JP2011236289A - Silicone composition for release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone composition for a release film which gives a layer of peelability which has adhesion further improved to a plastic film.SOLUTION: The silicone composition for a release film includes the following (A)-(C): (A) 100 pts.mass of curable organopolysiloxane composition; (B) addition product of the following diphenyl alkane derivative and organosilicon compound: (B1) 0-2.7 pts.mass of addition product of diphenyl alkane derivative with organosilane or organosiloxane derivative which has one or more organooxy groups, and (B-2) 0.3-3 pts.mass of addition product of diphenyl alkane derivative with organosiloxane derivative which has one or more hydrogen atoms (SiH group) which directly bond to a silicon atom (the sum total of (B1) and (B2) is 0.3-3 pts.mass); and (C) 0.1-2 pts.mass of isocyanurate derivative which has one or more epoxy groups or trialkoxysilyl groups which combine with a nitrogen atom in one molecule.

Description

  The present invention relates to a silicone composition for a release film, and more particularly to a silicone composition for a release film that provides a cured film having excellent adhesion to various film substrates.

  It is practiced to provide a layer on the surface of various base materials such as laminated paper and plastic film so that the base material can be peeled off. A silicone composition is used as a material for forming such a peelable layer. For example, a silicone composition comprising an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and a platinum compound is known (special feature). Japanese Utility Model Publication No. 62-86061: Patent Document 1).

  The silicone composition is frequently used because of its excellent curing property and good pot life. However, depending on the substrate, the adhesion of the cured film of the composition to the substrate may not be sufficient, and there is a problem that the substrate that can be applied is limited or the substrate needs to be pretreated. is there.

  In recent years, the use of plastic films with uniform and stable quality, high smoothness, and thinness as a base material is increasing, and there is a demand for improved adhesion between these plastic films and cured silicone films. Is getting stronger.

Various attempts have been made to improve adhesion. First, there is a method of blending a silicone composition with a material having better adhesion to a plastic such as an organic resin or a silane coupling agent than a silicone resin. However, the film obtained by this method tends to have low peelability. Further, a method for improving the adhesion is known by providing the base polymer structure of the silicone resin with a branched structure containing an RSiO _3/2 unit, but the adhesion is not sufficient (Japanese Patent Laid-Open No. 63-63). No. 251465, Japanese Patent Publication No. 3-19267, Japanese Patent Laid-Open No. 9-78032, Japanese Patent Laid-Open No. 11-193366: Patent Documents 2 to 5). A method of using a solvent-type silicone composition and a solventless silicone composition in combination is known for the purpose of reducing the speed dependency of the release performance, but in terms of adhesion, it exceeds the solvent-type silicone composition. (See JP 2000-169794 A, JP 2000-177058 A: Patent Documents 6 and 7). Furthermore, an additive having an excellent effect of improving adhesion, which is composed of a siloxane compound to which a hydrocarbon group having a specific structure is bonded is known (Japanese Patent Laid-Open Nos. 2000-265062 and 2005-2142: Patent Documents 8 and 9). Although the adhesion improver can obtain good results for a specific application, it cannot provide a satisfactory effect for a release film. In addition, the present inventors blended a base material by blending a silicone composition for release paper with a siloxane compound having two or more polycyclic hydrocarbon groups containing a carbon-carbon double bond in one molecule. It was found that a cured film having excellent adhesion to the resin was obtained (Japanese Patent Laid-Open No. 2005-15666: Patent Document 10). Furthermore, it has also been found that stable adhesion can be obtained for a wide range of substrate species by combining a diphenylalkane derivative and an isocyanurate derivative in combination (Japanese Patent Laid-Open No. 2007-9072: Patent Document 11).

  As described above, methods for improving the adhesion without affecting the peelability of the silicone film have been proposed so far, but further improvements are required.

JP-A-62-86061 JP-A-63-251465 Japanese Patent Publication No. 3-19267 JP-A-9-78032 JP-A-11-193366 JP 2000-169794 A JP 2000-177058 A JP 2000-265062 A Japanese Patent Laying-Open No. 2005-2142 Japanese Patent Laid-Open No. 2005-15666 JP 2007-9072 A

  This invention is made | formed in view of the said situation, and it aims at providing the silicone composition for peeling films which gives the peelable layer which has the adhesiveness further improved with respect to the plastic film.

  As a result of intensive studies to achieve the above object, the present inventors have found that a curable organopolysiloxane composition includes an adduct of a diphenylalkane derivative having a specific structure and an organosilicon compound, and one molecule. For a release film that provides a peelable layer with improved adhesion to a plastic film by incorporating a specific amount of an isocyanurate derivative having at least one epoxy group or trialkoxysilyl group bonded to a nitrogen atom The inventors have found that a silicone composition can be obtained, and have made the present invention.

〔式中、Ｒ⁴は互いに独立に、水素原子又はメチル基であり、Ｒ⁵は互いに独立に、水酸基又はメチル基であり、ａは０，１又は２であり、Ａは互いに独立に、下記一般式（ｉ）又は（ｉｉ）

（式中、Ｒ⁶は炭素数１〜１０の非置換又は置換１価炭化水素基であり、Ｒ⁷は酸素原子を介在してもよい炭素数１〜８の非置換又は置換１価炭化水素基であり、ｂは１〜３の整数であり、ｃは０又は１であり、但しｂ＋ｃは２又は３であり、ｘは１〜８の整数である。）
で表される基である。〕
で示される化合物であり、前記（Ｂ２）成分が、下記一般式（ＩＩＩ）又は（ＩＶ）

〔式中、Ｒ⁴、Ｒ⁵、ａは上記と同じ。Ｂは互いに独立に、下記一般式（ｉｉｉ）又は（ｉｖ）

（式中、Ｒ⁶は上記と同じ。Ｒ⁸は水素原子又は炭素数１〜８の非置換もしくは置換１価炭化水素基であり、Ｚは下記式

で表される置換基であり、ｄ、ｇは０又は１〜１０の整数、ｅ、ｈ、ｊは０又は１〜５の整数、ｆは０又は１〜３の整数、ｉは０又は１〜７の整数、但しｉ＋ｊは２〜７の整数であり、ｄ、ｆ、ｇ、ｉは１分子中に少なくとも１個のＳｉＨ基を有するように選ばれる。〕
で示される化合物であることを特徴とする請求項１〜３のいずれか１項に記載の剥離フィルム用シリコーン組成物。
〔請求項５〕
前記（Ｃ）成分が、下記一般式（５）で表される化合物であることを特徴とする請求項１〜４のいずれか１項に記載の剥離フィルム用シリコーン組成物。

