JP4646122B2 - Silicone composition for release film - Google Patents

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 (patent). References 1, 2).

  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 has been increasing, and there is a demand for improved adhesion between these plastics and cured silicone films. It 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. Moreover, although the method of improving adhesiveness is known by giving the base polymer structure of a silicone resin the branched structure containing a RSiO3 _{/ 2} unit, adhesiveness is not enough (patent documents 3-6). ). 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. It is not (see Patent Documents 7 and 8). Furthermore, an additive having an excellent effect of improving adhesion, which is composed of a siloxane chemical having a hydrocarbon group having a specific structure bonded thereto is known (Patent Documents 9 and 10). Although this adhesion improver can obtain good results for a specific application, it does not provide a satisfactory effect for a release film. Further, the present inventor has a release paper silicone composition, carbon - by incorporating the siloxane compound having two or more polycyclic hydrocarbon group containing a carbon double bond in one molecule, and the substrate It was found that a cured film having excellent adhesion was obtained (Patent Document 11).

Japanese Patent Publication No.49-26798 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 JP 2005-015666 A

  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. Then, this invention aims at providing the silicone composition which gives the peelable layer which has the further improved adhesiveness with respect to a plastic film.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by blending a silicone composition for release paper with a compound having a predetermined structure and an isocyanurate derivative. It was.

That is, the present invention relates to a release film silicone composition comprising an organopolysiloxane as a main component.
For 100 parts by mass of (A) organopolysiloxane,
(B) at least one diphenylalkane derivative selected from the group consisting of diphenylmethane, diphenylethane and diphenylpropane, the diphenylalkane derivative having an unsaturated substituent in at least one phenyl group, and at least one organooxy An adduct with an organopolysiloxane derivative having a group, SiH or SH group , and (C) isocyanurate, wherein at least one of the substituents bonded to the nitrogen atom is It is a silicone composition characterized by including 0.1-2 mass parts of isocyanurate which has an epoxy group or a trialkoxysilyl group.

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

In the present invention, (B) an adduct of a diphenylalkane derivative and an organopolysiloxane derivative having at least one organooxy group (hereinafter referred to as “adduct”) comprises an organosiloxane part and an aromatic part having different polarities. By having it, the adhesive force to the film of a silicone composition is improved. The production method of the adduct is not limited to a specific one. For example, an addition reaction between a diphenylalkane derivative having an unsaturated substituent in at least one phenyl group and a silicon compound having an active hydrogen such as a SiH group or a mercapto group. Can be obtained. Examples of the hydrocarbon substituent containing the double bond include 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.

ここで、Ｒ⁴互いに独立に水素原子又はメチル基である。Ｒ⁵は水酸基及びはメチル基からなる群より選ばれる基であり、aは０〜２であり、aが２である場合に、Ｒ⁵は水酸基とメチル基であってよい。Ｒ⁶は炭素数１〜１０の置換されていてよい一価炭化水素基であり、Ｒ⁷は炭素数１〜８の置換されていてよい一価炭化水素基である。Ｒ⁶、Ｒ⁷は同一であってよく、例えばメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基等のアルキル基；シクロヘキシル基等のシクロアルキル基；ビニル基、アリル基、プロペニル基、ブテニル基、ヘキセニル基等のアルケニル基；フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、あるいはこれらの基の水素原子の一部が塩素、フッ素、臭素といったハロゲン原子等で置換された基、例えばトリフルオロプロピル基などである。Ｒ⁶はメチル基であることが好ましい。Ｒ⁷としてはアルキル基及びアルコキシアルキル基が好ましく、工業的にはメチル基が最も好ましい。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、及びｘは１〜８の整数である。 Preferably, the (B) adduct contains a compound represented by the following general formula (I) or (II), and may be a mixture thereof. In the formula, A is a group represented by the formula (i) or (ii).

