 (OR 12) h4}} (R 13) h5 SiO (4-h3-h4-h5) / 2 (15)
(In the formula, R ¹¹ is a monovalent organic group containing an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms and may contain an ether bond, and some of them are hydrolyzed to become a hydroxyl group. R ¹³ is an unsubstituted or monovalent hydrocarbon group substituted with a halogen atom or a cyano group, h1 and h2 are integers satisfying 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, and h3 to h5 Is a positive number satisfying 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, and the partially hydrolyzed (co) condensed siloxane has a viscosity at 25 ° C. in the range of 0.001 to 1 Pa · s. (Selected from positive numbers.)
The partially hydrolyzed (co) condensed siloxane represented by the formula (15) of the (H) component is different from the (A) component and the (F) component in that it has an epoxy group.

In the above formulas (14) and (15), examples of the monovalent organic group containing an epoxy group represented by R ¹¹ include 3-glycidoxyalkyl groups such as 3-glycidoxypropyl group, 2- (3, And 2- (3,4-epoxycyclohexyl) alkyl group such as 4-epoxycyclohexyl) propyl group.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, and a hexyl group. Also, those containing ether bonds include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxypropyl group, ethoxypropyl group C1-C6 alkoxyalkyl groups such as methoxybutyl group and ethoxybutyl group, and the like, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, methoxymethyl group , Ethoxymethyl group, propoxymethyl group, butoxymethyl group, Tokishiechiru group, ethoxyethyl group are preferred. Further, examples of the OR ¹² group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group.

R ¹³ is an unsubstituted or substituted monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group or an allyl group. , An alkenyl group such as a propenyl group, an aryl group such as a phenyl group and a tolyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups as a substituent, a halogen atom such as fluorine, chlorine or bromine, cyano Unsubstituted or substituted monovalent groups that do not contain an aliphatic unsaturated bond having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a chloromethyl group, a trifluoropropyl group, or a cyanoethyl group substituted with a group Examples include hydrocarbon groups, and those that do not contain an aliphatic unsaturated bond are preferred, such as methyl, ethyl, propyl, butyl, cyclohexyl, phenyl It is more preferable.

  H1 and h2 are integers satisfying 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, and h3 to h5 are positive numbers satisfying 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3. The positive number satisfies the viscosity described later.

  The viscosity at 25 ° C. of the partially hydrolyzed (co) condensed siloxane represented by the above formula (15) is 0.001 to 1 Pa · s, preferably 0.001 to 0.1 Pa · s, particularly preferably 0.001 to 0.001. The range is preferably 0.05 Pa · s. If the viscosity is too low, the effect of improving the adhesion may be reduced, and if it is too high, the solubility or dispersibility in the composition may be reduced.

  The partially hydrolyzed (co) condensed siloxane represented by the formula (15) is obtained by adding water to the silane represented by the formula (14), such as hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, maleic acid, phosphoric acid, paratoluenesulfonic acid, etc. It is obtained by reacting in the presence of a catalyst and removing the produced alcohol by distillation. Alternatively, a partially hydrolyzed co-condensed silane can be obtained by mixing and reacting the silane represented by the formula (14) with other alkoxysilanes.

Specific examples of the component (H) include the following.

  When the component (H) is blended, the blending amount is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the component (A). If the amount is less than 0.1 parts by mass, the effect of improving the adhesion may not be obtained. If the amount exceeds 10 parts by mass, the residual adhesive force may be reduced.

In the present invention, a catalytic amount of an acid, an alkali, or a metal compound can be added in order to further bring out the adhesion improving effect of the component (H). Here, examples of the acid include formic acid, acetic acid, lactic acid, oxalic acid, maleic acid, malonic acid, benzoic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, ammonium chloride, ammonium sulfate, and the alkali. Ammonia, sodium acetate, sodium carbonate, sodium hydroxide, ammonium hydroxide and the like can be mentioned. Examples of the metal compound include aluminum chloride, trisacetylacetonate aluminum, iron octylate, iron trisacetylacetonate, trisacetylacetonate zircon and the like. Is mentioned.
These are also used to activate the functional group of the component (G), and the amount added is limited to a range that does not affect the curability, pot life, and storage stability of the composition. Preferably, it is 0.0001-0.01 mass part with respect to 100 mass parts of (A) component.

Component (I) Further, as component (I), a siloxane unit (M ^R1R2 unit) represented by the following general formula (16) and a siloxane unit (Q unit) represented by the following formula (17) are in a molar ratio (M ^R1R2 MQ resin having a unit / Q unit of 2/8 to 8/2 can be used.
R ² _(3-i1) R ¹ _i1 SiO _1/2 (16)
SiO _4/2 (17)
(Wherein, R ^1, R ² is as defined above, i1 is an integer of 0-3.)

In the above formula, R ¹ is the formula (1) can be exemplified the same alkenyl groups as R ^1, a vinyl group Of these, an allyl group, an alkenyl group such as a propenyl group is preferred. Moreover, R ² can exemplified monovalent hydrocarbon group not containing a similar aliphatic unsaturated bonds and R ² in the formula (1), a methyl group. Among these, an ethyl group, a propyl group, an isopropyl group, a butyl group , A pentyl group, a phenyl group, and a cyclohexyl group are preferred. i1 is an integer of 0 to 3, preferably 0, 1 or 2.