〔式中、Ｔは互いに独立に、下記式（ｖ）もしくは（ｖｉ）で示される基、又は炭素数１〜８のアルキル基、アリール基、アラルキル基又は単官能性アルケニル基であり、少なくとも１個のＴが下記式（ｖ）又は（ｖｉ）で示される基である。
（Ｒ¹Ｏ）₃Ｓｉ−Ｒ²− （ｖ）
（式中、Ｒ¹は炭素数１〜８のアルキル基であり、Ｒ²は炭素数２〜５のアルキレン基である。）
Ｑ−Ｒ³− （ｖｉ）
（式中、Ｑはエポキシ基であり、Ｒ³は炭素数１〜３のアルキレン基である。）〕 Therefore, this invention provides the silicone composition for peeling films shown below.
[Claim 1]
A silicone composition for a release film comprising the following components (A) to (C).
(A) Curable organopolysiloxane composition: 100 parts by mass,
(B) Adduct of the following diphenylalkane derivative and organosilicon compound (B1) Adduct of diphenylalkane derivative and organosilane or organosiloxane derivative having at least one organooxy group: 0 to 2.7 parts by mass ,
(B2) Adduct of a diphenylalkane derivative and an organosiloxane derivative having a hydrogen atom (SiH group) directly bonded to at least one silicon atom: 0.3 to 3 parts by mass
(However, the total amount of (B1) and (B2) is 0.3 to 3 parts by mass.)
(C) Isocyanurate derivatives having at least one epoxy group or trialkoxysilyl group bonded to a nitrogen atom in one molecule: 0.1 to 2 parts by mass.
[Claim 2]
The said (A) component consists of the following (1)-(3) component, The silicone composition for peeling films of Claim 1 characterized by the above-mentioned.
(1) an organopolysiloxane having at least two alkenyl groups in one molecule;
(2) An amount of an organohydrogenpolysiloxane having at least three SiH groups in one molecule, wherein the total number of moles of SiH groups is 1 to 10 times the total number of moles of alkenyl groups contained in (1),
(3) A catalytic amount of a platinum group metal catalyst.
[Claim 3]
The silicone composition for a release film according to claim 1, wherein the component (A) comprises the following components (a) to (c).
(A) an organopolysiloxane having at least two hydroxyl groups in one molecule;
(B) An organopolysiloxane having at least three SiH groups and / or hydrolyzable groups in one molecule, wherein the total number of moles of SiH groups and hydrolyzable groups is the total number of hydroxyl groups contained in (a) An amount equivalent to 5 to 200 times
(C) A catalytic amount of a condensation catalyst.
[Claim 4]
The component (B1) is represented by the following general formula (I) or (II)

[In the formula, R ⁴ independently represents a hydrogen atom or a methyl group, R ⁵ independently represents a hydroxyl group or a methyl group, a represents 0, 1 or 2, and A independently represents General formula (i) or (ii)

(In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms which may intervene with an oxygen atom. And b is an integer of 1 to 3, c is 0 or 1, provided that b + c is 2 or 3, and x is an integer of 1 to 8.)
It is group represented by these. ]
In which the component (B2) is represented by the following general formula (III) or (IV):

[Wherein R ⁴ , R ⁵ and a are the same as above. B are independently of each other the following general formula (iii) or (iv)

(In the formula, R ⁶ is the same as above. R ⁸ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and Z is the following formula:

D and g are 0 or an integer of 1 to 10, e, h and j are 0 or an integer of 1 to 5, f is an integer of 0 or 1 to 3, and i is 0 or 1 An integer of -7, wherein i + j is an integer of 2-7, and d, f, g, i are selected so as to have at least one SiH group in one molecule. ]
The silicone composition for a release film according to any one of claims 1 to 3, wherein the composition is a compound represented by formula (1).
[Claim 5]
The said (C) component is a compound represented by following General formula (5), The silicone composition for peeling films of any one of Claims 1-4 characterized by the above-mentioned.

[In the formula, T is independently of each other a group represented by the following formula (v) or (vi), an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, or a monofunctional alkenyl group; Each T is a group represented by the following formula (v) or (vi).
(R ¹ O) ₃ Si—R ² − (v)
(In the formula, R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² is an alkylene group having 2 to 5 carbon atoms.)
QR- ³ (vi)
(In the formula, Q is an epoxy group, and R ³ is an alkylene group having 1 to ³ carbon atoms.)]

  The cured film obtained from the silicone composition for a release film of the present invention has adhesive properties with a substrate that is remarkably superior to that of an organopolysiloxane film while having the release characteristics of an organopolysiloxane film.

The silicone composition for a release film of the present invention contains the following components (A) to (C).
(A) a curable organopolysiloxane composition (B) an adduct of a diphenylalkane derivative containing the following (B2) or the following (B1) and (B2) and an organosilicon compound (B1) a diphenylalkane derivative and at least one Adduct with organosilane or organosiloxane derivative having organooxy group (B2) Adduct with diphenylalkane derivative and organosiloxane derivative having hydrogen atom (SiH group) directly bonded to at least one silicon atom (C) Isocyanurate derivatives having at least one epoxy group or trialkoxysilyl group bonded to a nitrogen atom in one molecule

As the curable organopolysiloxane composition as the component (A) of the present invention, a known curing type organopolysiloxane composition can be used, but an addition reaction curable organopolysiloxane composition or a condensation curable organopolysiloxane. A siloxane composition is preferred. In this case, the addition reaction curable organopolysiloxane composition is:
(1) an organopolysiloxane having at least two alkenyl groups in one molecule;
(2) an organohydrogenpolysiloxane having at least three SiH groups in one molecule;
(3) What consists only of a platinum group metal catalyst is preferable, and as a condensation curable organopolysiloxane composition,
(A) an organopolysiloxane having at least two hydroxyl groups in one molecule;
(B) an organopolysiloxane having at least three SiH groups and / or hydrolyzable groups in one molecule;
(C) Those consisting only of a condensation catalyst are preferred.

Addition reaction curable organopolysiloxane composition The organopolysiloxane having at least two alkenyl groups in one molecule, which is the component (1) of the addition reaction curable organopolysiloxane composition, is represented by the following general formula (1). Those represented are preferred.