Here, R ^{4 is} independently a hydrogen atom or a methyl group. R ⁵ is a group selected from the group consisting of a hydroxyl group and a methyl group, a is 0 to 2, and when a is 2, R ⁵ may be a hydroxyl group and a methyl group. R ⁶ is an optionally substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ is an optionally substituted monovalent hydrocarbon group having 1 to 8 carbon atoms. R ⁶ and R ⁷ may be the same, for example, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group and octyl group; cycloalkyl group such as cyclohexyl group; vinyl group, allyl group and propenyl Groups, butenyl groups, alkenyl groups such as hexenyl groups; aryl groups such as phenyl groups, tolyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, etc., or some of the hydrogen atoms of these groups are chlorine, fluorine, bromine, etc. A group substituted with a halogen atom or the like, such as a trifluoropropyl group. R ⁶ is preferably a methyl group. R ⁷ is preferably an alkyl group or an alkoxyalkyl group, and most preferably a methyl group industrially. 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.

In formula (ii), when c is 1, it binds to a diphenylalkane molecule that reacts with the mercapto group, for example, a diphenylalkane molecule that is different from the diphenylalkane molecule to which the already reacted mercapto residue is bound. What is being done is also included.

Examples of the compound of the above formula (I) or (II) include the following.

(B) The adduct may be a mixture of two or more. A compounding quantity is 0.3-3 weight part with respect to 100 weight part of (A) organopolysiloxane, Preferably it is 0.5-2 weight part. 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.

The (C) isocyanurate of this invention is mix | blended with a composition with (B) an adduct, and is for improving the adhesiveness of the cured film formed. (B) Only the adducts have different adhesion improving effects depending on the substrate type and use conditions, but by using (C) isocyanurate in combination, higher adhesion can be obtained more stably. That is, although not intended to limit the present invention, a mechanism capable of obtaining high adhesion is considered as follows. (B) The biphenylalkane portion of the adduct interacts with the film substrate, and the alkoxysilyl group chemically bonds with the silicone film. Thereby, it acts so that a film base material and a silicone layer may be tied. (C) In the isocyanurate, it is considered that the isocyanurate group is mainly chemically bonded to the film substrate, 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 alkoxy group, a certain degree of adhesion improving effect can be obtained, but not as effective as isocyanurate. 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 (B) and (C) each having a site where the interaction between the film substrate and the silicone film is different from each other, the adhesion effect is increased, and at the same time, whether the type of film or the surface treatment state is affected. Regardless of whether or not it is possible to obtain a stable effect.

式中、少なくとも１つのＴが、下記式（iii）で表される有機基、
（Ｒ¹Ｏ）₃Ｓｉ−Ｒ²− （iii）
[式（iii）中、Ｒ¹は、炭素数１〜８のアルキル基、及びＲ²は炭素数２〜５のアルキレン基である]
又は、下記式（iv）で表される有機基であり、
Ｑ−Ｒ³− （iv）
[式（iv）中、Ｑはエポキシ基、Ｒ³は炭素数１〜３のアルキレン基である]
他のＴは、互いに独立に、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る。 (C) The isocyanurate derivative is an isocyanuric acid ester in which hydrogen on the nitrogen atom of isocyanuric acid is substituted, and at least one of the substituents includes an epoxy group or a trialkoxysilyl group. Preferably, what is represented by the following general formula (7) is used.

In the formula, at least one T is an organic group represented by the following formula (iii):
(R ¹ O) ₃ Si—R ² − (iii)
[In formula (iii), 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]
Or an organic group represented by the following formula (iv):
QR- ³ (iv)
[In Formula (iv), Q is an epoxy group, and R ³ is an alkylene group having 1 to ³ carbon atoms]
The other T is independently an alkyl group, an aryl group, an aralkyl group, or a monofunctional alkenyl group having 1 to 8 carbon atoms.

 The alkyl group containing 1 to 8 carbon atoms may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group And octyl group. Examples of the aryl group and aralkyl group include a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the monofunctional alkenyl group include a straight chain or branched chain group having 2 to 5 carbon atoms and one carbon-carbon double bond, such as a vinyl group, an allyl group, an iso group. A propenyl group, a butenyl group, a pentenyl group, etc. are mentioned. In these, an allyl group is preferable.