The MQ resin of the component (I) is a molar ratio (M ^R1R2 unit / ^Mr ) of the siloxane unit (M ^R1R2 unit) represented by the general formula (16) and the siloxane unit (Q unit) represented by the following formula (17). Q unit) is 2/8 to 8/2, and preferably 3/7 to 7/3. If the molar ratio is too small, the solubility or dispersibility in the composition may be lowered, and if it is too large, the effect may be reduced.

In addition, the difunctional R ² _(2-i2) R ¹ _i2 SiO _2/2 siloxane unit (wherein i2 is 0, 1 or 2; D ^R1R2 unit) as long as the effects of the present invention are not impaired. may contain trifunctional R ² SiO _3/2 siloxane units (T ^R2 units) or R ¹ SiO _3/2 siloxane units (T ^R1 units). Note that the ratio of the D ^R1R2 unit and the T ^R2 unit is smaller than both the M ^R1R2 unit and the Q unit, and from this ratio, since the structure different from the component (G) is adopted, the effect is also different. Become.
The component (I) is different from the component (A) in that it contains more Q units than the D ^R1R2 unit and the component (G) in that it contains more Q units than the T ^R2 unit.

  This component is generally used as a peel force control agent, but the effect of improving the exposure resistance can be obtained even with a small amount of the compound which does not exhibit a control effect. In the siloxane unit represented by the formula (16), the MQ resin composed only of il = 0 has an advantage that the effect of stably improving the exposure resistance can be obtained regardless of the usage method such as coating conditions. There is. On the other hand, the MQ resin having an alkenyl group where il is not 0 tends to be difficult to use because the variation in the effect of improving exposure resistance is large, but when used in combination with the branched organohydrogenpolysiloxane of the component (C), The exposure resistance improving effect can be stably and greatly extracted. It is presumed that the characteristics of the branched structure can be drawn more strongly by bonding with the branched organohydrogenpolysiloxane by addition reaction.

  The alkenyl group content of the component (I) MQ resin is preferably 0 to 2.4 mol, more preferably 0 to 2.0 mol, and still more preferably 0 as the alkenyl group content per 100 g of the organopolysiloxane. ~ 1.5 mol. If the content is too small, the effect of heavy peeling may decrease with time, and if the content is too large, the pot life may be shortened.

Specific examples of the component (I) include the following.

(I) As for the compounding quantity in the case of mix | blending a component, 1-100 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 5-50 mass parts. If it is less than 1 part by mass, the effect of improving the exposure resistance may be reduced, and if it exceeds 100 parts by mass, the heavy peeling may be increased.
When the component (I) to be blended has an alkenyl group, the ratio of the number of moles of SiH groups in the component (C) to the number of moles of alkenyl groups in the component (I) (SiH group / alkenyl group) is 1. As mentioned above, it is desirable from the point which can prevent the fall of sclerosis | hardening that the amount of (C) component of the quantity which will become 1-10 especially is added.

Component (J) Further, as the component (J), a nonionic surfactant having little influence on the addition reaction can be added. Specific examples of the component (J) include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene polyoxypropylene stearyl ether, and the like.

  The component (J) is also expected to improve the compatibility with a hydrophobic component such as a conductive agent component of a conductive polymer composition described later as a component that can be blended. Moreover, the improvement of the transparency and smoothness of a cured film can also be expected by improving leveling with (J) a nonionic surfactant.

  The addition of the component (J) is expected to improve the exposure resistance due to the antistatic action. For that purpose, 0.1 to 5 parts by mass, particularly 0.2 to 0.1 parts by mass with respect to 100 parts by mass of the component (A). The addition amount is preferably 4 parts by mass. Moreover, when there is too much addition amount, the sclerosis | hardenability of a composition may be reduced.

Other Components In the silicone composition of the present invention, a bath life extending agent such as 3-methyl-1-butyn-3-ol, ethynylcyclohexanol, ethynylcyclohexene, and the like is added in an amount of 0. About 01 to 1 part by mass can be blended.

The silicone composition of the present invention may contain other organic resins. The organic resin is a component blended for the purpose of processing bath stability, improvement of coating properties for various substrates, improvement of film formation, adjustment of peeling characteristics, adjustment of coating amount and viscosity, for example, polyvinyl Organic resins such as alcohol, poly (meth) acrylate, polyester, cellulose, and derivatives thereof can be used, and can be contained in an amount of 2 to 400 parts by mass with respect to 100 parts by mass of component (A). If it affects the characteristics, it may not be added.
Specific examples of the derivative include those obtained by etherifying a part of the hydroxy group of cellulose with an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and an ethyl group is preferable.

  The silicone composition of the present invention can be blended with a conductive polymer composition for the purpose of preventing static charge or imparting conductivity and / or improving the exposure to the atmosphere. The conductive polymer composition contains (a) a π-conjugated conductive polymer and (b) a polyanion doped in the (a) π-conjugated conductive polymer, and (c) a solubilizer or the like. It is desirable that the composition be dispersible and soluble in a solvent mainly containing an organic solvent. When the conductive polymer composition is blended, the blending amount is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the component (A).

[Release paper or release film]
The release paper or release film in the second aspect of the present invention comprises a base material made of paper or a plastic film and a release agent layer formed on at least one surface of the base material.
The release agent layer constituting the release paper or release film of the present invention is a layer formed by a cured film of the silicone composition.