（式中、Ｒ¹¹は脂肪族不飽和結合を有しない１価有機基であり、Ｒ¹²はアルケニル基であり、Ｘ¹は下記式

で示される基である。ａ１、ｂ１、ｃ１、ｄ１、ｅ１は、オルガノポリシロキサンの２５℃における粘度が０．１Ｐａ・ｓ以上、３０質量％トルエン溶液での２５℃における粘度が７０Ｐａ・ｓ以下であることを満たす正数であり、ｂ１、ｃ１、ｄ１、ｅ１は０であってもよい。α及びβはそれぞれ独立に０又は１〜３の整数であるが、１分子中にアルケニル基を２個以上有する。）

(In the formula, R ¹¹ is a monovalent organic group having no aliphatic unsaturated bond, R ¹² is an alkenyl group, and X ¹ is represented by the following formula:

It is group shown by these. a1, b1, c1, d1, and e1 are positive numbers satisfying that the viscosity of the organopolysiloxane at 25 ° C. is 0.1 Pa · s or more and the viscosity at 25 ° C. in a 30 mass% toluene solution is 70 Pa · s or less. And b1, c1, d1, and e1 may be zero. α and β are each independently an integer of 0 or 1 to 3, but have two or more alkenyl groups in one molecule. )

In formula (1), R ¹¹ is a monovalent organic group not containing an aliphatic unsaturated bond, preferably a group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. For example, C1-C12 alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, C4-C20 cycloalkyl groups, such as a cyclohexyl group, C6-C20, such as a phenyl group and a tolyl group Aryl groups, hydrogen atoms bonded to carbon atoms of these groups, some or all of which are substituted with halogen atoms, cyano groups, etc., unsubstituted or substituted monovalent groups such as chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. A C2-C20 epoxy group having a hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group or a methoxyethoxy group, and an epoxy group such as a glycidyl group or a glycidyloxy group An organic group selected from a substituted alkyl group and the like. In view of the properties of the cured film obtained, it is preferable that at least 80 mol% of R ¹¹ contained in the whole organopolysiloxane as component (1) is a methyl group.

R ¹² is preferably an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group, or a butenyl group, and is preferably a vinyl group industrially. (1) The number of alkenyl groups contained in one molecule of the organopolysiloxane is 2 or more, and preferably (1) the amount per 100 g of the organopolysiloxane is 0.001 to 0.1 mol. . When the amount of alkenyl group is less than the lower limit, curability is lowered, and when the amount exceeds the upper limit, mold releasability of the cured film is lowered.

  A1, b1, c1, d1, and e1 in the formula (1) are the viscosity of the organopolysiloxane at 25 ° C. of 0.1 Pa · s or more and the viscosity at 25 ° C. in a 30 mass% toluene solution of 70 Pa · s or less. It is a positive number that satisfies a certain condition, and b1, c1, d1, and e1 may be zero. α and β are each independently an integer of 0 or 1-3. More preferably, the number c1 + b1 × (1 + e1 + β) + 2α of alkenyl groups contained in one molecule is selected in the range of 2 to 1,500. Further, a1, b1, c1, d1, and e1 are more preferably selected so that the degree of polymerization a1 + c1 + b1 × (d1 + e1 + 1) +2 is in the range of 50 to 10,000.

  (1) The range of the viscosity at 25 ° C. of the organopolysiloxane is 0.1 Pa · s or more, particularly 0.15 Pa · s or more, and 30 Pa% or less, particularly 60 Pa · s or less in a 30% by mass toluene solution. Is preferred. If the viscosity is less than the lower limit, the release property of the cured film is lowered, and if the viscosity exceeds the upper limit, the coatability is lowered. The viscosity is a value of absolute viscosity at 25 ° C. measured by a rotational viscometer (hereinafter the same).

  (1) The main chain structure of the organopolysiloxane may be a straight chain or may include a branched structure in which b1 is not 0.

  Organohydrogen having at least 3, preferably 3 to 1,000 hydrogen atoms (SiH groups) directly bonded to silicon atoms in one molecule, which is component (2) of the addition reaction curable organopolysiloxane composition The polysiloxane is used as an addition reaction with the organopolysiloxane of component (1). As the component (2), those represented by the following average composition formula (2) are preferable.

R ¹¹ _f1 H _g1 SiO _{(4-f1-g1) / 2} (2)
(In the formula, R ¹¹ is the same as above. F1 is 0 ≦ f1 ≦ 3, g1 is 0 <g1 ≦ 3, preferably 0.2 ≦ g1 ≦ 1, provided that f1 + g1 is a positive number of 1 ≦ f1 + g1 ≦ 3. is there.)

  (2) The molecular structure of the organohydrogenpolysiloxane may be linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s.

(2) Examples of the organohydrogenpolysiloxane include those shown below.

Ｚは下記式で表される基である。

In the above formula, Y is a group represented by the following formula:

Z is a group represented by the following formula.

  In the above formula, h1, l1, and n1 are integers of 3 to 500, m1, p1, and s1 are integers of 1 to 500, i1, j1, k1, o1, q1, r1, t1, u1, v1, and w1 are It is 0 or an integer of 1 to 500.

  The above (2) organohydrogenpolysiloxane contains 1 to 10 times, particularly 1 to 5 times the total number of moles of alkenyl groups contained in the component (1). Used in quantity. (2) If the number of moles of SiH groups contained in the component is less than the lower limit, the curability is insufficient. On the other hand, even if the amount exceeds the upper limit, a significant increase in curability is not observed. In some cases, the peelability may decrease. The amount of typical (2) organohydrogenpolysiloxane in the above range is (1) 0.1 to 20 parts by mass with respect to 100 parts by mass of organopolysiloxane.

The platinum group metal catalyst which is component (3) of the addition reaction curable organopolysiloxane composition is a catalyst for addition reaction of (1) organopolysiloxane and (2) organohydrogenpolysiloxane. All known materials can be used. Examples of the platinum group metal catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, rhodium, rhodium-olefin complex, and the like.
The (3) platinum group metal catalyst is used in a catalytic amount, and usually 5 to 1,000 ppm (mass ratio) is added as the amount of platinum or rhodium with respect to the total mass of the components (1) and (2). For example, a sufficient cured film can be formed, but can be appropriately increased or decreased according to the reactivity of each component or the desired curing rate.

Condensation-Curable Organopolysiloxane Composition The organopolysiloxane having at least two hydroxyl groups in one molecule, which is component (a) of the condensation-curable organopolysiloxane composition, is represented by the following general formula (3) Is preferred.

（式中、Ｒ¹³は水酸基であり、Ｒ¹⁴は１価有機基であり、Ｘ²は下記式

で示される基である。ａ２、ｂ２、ｃ２、ｄ２、ｅ２は、オルガノポリシロキサンの２５℃における粘度が０．１Ｐａ・ｓ以上、３０質量％トルエン溶液での２５℃における粘度が７０Ｐａ・ｓ以下であることを満たす正数であり、ｂ２、ｃ２、ｄ２、ｅ２は０であってもよい。γ及びδはそれぞれ独立に０又は１であるが、１分子中に水酸基を２個以上有する。）

(Wherein R ¹³ is a hydroxyl group, R ¹⁴ is a monovalent organic group, and X ² is the following formula:

It is group shown by these. a2, b2, c2, d2, and e2 are positive numbers satisfying that the viscosity of the organopolysiloxane at 25 ° C is 0.1 Pa · s or more and the viscosity at 25 ° C in a 30 mass% toluene solution is 70 Pa · s or less. And b2, c2, d2, and e2 may be zero. γ and δ are each independently 0 or 1, but each molecule has two or more hydroxyl groups. )

In the formula (3), as the monovalent organic group for R ¹⁴ , in addition to the groups exemplified as the monovalent organic group not containing the aliphatic unsaturated bond of R ¹¹ , a vinyl group, an allyl group, a propenyl group, etc. Examples include alkenyl groups having 2 to 6 carbon atoms. From the viewpoint of the properties of the cured film obtained, it is preferable that at least 80 mol% of R ¹⁴ contained in the whole organopolysiloxane as the component (a) is a methyl group.