R ¹ in formula (iii) is an alkyl group having 1 to 8 carbon atoms and may be exemplified above. Preferred are a methyl group and an ethyl group, and most preferred is a methyl group. Examples 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 (iii) include a trimethoxysilylethyl group, a trimethoxysilylpropyl group, a triethoxysilylethyl group, and a triethoxysilylpropyl group. A trimethoxysilylpropyl group and a triethoxysilylpropyl group are preferred.

Examples of R ^{3 in} the organic group represented by the formula (iv) include a methylene group, an ethylene group, and a propylene group. Examples of the organic group of the formula (iv) include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group and the like. Of these, 2,3-epoxypropyl groups are preferred.

Isocyanurate represented by the formula (7), an organic isocyanate of the following formula (9), for example, cyclized with phosphines, alkali metal alcoholates alkoxide, or such basic catalyst organic tin salts Can be obtained.
T-NCO (9)
(T is as defined above.)

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と同じであるか、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。 However, the isocyanurate having a Q—R ³ — group represents a carbon-carbon double bond in the group K of the isocyanurate substituted with the aliphatic unsaturated group K represented by the following formula (10). For example, it can be obtained by oxidation with a peracid such as performic acid or peracetic acid.

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

The isocyanurate having a group of formula (iii), (R ¹ O) ₃ Si—R ² —, is an isocyanurate represented by the above formula (10), an organosilicon compound represented by the following general formula (11) Can also be obtained by reacting in the presence of a platinum catalyst.
(R ¹ O) ₃ Si—R ² —H (11)
(Wherein R ¹ and R ² are the same as above)

As for (C) isocyanurate, the target substance may be isolated after completion of the reaction, but it is also possible to use a reaction mixture from which unreacted substances, by-products and catalysts have been removed.

Examples of (C) isocyanurates include those represented by the following structural formula. In the following formula, Ph represents a phenyl group. Mixtures of these compounds may be used.

The blending amount of (C) is 0.1 to 2 parts by weight, preferably 0.2 to 1 part by weight, based on 100 parts by weight of (A) organopolysiloxane. When the blending amount is less than the lower limit value, the adhesion of the silicone film is not sufficiently improved. On the other hand, when the blending amount exceeds the upper limit value, the curability of (A) organopolysiloxane may be inhibited.

Said (B) and (C) can be mix | blended with the well-known arbitrary silicone composition for peeling films which have (A) organopolysiloxane as a main component. There are two types of known silicone compositions, one that is cured by an addition reaction and the other that is cured by a condensation reaction.

式中、Ｒ¹²はアルケニル基、Ｒ¹¹は不飽和結合を有しない一価炭化水素基を示し、Ｘ¹は以下の組成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、２５℃における３０％トルエン溶液での粘度が７０Ｐａ・ｓ以下を満たす正の数から選ばれ、ｂ１、ｃ１、ｄ１、ｅ１は０であってもよい。α及びβは、０または１〜３の整数である。 The silicone composition which cures by addition reaction is an organopolysiloxane in which (A) organopolysiloxane has (A1) at least two alkenyl groups in one molecule, and is represented by the following formula (1).

In the formula, R ¹² represents an alkenyl group, R ¹¹ represents a monovalent hydrocarbon group having no unsaturated bond, and X ¹ represents a group represented by the following composition formula.

a1, b1, c1, d1, and e1 are selected from positive numbers in which the viscosity of the organopolysiloxane at 25 ° C. is 0.1 Pa · s or more and the viscosity in a 30% toluene solution at 25 ° C. is 70 Pa · s or less, b1, c1, d1, and e1 may be 0. α and β are 0 or an integer of 1 to 3.