  The thickness of the release film is preferably 2 to 500 μm, more preferably 10 to 100 μm. Moreover, 10-1,000 micrometers is preferable and, as for the thickness of release paper, 50-300 micrometers is more preferable. These thicknesses can be measured by a known thickness measuring instrument (thickness gauge) such as a dial gauge or an ultrasonic thickness gauge.

  In the release paper and release film, the thickness of the release agent layer is preferably 0.1 to 5.0 μm, and more preferably 0.1 to 2.0 μm. Here, the “thickness of the release agent layer” can be measured by a fluorescent X measuring device.

Examples of the resin material constituting the plastic film include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacryl, polycarbonate, polyvinylidene fluoride, polyarylate, and styrene. Examples include elastomers, polyester-based elastomers, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Among these resin materials, polyethylene terephthalate is preferable in terms of transparency, flexibility, antifouling property, strength, and the like.
As the paper, fine paper, kraft paper, coated paper, and the like can be used.

  Examples of the method for producing a release paper or release film include a method including applying the silicone composition to at least one surface of a paper or a plastic film and drying to obtain a release paper or a release film.

As a coating method, for example, a method using a coating machine such as a bar coater, a gravure coater, an air knife coater, a roll coater, or a wire bar is applied. Although there is no restriction | limiting in particular as an application quantity, Usually, it is set as the range of 0.1-5.0 g / m < ² > as solid content.

  Examples of the drying method include a method of removing volatile components and solvent components by heating. Specifically, a hot air dryer, IR dryer, etc. are mentioned. Or you may leave as it is at normal temperature. 50-200 degreeC is preferable and the temperature at the time of drying has more preferable 70-180 degreeC. The time for drying is preferably 1 to 120 seconds, more preferably 5 to 90 seconds.

  The release paper or release film according to the second aspect of the present invention is provided with a release agent layer composed of a cured film of the above silicone composition, and therefore has excellent exposure resistance and peelability. Therefore, it is suitable to use the release paper or release film of the present invention as an adhesive sheet for optical or electronic / electrical components.

Examples , Reference Examples and Comparative Examples are shown below, but the present invention is not limited to the following Examples. In the following examples, the viscosity was measured at 25 ° C. using a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.). In the following examples, “part” means “part by mass”, and “%” means “mass%”.

[ Reference Example 1 ]
As component (A), a 30% toluene solution having a viscosity at 25 ° C. of 20 Pa · s and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2 The main skeleton that is blocked with a silyl group and the main skeleton excluding the terminal is 0.7% by mole of a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2 . 100 parts of organopolysiloxane (A-1) (vinyl group content = 0.01 mol / 100 g) composed of 99.3 mol% of the dimethylsiloxane unit represented, and toluene (E -1) 1,140 parts and 2-butanone (E-2) 1,140 parts were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, 15 parts of 1-octadecene (B-1) (unsaturated group content = 0.4 mol / 100 g) as component (B), (C) component, It is blocked with a trimethylsilyl group represented by CH ₃ ) ₃ SiO _1/2 , contains 95 mol% of a methylhydrogensiloxane unit represented by (CH ₃ ) HSiO _2/2 , and has a viscosity of 0.03 Pa at 25 ° C. 5 parts of linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) which is s (the number of moles of hydrogen atoms directly bonded to silicon atoms is (A) B) 1.3 times the total number of moles of unsaturated groups contained in the component), 1 part of 3-methyl-1-butyn-3-ol as a bath life extender is blended, and 20 to 40 ° C. And stirred for 1 hour.
Immediately before coating the obtained solution, a platinum-vinylsiloxane complex was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst for component (D) to give a coating composition.

[Example 1 ]
As component (A), a 30% toluene solution has a viscosity of 10 Pa · s at 25 ° C., and the end of the molecular chain is represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2. 2.8 mol% of a methylvinylsiloxane unit blocked with a group and represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and a dimethylsiloxane unit represented by (CH ₃ ) ₂ SiO _2/2 96.9 mol% and (CH ₃ ) organopolysiloxane (A-2) containing 0.1 mol% of a methylsiloxane unit represented by SiO _3/2 (vinyl group content = 0.04 mol / 100 g) ) And 100 parts of component (E), 1,102 parts of toluene (E-1), 2-butanone and 1,102 parts of (E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, 5 parts of 1,7-octadiene (B-2) (unsaturated group content = 1.8 mol / 100 g) as component (B), and component (C) of Reference Example 1 were used. 8 parts of linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g), and 100 mol% of methylhydrogensiloxane unit represented by (CH ₃ ) HSiO _2/2 The cyclic organohydrogenpolysiloxane (C-2) (SiH content = 1.7 mol / 100 g) having a viscosity of 0.005 Pa · s at 25 ° C. is added to 3 parts ((C) component silicon atoms) As a bath life extender, the total number of directly connected hydrogen atoms is 1.3 times the total number of unsaturated groups contained in the component (A) and the component (B). Contains 1 part butyn-3-ol The mixture was stirred and mixed at 20 to 40 ° C. for 1 hour.
Immediately before coating the obtained solution, a platinum-vinylsiloxane complex was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst for component (D) to give a coating composition.