  (I) The number of hydroxyl groups contained in one molecule of the organopolysiloxane is 2 or more. Desirably, (a) the content per 100 g of the organopolysiloxane is 0.0001 to 0.1 mol. When the amount of the hydroxyl group is less than the lower limit, curability is lowered, and when the amount exceeds the upper limit, the pot life is shortened and handling may be difficult.

  A2, b2, c2, d2, and e2 in the formula (3) are those in which the viscosity of the organopolysiloxane at 25 ° C. is 0.1 Pa · s or more and the viscosity at 25 ° C. in a 30 mass% toluene solution is 70 Pa · s or less. It is a positive number that satisfies a certain condition, and b2, c2, d2, and e2 may be zero. γ and δ are each independently 0 or 1. More preferably, the number of hydroxyl groups c2 + b2 × (e2 + δ) + 2γ contained in one molecule is selected in the range of 2 to 150. Further, a2, b2, c2, d2, and e2 are more preferably selected such that the degree of polymerization a2 + c2 + b2 × (d2 + e2 + 1) +2 is in the range of 50 to 20,000.

  (I) The viscosity range at 25 ° C. of the organopolysiloxane is 0.1 Pa · s or more, particularly 0.15 Pa · s or more, and 70 Pa · s or less, particularly 60 Pa · s or less in a 30% by mass toluene solution. Is preferred. When the viscosity is less than the lower limit, it is difficult to apply the silicone composition for a release film. When the viscosity exceeds the upper limit, workability is reduced.

  (A) The main chain structure of the organopolysiloxane may be a straight chain or may include a branched chain structure in which b2 is not 0.

  The organopolysiloxane having at least 3, preferably 3 to 1,000, SiH groups and / or hydrolyzable groups in one molecule, which is the component (b) of the condensation curable organopolysiloxane composition, is ) Subject to condensation reaction with organopolysiloxane. When the component (b) is an organopolysiloxane having a SiH group, the same component as the component (2) can be used.

In addition, as the organopolysiloxane having at least three hydrolyzable groups in one molecule, those represented by the following average composition formula (4) can be used.
R ¹¹ _f2 W _g2 SiO _{(4-f2-g2) / 2} (4)
(In the formula, R ¹¹ is the same as above. W represents a hydrolyzable group, f2 is a positive number satisfying 0 ≦ f2 ≦ 3, g2 is 0 <g2 ≦ 3, and f2 + g2 is 1 ≦ f2 + g2 <3.)

  In the above formula, the hydrolyzable group W includes an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group and an isopropenoxy group directly bonded to a silicon atom, an acyloxy group such as an acetoxy group, and ethylamino. And an amino group such as a group, an amide group, an oxime group such as an ethylmethylbutanoxime group, and a halogen atom such as chlorine and bromine.

  The molecular structure of the organopolysiloxane having a hydrolyzable group may be linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s.

As the organopolysiloxane having a hydrolyzable group, for example, the following organopolysiloxane can be used.

In the formula, W _{is, CH 3 COO-, CH 3 (} C 2 H 5) C = NO -, (C 2 H 5) 2 N-, CH 3 CO (C 2 H 5) N-, CH 2 = A hydrolyzable group such as (CH ₃ ) CO— is shown, and x2, y2, and z2 are 0 or an integer in the range of 1 to 500.

  As the component (b), an organopolysiloxane having a SiH group may be used alone, an organopolysiloxane having a hydrolyzable group may be used alone, or a mixture thereof may be used. Moreover, you may use what has both a hydrolysable group and SiH group in 1 molecule.

  The component (b) is used in such an amount that the total number of moles of SiH groups and hydrolyzable groups contained is 5 to 200 times the number of moles of hydroxyl groups contained in the component (a). . (B) If the total number of moles of SiH groups and hydrolyzable groups contained in the component is less than the lower limit, the amount of crosslinking bonds due to the chemical reaction between hydroxyl groups and SiH groups or hydroxyl groups and hydrolyzable groups is sufficient. However, the peelability tends to be reduced. On the other hand, even if blended in excess of the above upper limit, there is no significant increase in the effect of improving the peelability, but there is a tendency to reduce the pot life of the silicone composition for a release film. In the case of typical organopolysiloxane, the amount is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of component (a).

  The (c) condensation catalyst of the condensation curable organopolysiloxane composition is used when the (a) component and the (b) component are reacted, and promotes the condensation reaction to cross-link, thereby releasing the cured film and durability. Used to enhance the sex. Examples of the (c) condensation catalyst include hydrochloric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, maleic acid, trifluoroacetic acid and other acids, sodium hydroxide, potassium hydroxide, sodium ethoxide, tetraethylammonium hydroxide, and the like. Salts such as alkalis, ammonium chloride, ammonium acetate, ammonium fluoride, sodium carbonate, organic acid salts of metals such as magnesium, aluminum, zinc, iron, zirconium, cerium, titanium, tin, and organic metals such as alkoxides and chelate compounds Compounds. For example, zinc dioctate, titanium tetraisopropoxide, aluminum tributoxide, zirconium tetraacetylacetonate, dioctyltin dioctate and the like can be mentioned.

  (C) The condensation catalyst is used in a catalytic amount, and is usually blended in an amount of 0.1 to 5% (mass ratio) as an active ingredient with respect to the total mass of components (A) and (B) in component (A). However, it can be appropriately increased or decreased depending on the reactivity of each component or the desired curing rate.

Next, the adduct of the diphenylalkane derivative and the organosilicon compound (hereinafter referred to as “adduct”), which is the component (B) of the present invention, has an organosilane or organosiloxane part and an aromatic part having different polarities. Thereby, the adhesive force to the film of the silicone composition for peeling films is improved.
Examples of the adduct include the following components (B1) and (B2). In the present invention, the component (B2) is essential, preferably the component (B2) alone, or the components (B1) and (B2). Are blended.
(B1) an adduct of a diphenylalkane derivative and an organosilane or organosiloxane derivative having at least one organooxy group,
(B2) An adduct of a diphenylalkane derivative and an organosiloxane derivative having a hydrogen atom (SiH group) directly bonded to at least one silicon atom.

The production method of the adduct is not limited to a specific one. For example, a diphenylalkane derivative having at least one unsaturated substituent in the phenyl group and a silicon compound having an active hydrogen such as a SiH group or a mercapto group (organosilane or It can be obtained by addition reaction with an organosiloxane derivative). Examples of the unsaturated substituent include a hydrocarbon substituent containing a double bond, for example, a vinyl group (CH ₂ ═CH—). The vinyl group and the SiH group or SH group react to form a bond represented by —CH ₂ —CH ₂ —Si— or —CH ₂ —CH ₂ —S—.

〔式中、Ｒ⁴は互いに独立に、水素原子又はメチル基であり、Ｒ⁵は互いに独立に、水酸基又はメチル基であり、ａは０，１又は２であり、Ａは互いに独立に、下記一般式（ｉ）又は（ｉｉ）

（式中、Ｒ⁶は炭素数１〜１０の非置換又は置換１価炭化水素基であり、Ｒ⁷は酸素原子を介在してもよい炭素数１〜８の非置換又は置換１価炭化水素基であり、ｂは１〜３の整数であり、ｃは０又は１であり、但しｂ＋ｃは２又は３であり、ｘは１〜８の整数である。）
で表される基である。〕 As the component (B1), compounds represented by the following general formulas (I) and (II) are preferable.

[In the formula, R ⁴ independently represents a hydrogen atom or a methyl group, R ⁵ independently represents a hydroxyl group or a methyl group, a represents 0, 1 or 2, and A independently represents General formula (i) or (ii)

(In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms which may intervene with an oxygen atom. And b is an integer of 1 to 3, c is 0 or 1, provided that b + c is 2 or 3, and x is an integer of 1 to 8.)
It is group represented by these. ]

R ⁶ may be the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl Alkyl group such as cyclohexyl group; cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group, propenyl group, butenyl group, hexenyl group; aryl group such as phenyl group, tolyl group; benzyl group, phenylethyl group, etc. Or a group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as chlorine, fluorine or bromine, such as a trifluoropropyl group. Among these, a methyl group is preferable.
R ⁷ may be the same or different, and is a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 7 carbon atoms that may intervene an oxygen atom, specifically exemplified by R ⁶ above. And an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and an ethoxyethyl group. Among these, an alkyl group and an alkoxyalkyl group are preferable, and a methyl group is most preferable industrially.

  In the formula (ii), when c is 1, a diphenylalkane molecule different from that in which the mercapto group is reacted, for example, a diphenylalkane molecule to which a previously reacted mercapto residue is bonded. Also includes those that are joined.

Examples of the compounds represented by the above formulas (I) and (II) include the following.

Component (B1) may be a single type or a mixture of two or more types.
(B1) The compounding quantity of component is 0-2.7 mass part with respect to 100 mass parts of (A) curable organopolysiloxane composition, Preferably it is 0.1-2.6 mass part. If the blending amount exceeds the upper limit, the release property of the cured film is lowered.

〔式中、Ｒ⁴、Ｒ⁵、ａは上記と同じ。Ｂは互いに独立に、下記一般式（ｉｉｉ）又は（ｉｖ）

（式中、Ｒ⁶は上記と同じ。Ｒ⁸は水素原子又は炭素数１〜８の非置換もしくは置換１価炭化水素基であり、Ｚは下記式

で表される置換基であり、ｄ、ｇは０又は１〜１０の整数、ｅ、ｈ、ｊは０又は１〜５の整数、ｆは０又は１〜３の整数、ｉは０又は１〜７の整数、但しｉ＋ｊは２〜７の整数であり、ｄ、ｆ、ｇ、ｉは１分子中に少なくとも１個、好ましくは少なくとも２個のＳｉＨ基を有するように選ばれる。〕 As the component (B2), compounds represented by the following general formulas (III) and (IV) are preferable.

[Wherein R ⁴ , R ⁵ and a are the same as above. B are independently of each other the following general formula (iii) or (iv)

(In the formula, R ⁶ is the same as above. R ⁸ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and Z is the following formula:

D and g are 0 or an integer of 1 to 10, e, h and j are 0 or an integer of 1 to 5, f is an integer of 0 or 1 to 3, and i is 0 or 1 An integer of ˜7, where i + j is an integer of 2-7, and d, f, g, i are selected to have at least 1, preferably at least 2, SiH groups in one molecule. ]

R ⁸ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and the monovalent hydrocarbon group is the same as the one having 1 to 8 carbon atoms exemplified for R ⁶ above. Is mentioned.

（式中、ｄ’は１〜１０の整数、ｅ’は１〜５の整数、ｊ’は１〜５の整数、但しｉ＋ｊは２〜７の整数である。） Specific examples of the substituent represented by the above formulas (iii) and (iv) include the following.

(In the formula, d ′ is an integer of 1 to 10, e ′ is an integer of 1 to 5, j ′ is an integer of 1 to 5, provided that i + j is an integer of 2 to 7)

Examples of the compounds represented by the above formulas (III) and (IV) are as follows.

Component (B2) may be a single type or a mixture of two or more types.
(B2) The compounding quantity of a component is 0.3-3 mass parts with respect to 100 mass parts of (A) curable organopolysiloxane composition, Preferably it is 0.4-3 mass parts. If the blending amount is less than the lower limit, the effect of improving adhesion is small, and if the blending amount exceeds the upper limit, the curability is lowered.

  The component (B) may be the component (B2) used alone or may be a mixture of two or more types including the component (B2). (B) The total compounding quantity of a component is 0.3-3 mass parts with respect to 100 mass parts of (A) curable organopolysiloxane composition, It is preferable that it is 0.5-2 mass parts especially. If the blending amount is less than the lower limit value, satisfactory adhesiveness cannot be obtained, and even if the blending amount exceeds the upper limit value, an improvement in adhesion proportional to the blending amount cannot be obtained.

  (C) component of this invention is an isocyanurate derivative, Comprising to the silicone composition for peeling films with (B) component, it is for improving the adhesiveness of the cured film formed. Although only the component (B) has different adhesion improving effects depending on the substrate type and use conditions, the combined use of the component (C) makes it possible to obtain higher adhesion more stably. That is, although not intended to limit the present invention, a mechanism capable of obtaining high adhesion is considered as follows. The biphenylalkane part of the component (B) interacts with the film substrate, the alkoxysilyl group chemically bonds with the silicone film, and the SiH group similarly chemically bonds with the silicone film. Thereby, it acts so that a film base material and a silicone layer may be tied. In the component (C), it is considered that the isocyanurate group is mainly chemically bonded to the film base material, and the epoxy group or alkoxysilyl group is mainly bonded to the silicone layer to adhere both layers. Even with only an epoxy group and / or an alkoxysilyl group, a certain degree of adhesion improving effect can be obtained, but not as effective as an isocyanurate group. On the other hand, the isocyanurate group alone has low compatibility with the silicone layer and can also act as a catalyst poison. In this way, by using together the component (B) and the component (C) each having a different part of the interaction between the film substrate and the silicone film, the adhesion effect is increased, and at the same time, the type and surface treatment state of the film Regardless of the case, it is considered that a stable effect can be obtained.