[Example 2 ]
As the component (A), 100 parts of the organopolysiloxane (A-1) (vinyl group content = 0.01 mol / 100 g) of Reference Example 1 and toluene (E-1) 1,121 as the component (E) And 1,121 parts of 2-butanone (E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, as the component (B), the following formula CH ₂ ═CH—C ₈ H ₁₆ —Si (CH ₃ ) ₃
A linear organohydrogenpolysiloxane (C-1) of Reference Example 1 using 10 parts of the silane (B-3) (unsaturated group content = 0.47 mol / 100 g) represented by formula (C) as a component. 4 parts of (SiH content = 1.5 mol / 100 g), and both ends of the molecular chain are blocked with a dimethylhydrogensilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , and (CH ₃ ) HSiO _{2 The} methyl hydrogen siloxane unit represented by _{/ 2} contains 70 mol%, the dimethylsiloxane unit represented by (CH ₃ ) ₂ SiO _2/2 contains 25 mol%, and the viscosity at 25 ° C. is 0.04 Pa · s. 4 parts of a certain linear organohydrogenpolysiloxane (C-3) (SiH content = 1.2 mol / 100 g) (total number of moles of hydrogen atoms directly connected to silicon atoms of component (C) is (A) Of component and component (B) 1 part of 3-methyl-1-butyn-3-ol as a bath life extender and mixed with stirring at 20 to 40 ° C. for 1 hour. did.
Immediately before coating the obtained solution, a platinum-vinylsiloxane complex was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst for component (D) to give a coating composition.

で示されるジシロキサン（Ｂ−４）（不飽和基含有量＝０．５６モル／１００ｇ）を１０部、（Ｃ）成分として、参考例１の直鎖状オルガノハイドロジェンポリシロキサン（Ｃ−１）（ＳｉＨ含有量＝１．５モル／１００ｇ）を４部、及び（ＣＨ₃）₂ＨＳｉＯ_1/2で表されるジメチルハイドロジェンシリル基が５０モル％、（ＣＨ₃）ＳｉＯ_3/2で表されるメチルシロキサン単位が５０モル％からなり、２５℃における粘度が０．０１Ｐａ・ｓである分岐状オルガノハイドロジェンポリシロキサン（Ｃ−４）（ＳｉＨ含有量＝０．７５モル／１００ｇ）を４部（（Ｃ）成分のケイ素原子に直結した水素原子の合計モル数が（Ａ）成分と（Ｂ）成分の含有する不飽和基の合計モル数に対し１．４倍に相当）、バスライフ延長剤として、３−メチル−１−ブチン−３−オールを１部配合し、２０〜４０℃で１時間撹拌混合した。
得られた溶液を塗工する直前に、（Ｄ）成分の触媒として、白金−ビニルシロキサン錯体を白金量０．０２部（２０ｍｇ）相当の量添加して塗工用組成物とした。 [Example 3 ]
As component (A), a 30% toluene solution has a viscosity at 25 ° C. of 15 Pa · s, and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2. The main skeleton, which is blocked with a silyl group, and the main skeleton excluding the terminal is 1.5 mol% of a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2 100 parts of organopolysiloxane (A-3) (vinyl group content = 0.02 mol / 100 g) composed of 98.5 mol% of the dimethylsiloxane unit represented, toluene (E -1) 1,121 parts and 1,121 parts of 2-butanone (E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the obtained solution, as the component (B), the following formula

As a component (C), 10 parts of the disiloxane (B-4) (unsaturated group content = 0.56 mol / 100 g) represented by the linear organohydrogenpolysiloxane (C-1) of Reference Example 1 ) (SiH content = 1.5 mol / 100 g), and 4 parts of dimethylhydrogensilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , (CH ₃ ) SiO _3/2 A branched organohydrogenpolysiloxane (C-4) (SiH content = 0.75 mol / 100 g) having a methylsiloxane unit represented by 50 mol% and a viscosity at 25 ° C. of 0.01 Pa · s. 4 parts (the total number of moles of hydrogen atoms directly connected to silicon atoms in component (C) is 1.4 times the total number of moles of unsaturated groups in components (A) and (B)), bath 3-methyl as a life extender 1-butyn-3-ol were blended 1 part and mixed with stirring for 1 hour at 20 to 40 ° C..
Immediately before coating the obtained solution, a platinum-vinylsiloxane complex was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst for component (D) to give a coating composition.

[Example 4 ]
As component (A), a 30% toluene solution has a viscosity at 25 ° C. of 15 Pa · s, and both ends of the molecular chain are represented by (CH ₃ ) ₂ (CH ₂ ═CH) SiO _1/2. The main skeleton blocked by a silyl group and excluding the terminal is represented by 4 mol% of a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ ═CH) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2. Organopolysiloxane (A-4) composed of 91 mol% of dimethylsiloxane units and 5 mol% of diphenylsiloxane units represented by (C ₆ H ₅ ) ₂ SiO _2/2 (vinyl group content = 0. (04 mol / 100 g) as 100 parts, (E) component, 1,121 parts of toluene (E-1) and 1,121 parts of 2-butanone (E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C. did.
In the obtained solution, as component (B), 10 parts of disiloxane (B-4) (unsaturated group content = 0.56 mol / 100 g) of Example 3 and (C) component as reference example 1 4 parts of a linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) and a dimethylhydrogensilyl group represented by (CH ₃ ) ₂ HSiO _1/2 45 mol%, (CH ₃ ) ₂ SiO _2/2 dimethylsiloxane unit represented by 10 mol%, SiO _4/2 siloxane unit represented by 45 mol%, viscosity at 25 ° C. is 0.01 Pa -The total number of moles of hydrogen atoms in which 4 parts of the branched organohydrogenpolysiloxane (C-5) (SiH content = 0.75 mol / 100 g) which is s (directly linked to the silicon atom of the component (C)) is ( Of component A) and component (B) 1 part of 3-methyl-1-butyn-3-ol as a bath life extender and mixed with stirring at 20 to 40 ° C. for 1 hour. did.
Immediately before coating the obtained solution, a platinum-vinylsiloxane complex was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst for component (D) to give a coating composition.