〔式中、Ｔは互いに独立に、下記式（ｖ）もしくは（ｖｉ）で示される基、又は炭素数１〜８のアルキル基、アリール基、アラルキル基又は単官能性アルケニル基であり、少なくとも１個のＴが下記式（ｖ）又は（ｖｉ）で示される基である。
（Ｒ¹Ｏ）₃Ｓｉ−Ｒ²− （ｖ）
（式中、Ｒ¹は炭素数１〜８のアルキル基であり、Ｒ²は炭素数２〜５のアルキレン基である。）
Ｑ−Ｒ³− （ｖｉ）
（式中、Ｑはエポキシ基であり、Ｒ³は炭素数１〜３のアルキレン基である。）〕 Component (C) is an isocyanuric acid ester in which a hydrogen atom bonded to a nitrogen atom of isocyanuric acid is substituted, and at least one of the substituents is an epoxy group or a trialkoxysilyl group. Preferably, what is represented by the following general formula (5) is used.

[In the formula, T is independently of each other a group represented by the following formula (v) or (vi), an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, or a monofunctional alkenyl group; Each T is a group represented by the following formula (v) or (vi).
(R ¹ O) ₃ Si—R ² − (v)
(In the formula, R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² is an alkylene group having 2 to 5 carbon atoms.)
QR- ³ (vi)
(In the formula, Q is an epoxy group, and R ³ is an alkylene group having 1 to ³ carbon atoms.)]

  In the above formula (5), as the alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, A pentyl group, a hexyl group, an octyl group, etc. are mentioned. Examples of the aryl group and aralkyl group include those having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of monofunctional alkenyl groups include linear or branched alkenyl groups having 2 to 5 carbon atoms and one carbon-carbon double bond, such as vinyl, allyl, and isopropenyl groups. , Butenyl group, pentenyl group and the like. In these, an allyl group is preferable.

R ¹ in formula (v) is an alkyl group having 1 to 8 carbon atoms, the same alkyl groups as exemplified above can be exemplified. A methyl group and an ethyl group are preferable, and a methyl group is more preferable. Examples of the alkylene group having 2 to 5 carbon atoms of R ² include an ethylene group, a propylene group, a butylene group, and a pentylene group. Among these, a propylene group is preferable. Examples of the organic group represented by the formula (v) include a trimethoxysilylethyl group, a trimethoxysilylpropyl group, a triethoxysilylethyl group, and a triethoxysilylpropyl group. A trimethoxysilylpropyl group and a triethoxysilylpropyl group are preferred.

R ³ in formula (vi) is an alkylene group having 1 to 3 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Examples of the organic group represented by the formula (vi) include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, and the like. Of these, 2,3-epoxypropyl groups are preferred.

The isocyanurate derivative represented by the formula (5) is obtained by cyclizing an organic isocyanate represented by the following general formula (6) using a basic catalyst such as phosphine, an alkali metal alkoxide, or an organic tin salt. Can be obtained.
T-NCO (6)
(Wherein T is the same as above)

However, the isocyanurate having a Q—R ³ — group has a carbon-carbon double bond of an aliphatic unsaturated group-substituted isocyanurate represented by the following formula (7), such as formic acid and peracetic acid. It can be obtained by oxidizing with a peracid.

（式中、Ｋは単官能性アルケニル基を示し、Ｔについて上記した単官能アルケニル基であってよい。ＬはＫ、又は単官能アルケニル基以外のＴから選択される基を示す。）

(In the formula, K represents a monofunctional alkenyl group and may be the monofunctional alkenyl group described above for T. L represents a group selected from K or T other than the monofunctional alkenyl group.)

The isocyanurate having a (R ¹ O) ₃ Si—R ² — group is an organosilicon compound represented by the following general formula (8) and an isocyanurate represented by the above formula (7) and the presence of a platinum catalyst. It can also be obtained by reacting below.
(R ¹ O) ₃ Si—R ² —H (8)
(In the formula, R ¹ and R ² are the same as above.)

  In the production of the component (C), the target substance may be isolated after completion of the reaction, but a reaction mixture from which unreacted substances, by-products and catalysts have been removed can also be used.

(C) As a component, what is shown with the following structural formula is illustrated. In the following formula, Ph represents a phenyl group. In addition, these compounds may be used individually by 1 type, and may use 2 or more types of mixtures.

  (C) The compounding quantity of a component is 0.1-2 mass parts with respect to 100 mass parts of curable organopolysiloxane composition of (A) component, Preferably it is the range of 0.2-1 mass part. When the blending amount is less than the lower limit value, the effect of improving the adhesion of the resulting silicone film is not sufficient. On the other hand, when the blending amount exceeds the upper limit value, the curability of the release film silicone composition may be inhibited.

The silicone composition for a release film of the present invention may further contain (D) an organic solvent for the purpose of improving treatment bath stability and coating properties on various substrates, and adjusting coating amount and viscosity. As the organic solvent, for example, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, hexane and the like can be used.
(D) When mix | blending component, the compounding quantity becomes like this. Preferably it is the range of 10-10,000 mass parts with respect to 100 mass parts of curable organopolysiloxane composition of (A) component, More preferably, it is 20-8. , 000 parts by mass.

  Additives such as pigments, leveling agents, bath life extenders and the like may be added to the silicone composition for a release film of the present invention as long as the purpose of the present invention is not impaired.

  The silicone composition for a release film of the present invention can be easily produced by uniformly mixing the above components. Specifically, when component (A) is an addition reaction curable organopolysiloxane composition, each of (1), (2), (3), (B), (C), and (D) as desired Although it can manufacture easily by mixing a component uniformly, in order to ensure sufficient pot life, it is preferable to add and mix the (3) platinum group metal catalyst immediately before coating. In addition, when (D) an organic solvent is used, it is advantageous to mix the other components after the component (1) is uniformly dissolved in the component (D). In addition, when the component (A) is a condensation curable organopolysiloxane composition, the components (A), (B), (C), (B), (C), and (D) as required may be uniform. However, in order to ensure a sufficient pot life, the (c) condensation catalyst is preferably added and mixed immediately before coating. When (D) an organic solvent is used, it is advantageous to mix (a) component uniformly in (D) component and then mix other components.