[ Reference Example 2 ]
As component (A), 100 parts of organopolysiloxane (A-1) (vinyl group content = 0.01 mol / 100 g) of Reference Example 1 and toluene (E-1) 1,168 as component (E) And 1,168 parts of 2-butanone (E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.
In the resulting solution, as the component (B), the following formula CH ₂ ═CH—C ₁₄ H ₂₉
15 parts THAT indicated by 1-hexadecene (B-5) (unsaturated group content = 0.45 mol / 100 g), as the component (C), straight-chain organohydrogenpolysiloxane of Reference Example 1 (C- 1) 6 parts of (SiH content = 1.5 mol / 100 g), and both ends of the molecular chain are blocked with a dimethylhydrogensilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , excluding the ends skeleton (CH ₃₎ HSiO _2/2 expressed methylhydrogensiloxane units 60 mole% and are in (CH _{3) 3} SiO _1/2 represented dimethylsiloxane units 20 mole% and are in (C ₆ H _{5) 2} Linear organohydrogenpolysiloxane (C-6) composed of 20 mol% of diphenylsiloxane units represented by SiO _{2/2 and} having a viscosity at 25 ° C. of 0.5 Pa · s (SiH content = 0. 68 moles / 100g) 2 parts (total moles of hydrogen atoms directly connected to silicon atoms of component (C) are 1.3 times the total moles of unsaturated groups contained in components (A) and (B) ), 1 part of 3-methyl-1-butyn-3-ol was blended as a bath life extender, and the mixture was stirred and mixed at 20 to 40 ° C. for 1 hour.
Immediately before coating the obtained solution, a platinum-vinylsiloxane complex was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst for component (D) to give a coating composition.

[ Reference Example 3 ]
In Reference Example 1 , as a component (F), the viscosity of a 30% toluene solution at 25 ° C. is 40 Pa · s, both ends of the molecular chain are blocked with dimethylhydroxylsilyl groups, and the main skeleton excluding the ends is dimethylsiloxane. 1 part of an organopolysiloxane (F) (hydroxyl group content = 0.0002 mol / 100 g) composed of 100 mol% unit is added and the component (C) is added to the linear organohydro of Reference Example 1. Genpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) was blocked with 5 parts, and dimethylhydrogensilyl groups represented by (CH ₃ ) ₂ HSiO _1/2 at both ends of the molecular chain. is, (CH ₃₎ dimethylsiloxane units represented by ₂ SiO _2/2 containing 90 mole%, the linear organohydrogen a viscosity at 25 ° C. is at 0.02 Pa · s 5 parts of polysiloxane (C-7) (SiH content = 0.1 mol / 100 g) (total component number of hydrogen atoms directly connected to silicon atom of component (C) is component (A), component (B) Component and (F) equivalent to 1.3 times the total number of moles of unsaturated groups contained in the component), and (E) component is added to 1,197 parts of toluene (E-1) and 2-butanone ( E-2) A composition was prepared in the same manner as in Reference Example 1 except that the amount was increased to 1,197 parts.

[Example 5 ]
In Example 3 , as component (G), the viscosity at 25 ° C. is 0.03 Pa · s, the ends of the molecular chains are blocked with dimethylvinylsilyl groups, and the main skeleton excluding the ends is (CH ₃ ) ₂ CH ₂ = Additional 20 parts of organopolysiloxane (G) (vinyl group content = 0.6 mol / 100 g) composed of 50 mol% of CHSiO _1/2 units and 50 mol% of CH ₃ SiO _3/2 units (C) component, 11 parts of linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) of Reference Example 1 , and branched organohydro of Example 3 Genopolysiloxane (C-4) (SiH content = 0.75 mol / 100 g) 11 parts (total moles of hydrogen atoms directly bonded to silicon atoms in component (C) are component (A) and component (B) And (G) component contains (Equivalent to 1.3 times the total number of moles of the sum group), and the component (E) is increased to 1,444 parts of toluene (E-1) and 1,444 parts of 2-butanone (E-2). A composition was prepared in the same manner as in Example 3 except that.

[Example 6 ]
In Example 3 , as the component (H), the following average composition formula (CH ₃ O) _a R ^Ep _b SiO _{(4-ab) / 2}
(In the formula, ^Rep is a glycidoxypropyl group, a is 1.7, and b is 1.)
3 parts of siloxane oligomer (H) having an epoxy group with an average polymerization degree of 3 and a viscosity of 0.1 Pa · s at 25 ° C. is added, and the component (E) is toluene (E-1) 1 , 149 parts and 2-butanone (E-2) 1,149 parts except that the composition was prepared in the same manner as in Example 3 .