  When applying the silicone composition for a release film of the present invention to a substrate, a bar coater, roll coater, reverse coater, gravure coater, air knife coater, and for coating a thin film, a high-precision offset coater, multistage It is applied to a substrate such as a plastic film by a known application method such as a roll coater.

  Here, examples of the substrate include plastic films such as OPP (biaxially stretched polypropylene) film, PET (polyethylene terephthalate) film, PE (polyethylene) film, and vinyl chloride film.

The coating amount of the base material of the release film for the silicone composition of the present invention varies depending on the kind of the material of the substrate, the range of 0.05-5 g / m ² is preferred as the amount of solids. By heating the base material coated with the silicone composition for a release film of the present invention at 80 to 150 ° C. for 5 to 60 seconds by the above methods, a cured film is formed on the surface of the base material to obtain a release film. Can do.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. The viscosity is a value of absolute viscosity at 25 ° C. measured by a rotational viscometer.

[Synthesis Example 1]
A three-necked round bottom flask equipped with a thermometer, a magnetic stirrer, a reflux condenser, and a nitrogen introduction tube was purged with nitrogen, and then 1 mol of an allyl ether compound represented by the following formula (9), 2 mol of γ-mercaptopropyltrimethoxysilane 2,2′-azobis (2-methylbutyronitrile) 0.5 g was added, and the mixture was heated to 80 ° C. for reaction. During the reaction, after confirming the disappearance of the peak of γ-mercaptopropyltrimethoxysilane by gas chromatography, the mixture was heated for 5 hours. Thereafter, impurities were distilled off at 160 ° C./20 mmHg to obtain an adduct 1 represented by the following formula (10).

[Synthesis Example 2]
An adduct 2 represented by the following formula (11) was obtained in the same manner as in Synthesis Example 1 except that 1 mol of the allyl ether compound represented by the above formula (9) and 2 mol of trimethoxysilane were used.

[Synthesis Example 3]
A three-necked round bottom flask equipped with a thermometer, a magnetic stirrer, a reflux condenser, and a nitrogen introduction tube was purged with nitrogen, and then 1 mol of an allyl ether compound represented by the above formula (9), 2 mol of tetramethyltetrahydrocyclotetrasiloxane Then, platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) 300 ppm was added, and the mixture was heated to 80 ° C. for reaction. After confirming that the heat of reaction had subsided, the mixture was heated for 5 hours. Thereafter, impurities were distilled off at 160 ° C./20 mmHg to obtain an adduct 3 represented by the following formula (12).

（２）下記式で示されるメチルハイドロジェンポリシロキサン（２５℃での粘度が２５ｍＰａ・ｓ、ＳｉＨ基含有量＝１．５モル／１００ｇ）を５質量部（（１）成分のアルケニル基モル数の２倍に相当するＳｉＨ基を含有）、

（３）触媒として白金−ビニルシロキサン錯体を、白金として（１）、（２）成分の合計質量に対して１００ｐｐｍ、
（Ｂ１）合成例２で得られた付加物２を１質量部、
（Ｂ２）合成例３で得られた付加物３を１質量部、
（Ｃ）下記式で示されるイソシアヌレートを１質量部、

（Ｄ）トルエンを１，９５７質量部
上記（３）成分以外の各成分を均一に混合し、使用直前に（３）成分を混合してシリコーン組成物を得た。 [Example 1]
(A) 100 parts by mass of a curable organopolysiloxane composition comprising the following (1) to (3) (1) an organopolysiloxane represented by the following formula (the viscosity of a 30% by mass toluene solution at 25 ° C. is 10 Pa · s , Vinyl group content = 0.03 mol / 100 g)

(2) Methyl hydrogen polysiloxane represented by the following formula (viscosity at 25 ° C .: 25 mPa · s, SiH group content = 1.5 mol / 100 g) 5 parts by mass ((1) component alkenyl group moles) Containing SiH groups corresponding to twice that of

(3) A platinum-vinylsiloxane complex as a catalyst, platinum as (1), 100 ppm relative to the total mass of the components (2),
(B1) 1 part by mass of the adduct 2 obtained in Synthesis Example 2
(B2) 1 part by mass of the adduct 3 obtained in Synthesis Example 3
(C) 1 part by mass of an isocyanurate represented by the following formula:

(D) 1,957 parts by mass of toluene Each component other than the component (3) was mixed uniformly, and the component (3) was mixed just before use to obtain a silicone composition.

（ロ）下記式で示されるメチルハイドロジェンポリシロキサン（２５℃での粘度が２５ｍＰａ・ｓ、ＳｉＨ基含有量＝１．５モル／１００ｇ）を１質量部（（イ）成分の水酸基モル数の３０倍に相当するＳｉＨ基を含有）、

（ハ）触媒としてジオクチル錫ジオクテートを５質量部、
（Ｂ１）合成例１で得られた付加物１を１質量部、
（Ｂ２）合成例３で得られた付加物３を１質量部、
（Ｃ）実施例１で使用したのと同じイソシアヌレートを１質量部、
（Ｄ）トルエンを１，９５７質量部
上記（ハ）成分以外の各成分を均一に混合し、使用直前に（ハ）成分を混合してシリコーン組成物を得た。 [Example 2]
(A) 100 parts by mass of a curable organopolysiloxane composition comprising the following (a) to (c):
(Ii) 100 parts by mass of an organopolysiloxane represented by the following formula (the viscosity of a 30% by mass toluene solution at 25 ° C. is 10 Pa · s, silanol group content = 0.0005 mol / 100 g),

(B) 1 part by mass of the methyl hydrogen polysiloxane represented by the following formula (viscosity at 25 ° C. is 25 mPa · s, SiH group content = 1.5 mol / 100 g) Containing SiH groups corresponding to 30 times),

(C) 5 parts by mass of dioctyltin dioctate as a catalyst,
(B1) 1 part by mass of the adduct 1 obtained in Synthesis Example 1
(B2) 1 part by mass of the adduct 3 obtained in Synthesis Example 3
(C) 1 part by mass of the same isocyanurate used in Example 1,
(D) 1,957 parts by mass of toluene Each component other than the component (c) was mixed uniformly, and the component (c) was mixed just before use to obtain a silicone composition.

Example 3
In Example 1, a silicone composition was prepared in the same manner as in Example 1, except that the component (B1) was not blended and 2 parts by mass of the component (B2) was blended.

Example 4
In Example 2, a silicone composition was prepared in the same manner as in Example 2, except that the component (B1) was not blended and 2 parts by mass of the component (B2) was blended.

[Comparative Example 1]
In Example 1, a silicone composition was prepared in the same manner as in Example 1 except that the component (B2) was not blended.

[Comparative Example 2]
In Example 2, a silicone composition was prepared in the same manner as in Example 2 except that the component (B2) was not blended.