[Example 7 ]
In Example 4 , as component (I), CH ₂ ═CH (CH ₃ ) ₂ SiO _1/2 unit 5 mol%, (CH ₃ ) ₃ SiO _1/2 unit 45 mol%, SiO _4/2 unit 50 mol 20 parts of an organopolysiloxane (I-1) (vinyl group content 0.07 mol / 100 g) having an average degree of polymerization of 100% is added, and the component (C) is used as the linear organohydro of Reference Example 1. 8 parts of Genpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) and the branched organohydrogenpolysiloxane (C-5) of Example 4 (SiH content = 0.75 mol) / 100g) is 6 parts (total moles of hydrogen atoms directly connected to silicon atoms of component (C) with respect to the total moles of unsaturated groups contained in components (A), (B) and (I) (Equivalent to 1.5 times) Down except for increasing (E-1) 1,368 parts of 2-butanone (E-2) in 1,368 parts was prepared in the same manner as the compositions of Example 4.

[ Reference Example 4 ]
Reference Example 1 as component (I), (CH _{3) 3} SiO _1/2 units 55 mole%, the organopolysiloxane (I-2) having an average polymerization degree of 70 made SiO _4/2 units 45 mole% 2 parts Was added, and the composition was prepared in the same manner as in Reference Example 1 except that the component (E) was increased to 1,159 parts of toluene (E-1) and 1,159 parts of 2-butanone (E-2). did.

[ Reference Example 5 ]
In Reference Example 1 , as the component (J), 1 part of a nonionic surfactant (J) represented as polyoxyethylene dodecyl ether (oxyethylene bond number 5 to 15) is additionally blended, and the component (E) A composition was prepared in the same manner as in Reference Example 1 except that 1,149 parts of toluene (E-1) and 1,149 parts of 2-butanone (E-2) were used.

[Example 8 ]
As the component (A), the viscosity at 25 ° C. is 0.5 Pa · s, the end of the molecular chain is blocked with a dimethylvinylsilyl group, the dimethylsiloxane unit is represented by 97 mol%, and represented by CH ₃ SiO _3/2. 100 parts of a branched organopolysiloxane (A-5) (vinyl group content = 0.02 mol / 100 g) containing 1 mol% of a methylsiloxane unit, and the disiloxane of Example 3 (B) component ( B-4) 10 parts of (unsaturated group content = 0.56 mol / 100 g) as component (C), linear organohydrogenpolysiloxane (C-1) of Reference Example 1 (SiH content = 1.5 moles / 100 g) is 17 parts (the number of moles of hydrogen atoms directly connected to the silicon atoms of the component (C) is the total moles of dissociable groups contained in the components (A), (B) and (G)) Equivalent to 1.3 times the number), ( G) Organopolysiloxane (G) consisting of (CH ₃ ) ₂ CH ₂ ═CHSiO _1/2 units 50 mol% and CH ₃ SiO _3/2 units 50 mol% in Example 5 (vinyl group content = 0.6 mol / 100 g) as a bath life extender, 1 part of 3-methyl-1-butyn-3-ol is blended, and (E) component is not blended at 20 to 40 ° C. for 1 hour. Stir and mix.
As a catalyst for the component (D), a platinum-vinylsiloxane complex was added in an amount corresponding to a platinum amount of 0.02 part (20 mg) to prepare a composition.

[Comparative Example 1]
In Reference Example 1 , the component (B) was omitted, and the linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) of Reference Example 1 was 1 as the component (C). (E) The number of moles of hydrogen atoms directly bonded to silicon atoms is maintained at 1.3 times the total number of moles of unsaturated groups contained in the components (A) and (B). A composition was prepared in the same manner as in Reference Example 1 except that 959 parts of toluene (E-1) and 959 parts of 2-butanone (E-2) were used.

<Evaluation>
[Curing property]
The obtained composition (release agent) was applied to PE laminated paper having a thickness of 100 μm by a # 14 bar coater and heated in a hot air dryer at 120 ° C. for 1 minute to form a release agent layer. The composition of Reference Example 5 was applied using an IR tester and dried at 120 ° C. for 30 seconds to form a release agent layer. In both cases, the transfer amount was adjusted so that the coating amount was 0.8 g / m ² in terms of solid content. The release agent layer was rubbed 10 times with a finger, and then the presence or absence of cloudiness and dropping off was visually observed and evaluated according to the following criteria.
A: Cloudy and omission were not seen.
B: Cloudy or falling off was observed.

[Adhesion]
The obtained composition (release agent) was applied to a PET film having a thickness of 38 μm with a # 5 bar coater and heated in a hot air dryer at 120 ° C. for 1 minute to form a release agent layer. The composition of Reference Example 5 was applied using an IR tester and dried at 120 ° C. for 30 seconds to form a release agent layer. In both cases, the transfer amount was adjusted so that the coating amount was 0.2 g / m ² in terms of solid content. The release agent layer was stored at 25 ° C. and 50% RH for one week or at 60 ° C. and 90% RH for one week. After the release agent layer was rubbed 10 times with a finger, the presence or absence of cloudiness and dropping off was visually observed and evaluated according to the following criteria.
A: Clouding and dropping off were not observed even after one week at 60 ° C. and 90% RH.
B: Clouding and dropping off were observed after one week at 60 ° C. and 90% RH, but at 25 ° C. and 50% R
H Clouding or shedding was not observed in one week.
C: Clouding or dropping off was observed at 25 ° C. and 50% RH for one week.

[Peeling force]
A release agent layer is formed in the same manner as in the above sclerosis evaluation, and a 50 mm wide polyester adhesive tape (Nitto 31B, trade name, manufactured by Nitto Denko Corporation) is placed on the surface of the release agent layer, and then on the adhesive tape. A load of 1,976 Pa was applied and heat treatment was performed at 70 ° C. for 20 hours, and a polyester adhesive tape was bonded to the release agent layer. Then, using a tensile tester, the polyester adhesive tape was peeled from the release agent layer at an angle of 180 ° (peeling speed 0.3 m / min), and the peeling force was measured.

[Residual adhesion rate]
Similarly to the measurement of the peeling force, a polyester adhesive tape was bonded to the release agent layer. Thereafter, the polyester adhesive tape was peeled off from the release agent layer, and the polyester adhesive tape was attached to a stainless steel plate. Subsequently, the polyester adhesive tape was peeled from the stainless steel plate using a tensile tester, and the peeling force X was measured.
Moreover, the polyester adhesive tape was bonded to the tetrafluoroethylene board instead of the releasing agent layer, it processed similarly, and the measured peeling force Y was measured.
And the residual adhesive rate was calculated | required from the formula of (peeling force X / peeling force Y) x100 (%).
The higher the residual adhesive rate, the better the release property of the release agent layer, and the lowering of the adhesive strength of the polyester pressure-sensitive adhesive tape due to bonding to the release agent layer is suppressed.

[Exposure resistance]
A release agent layer was formed in the same manner as in the above curable evaluation, and the release agent layer was left indoors at 25 ° C. and 50% RH for 8 hours and 1 day to be exposed to the atmosphere. The release agent layer was treated in the same manner as the above peel force, and the peel force after exposure to the atmosphere was measured.

Claims (9)

(A) Organopolysiloxane represented by the following general formula (1) and having at least two alkenyl groups in one molecule: 100 parts by mass

Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X ¹ is independently The following general formula (2-1), X ² is independently the following general formula (2-2), X ³ is independently the following general formula (2-3)

X ⁴ is each independently the following general formula (3-1), X ⁵ is each independently the following general formula (3-2), and X ⁶ is each independently the following general formula (3-3). )

It is group shown by these. R ¹ and R ² are as described above, and a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3. a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, a63 is 0 or a positive number, and these are the viscosity of the organopolysiloxane at 25 ° C. In the range of 0.05 Pa · s or more and 30% by mass toluene diluted viscosity of 70 Pa · s or less. )
Carbon atoms having (B) under following general formula (5) alkadienes 10 to 32 carbon atoms and having an unsaturated bond at both terminals represented, the unsaturated bond at the terminal represented by the following general formula (6) 8-30 One or more selected from silanes having 1 to 4 alkenyl groups and disiloxanes having 2 to 6 alkenyl groups having 8 to 30 carbon atoms having an unsaturated bond at the terminal represented by the following general formula (7) Compound: 5-20 parts by mass,
^{_{C H 2 = CH-R 3}} -CH = CH 2 (5)
^{_{(CH 2 = CH-R 3}} ) b1 SiR 4 4-b1 (6)

(Wherein R ³ is each independently a divalent hydrocarbon group having 6 to 28 carbon atoms, R ⁴ is independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 10 carbon atoms, b1 is An integer of 1 to 4, b2 is an integer of 1 to 3 independently.)
(C) The following average composition formula (8)
R ² _c1 H _c2 SiO _{(4-c1-c2) / 2} (8)
(In the formula, R ² independently represents a monovalent hydrocarbon group which is unsubstituted or does not contain an aliphatic unsaturated bond, or is substituted with a halogen atom or a cyano group, c1 is a positive number of 0.1 to 2, and c2 is 0.8. It is a positive number of 01 to 2, c1 + c2 is a positive number of 3 or less, has 2 or more SiH groups in one molecule, and has a viscosity at 25 ° C. in the range of 0.005 to 10 Pa · s. To be elected.)
An organohydrogenpolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule , wherein R ² ₂ HSiO _1/2 units (R ² does not contain an aliphatic unsaturated bond) (A non-substituted or halogen atom or cyano group-substituted monovalent hydrocarbon group) having two or more per molecule, or a mixture partially containing the organohydrogen polysiloxane : C) An amount corresponding to 1 to 20 times the total number of moles of alkenyl groups and unsaturated groups in the components (A) and (B), wherein the number of moles of hydrogen atoms bonded to silicon atoms in the component;
(D) a catalytic amount of a platinum group metal catalyst,
(E) Organic solvent: addition reaction curable type release paper or release film silicone composition containing 0 to 100,000 parts by mass. The silicone composition for release paper or release film according to claim 1, wherein the component (C) is an organohydrogenpolysiloxane represented by the following general formula (9) and / or the following general formula (10): .