[Comparative Example 3]
In Example 1, a silicone composition was prepared in the same manner as in Example 1 except that the component (B1), the component (B2), and the component (C) were not blended.

[Comparative Example 4]
In Example 2, a silicone composition was prepared in the same manner as in Example 2 except that the component (B1), the component (B2), and the component (C) were not blended.

[Comparative Example 5]
In Example 1, a silicone composition was prepared in the same manner as in Example 1 except that 3 parts by mass of the (C) component was blended without blending the (B1) component and the (B2) component.

[Comparative Example 6]
In Example 1, a silicone composition was prepared in the same manner as in Example 1 except that the component (C) was not blended and 3 parts by mass of the component (B2) was added.

Evaluation method Each of the silicone compositions was evaluated according to the following method. The results are shown in Table 1.

1) Curability The silicone composition 10 minutes after the addition of the catalyst was applied to a polyethylene terephthalate (PET) film (thickness 38 μm) at a solid content of 0.5 g / m ² using a bar coater, and dried with hot air circulation at 80 ° C. The time until the cured film was completely formed by heat treatment with a machine for a predetermined time was measured. Whether or not the film was completely cured was determined by rubbing the surface of the cured film with a finger and no longer being cloudy or falling off.

2) Peeling force The silicone composition 10 minutes after the addition of the catalyst was applied to a PET film (38 μm) at a solid content of 0.5 g / m ² , and heat-treated for 30 seconds with a 100 ° C. hot air circulating dryer for a cured film. The separator for evaluation was produced.
After leaving the produced separator at 25 ° C. and 50% RH for 1 day, an acrylic solvent adhesive (Olivein BPS-5127, manufactured by Toyo Ink Co., Ltd.) was applied to the cured film surface and heat treated at 100 ° C. for 3 minutes. did. Next, a PET film (38 μm) was laminated on the pressure-sensitive adhesive layer, and the PET film was pressure-bonded to the pressure-sensitive adhesive layer by reciprocating once with a 2 kg roller, and aged at 25 ° C. for 20 hours. After cutting, using a tensile tester, the laminated paper was pulled at an angle of 180 ° at a peeling speed of 0.3 m / min, and the force (N) required for peeling was measured.

3) Adhesiveness A PET film (38 μm) substrate separator produced in the same manner as in 2) and a separator produced in the same manner as 2) except that the substrate was replaced with a biaxially oriented polypropylene (OPP) film (40 μm), The cured film surface was rubbed with a finger in a normal state of 25 ° C. and 50% RH and a heating accelerated state of 40 ° C. and 50% RH, and the number of days until the film surface was clouded and dropped was examined. The results are shown as follows: PET substrate at 25 ° C. and 50% RH is adhesion A, OPP substrate is adhesion B, PET substrate at 40 ° C. and 50% RH is adhesion C, and OPP substrate is adhesion D. displayed.

  As can be seen from Table 1, the cured film obtained from the silicone composition of the present invention has remarkably excellent adhesion. The adhesion cannot be obtained by containing a large amount of (B) adduct and (C) isocyanurate (Comparative Examples 5 and 6), and (B) adduct and (C) isocyanurate. It can be seen that this is a synergistic effect.

  The silicone composition for release film of the present invention provides a release layer having excellent adhesion to a substrate, and is useful for various release film applications.

Claims (5)

A silicone composition for a release film comprising the following components (A) to (C).
(A) Curable organopolysiloxane composition: 100 parts by mass,
(B) Adduct of the following diphenylalkane derivative and organosilicon compound (B1) Adduct of diphenylalkane derivative and organosilane or organosiloxane derivative having at least one organooxy group: 0 to 2.7 parts by mass ,
(B2) Adduct of a diphenylalkane derivative and an organosiloxane derivative having a hydrogen atom (SiH group) directly bonded to at least one silicon atom: 0.3 to 3 parts by mass
(However, the total amount of (B1) and (B2) is 0.3 to 3 parts by mass.)
(C) Isocyanurate derivatives having at least one epoxy group or trialkoxysilyl group bonded to a nitrogen atom in one molecule: 0.1 to 2 parts by mass. The said (A) component consists of the following (1)-(3) component, The silicone composition for peeling films of Claim 1 characterized by the above-mentioned.
(1) an organopolysiloxane having at least two alkenyl groups in one molecule;
(2) An amount of an organohydrogenpolysiloxane having at least three SiH groups in one molecule, wherein the total number of moles of SiH groups is 1 to 10 times the total number of moles of alkenyl groups contained in (1),
(3) A catalytic amount of a platinum group metal catalyst. The silicone composition for a release film according to claim 1, wherein the component (A) comprises the following components (a) to (c).
(A) an organopolysiloxane having at least two hydroxyl groups in one molecule;
(B) An organopolysiloxane having at least three SiH groups and / or hydrolyzable groups in one molecule, wherein the total number of moles of SiH groups and hydrolyzable groups is the total number of hydroxyl groups contained in (a) An amount equivalent to 5 to 200 times
(C) A catalytic amount of a condensation catalyst. The component (B1) is represented by the following general formula (I) or (II)

[In the formula, R ⁴ independently represents a hydrogen atom or a methyl group, R ⁵ independently represents a hydroxyl group or a methyl group, a represents 0, 1 or 2, and A independently represents General formula (i) or (ii)

(In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms which may intervene with an oxygen atom. And b is an integer of 1 to 3, c is 0 or 1, provided that b + c is 2 or 3, and x is an integer of 1 to 8.)
It is group represented by these. ]
In which the component (B2) is represented by the following general formula (III) or (IV):

[Wherein R ⁴ , R ⁵ and a are the same as above. B are independently of each other the following general formula (iii) or (iv)

(In the formula, R ⁶ is the same as above. R ⁸ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and Z is the following formula:

D and g are 0 or an integer of 1 to 10, e, h and j are 0 or an integer of 1 to 5, f is an integer of 0 or 1 to 3, and i is 0 or 1 An integer of -7, wherein i + j is an integer of 2-7, and d, f, g, i are selected so as to have at least one SiH group in one molecule. ]
The silicone composition for a release film according to any one of claims 1 to 3, wherein the composition is a compound represented by formula (1). The said (C) component is a compound represented by following General formula (5), The silicone composition for peeling films of any one of Claims 1-4 characterized by the above-mentioned.

[In the formula, T is independently of each other a group represented by the following formula (v) or (vi), an alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, or a monofunctional alkenyl group; Each T is a group represented by the following formula (v) or (vi).
(R ¹ O) ₃ Si—R ² − (v)
(In the formula, R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² is an alkylene group having 2 to 5 carbon atoms.)
QR- ³ (vi)
(In the formula, Q is an epoxy group, and R ³ is an alkylene group having 1 to ³ carbon atoms.)]