(In the formula, Me is a methyl group, R ² is an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group independently containing no aliphatic unsaturated bond, and R ⁵ is independently a hydrogen atom. Or an unsubstituted or unsubstituted monovalent hydrocarbon group substituted with a halogen atom or a cyano group, wherein R ⁶ and R ⁷ are each independently an unsubstituted group other than Me that does not contain an aliphatic unsaturated bond, or A monovalent hydrocarbon group substituted with a halogen atom or a cyano group, Y ³ is each independently the following general formula (11-1), Y ⁴ is each independently the following general formula (11-2), and Y ⁵ is each independently The following general formula (11-3)

Y ⁶ is each independently the following general formula (12-1), Y ⁷ is each independently the following general formula (12-2), and Y ⁸ is each independently the following general formula (12-3) )

R ⁵ , R ⁶ and R ⁷ are as described above, c11, c12, c31, c41, c51, c61, c71 and c81 are each independently an integer of 0 to 3, c23 is 2 C13-c19, c24-c29, c32-c38, c42-c48, c52-c58, c62-c66, c72-c76, c82-c86 are integers greater than or equal to 0, c23 + c24 + c25 + c26 + c27 + c28 + c29 is an integer greater than or equal to 3. One molecule has hydrogen atoms bonded to two or more silicon atoms, and the viscosity at 25 ° C. is selected in the range of 0.005 to 10 Pa · s. ) Component (C) is a mixture of (C1) an organohydrogenpolysiloxane containing no aromatic substituent and (C2) an organohydrogenpolysiloxane containing an aromatic substituent, and these (C1) and (C 3. The silicone composition for release paper or release film according to claim 1 or 2 , wherein the mass ratio (C1) / (C2) of component C2) is from 1/9 to 9/1. Furthermore, as the component (F), any one of claims 1 to 3 containing 0.1 to 30 parts by mass with respect to the organopolysiloxane (A) 100 parts by weight of component represented by the following general formula (13) The silicone composition for release paper or release film described in 1.

(In the formula, Me is a methyl group, R ⁸ is independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group, and R ⁹ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and a non-aliphatic unsaturated bond. A substituted or halogen atom or a cyano group-substituted monovalent hydrocarbon group, and R ¹⁰ is independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an unsubstituted or halogen atom or cyano group other than Me containing no aliphatic unsaturated bond It is a substituted monovalent hydrocarbon group, f1 and f2 are integers of 1 to 3, and f3 to f5 are the viscosity of organopolysiloxane at 25 ° C. of 1 Pa · s or more and 30% by mass in toluene diluted viscosity of 100 Pa · s. (An integer chosen to fall within the following range.) Furthermore, as component (G), it has at least two alkenyl groups, and R ² _(3-g1) R ¹ _g1 SiO _1/2 siloxane unit (M ^R1R2 unit), R ² SiO _3/2 siloxane unit (T ^R2 unit) (wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, and g1 is Is an integer of 1 to 3)), the molar ratio of M ^R1R2 units / TR ² units satisfies 2/8 to 8/2, and the viscosity at 25 ° C. is in the range of 0.001 to 1 Pa · s. 10 to 100 parts by mass of an organopolysiloxane having a molecular end of M ^R1R2 unit, or an M ^R1R2 unit and a part of which is a silanol group or an alkoxy group. 4. For release paper or release film according to any one of 4 Silicone composition. Furthermore, as the component (H), organosilane represented by the following general formula (14) having at least an epoxy group and an alkoxysilyl group in one molecule and / or partial hydrolysis thereof represented by the following average composition formula (15) ( The silicone composition for release paper or release film according to any one of claims 1 to 5 , comprising 0.1 to 10 parts by mass of (co) condensed siloxane with respect to 100 parts by mass of component (A).
R ¹¹ _{h 1} (OR ¹² ) _{h 2} Si (R ¹³ ) _{(4-h 1 -h 2)} (14)
_{^{R 11 h3 (OR 12) h4}} (R 13) h5 SiO (4-h3-h4-h5) / 2 (15)
(In the formula, R ¹¹ is a monovalent organic group containing an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms and may contain an ether bond, and some of them are hydrolyzed to become a hydroxyl group. R ¹³ is an unsubstituted or monovalent hydrocarbon group substituted with a halogen atom or a cyano group, h1 and h2 are integers satisfying 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, and h3 to h5 Is a positive number satisfying 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, and the partially hydrolyzed (co) condensed siloxane has a viscosity at 25 ° C. in the range of 0.001 to 1 Pa · s. (Selected from positive numbers.) Furthermore, as a component (I), a siloxane unit (M unit) represented by the following general formula (16) and a siloxane unit (Q unit) represented by the following formula (17) are used in a molar ratio (M unit / Q unit). The silicone composition for release paper or release film according to any one of claims 1 to 6 , comprising 1 to 100 parts by mass of MQ resin having 2/8 to 8/2 per 100 parts by mass of component (A). object.
R ² _(3-i1) R ¹ _i1 SiO _1/2 (16)
SiO _4/2 (17)
Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen- or cyano-substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and i1 is 0 to 3 Is an integer.) Further, (J) as the component, a release paper or a release according to any one of claims 1 to 7, containing 0.1 to 5 parts by weight of the nonionic surfactant component (A) 100 parts by weight Silicone composition for film. The release paper or release film in which the cured film of the silicone composition for release paper or release film of any one of Claims 1-8 was formed.