R ¹¹ is a monovalent hydrocarbon group containing no 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 , A chloromethyl group, a trifluoropropyl group, a cyanoethyl group or the like in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, or the like, and a methoxy group, It is an organic group selected from an alkoxy group having 1 to 12 carbon atoms such as an ethoxy group, a propoxy group and a methoxyethoxy group, and an epoxy group having 2 to 20 carbon atoms. (A1) R ¹¹ contained in the whole organopolysiloxane is preferably at least 80% methyl group in view of the properties of the resulting cured film.

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.

(A1) One molecule of the organopolysiloxane has two or more alkenyl groups, and desirably, (A1) the content is 100 to 0.1 mol per 100 g of the organopolysiloxane. The a1, b1, c1, d1, and e1 of the formula (1) and the substituent X ¹ are selected so that the number of alkenyl groups c1 + b1 × (1 + e1 + β) + 2α of one molecule is in the range of 2 to 1,500. .

  (A1) The main chain structure of the organopolysiloxane may be linear or may include a branched structure in which b1 is not 0.

(D1) An organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) directly bonded to a silicon atom in one molecule is used as an addition reaction with the (A1) organopolysiloxane. (D1) is represented by the following composition formula (12).
R ¹¹ _f H _g SiO _{(4-fg) / 2} (12)
(Wherein R ¹¹ represents the same meaning as above, f is 0 ≦ f ≦ 3, g is 0 <g ≦ 3, preferably 0.2 ≦ g ≦ 1, provided that f + g is 1 ≦ f + g ≦ 3. Is the number of

  The molecular structure of (D1) may be linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s. (D1) Examples of the organohydrogenpolysiloxane include the following organopolysiloxanes.

Ｚは下記式で表される基である。

また、上記構造式及び組成式において、ｈからｗは次に示される範囲の整数である。ｈ，ｌ，ｎは３〜５００、ｍ，ｐ，ｓは１〜５００、ｉ，ｊ，ｋ，ｏ，ｑ，ｒ，ｔ，ｕ，ｖ，ｗは０〜５００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 structural formula and composition formula, h to w are integers in the following range. h, l, and n are 3 to 500, m, p, and s are 1 to 500, and i, j, k, o, q, r, t, u, v, and w are 0 to 500.

  The (D1) organohydrogenpolysiloxane is used in such an amount that the number of moles of SiH groups contained corresponds to 1 to 5 times the total number of moles of alkenyl groups contained in (A1). When the number of moles of SiH groups contained in (D1) is less than the lower limit, curability is insufficient. On the other hand, not only a significant increase in curability is observed even if the amount exceeds the upper limit, but peeling May decrease. The amount of typical (D1) organohydrogenpolysiloxane in the above range is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A1) polyorganosiloxane.

  As the catalyst (E1) for the addition reaction of (A1) organopolysiloxane and (D1) organohydrogenpolysiloxane, any conventionally known catalyst can be used. Examples thereof include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, rhodium, rhodium-olefin complex, and the like. The above (E1) catalyst is usually sufficiently cured if blended in an amount of 5 to 1000 ppm (mass ratio) as platinum or rhodium with respect to the total weight of (A1), (B), (C) and (D1). A film can be formed, but can be appropriately increased or decreased depending on the reactivity of each component or the desired curing rate.

  The composition of the present invention may further contain (F) an organic solvent for the purpose of improving the stability of the treatment bath, improving the coating property to various substrates, and adjusting the coating amount and the viscosity. For example, toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, hexane and the like can be used.

  The composition of the present invention can be easily produced by uniformly mixing the components (A1), (B), (C), (D1), (E1) and, if desired, (F). However, in order to ensure a sufficient pot life, the catalyst (E1) is preferably added and mixed immediately before coating. When (F) an organic solvent is used, it is advantageous to mix (A1) in (F) uniformly and then mix other components.

  In the composition of the present invention, additives such as pigments, leveling agents, bath life extenders and the like can be blended as necessary.

  When coating using the composition of the present invention, a bar coater, a roll coater, a reverse coater, a gravure coater, an air knife coater, and a high-precision offset coater, a multi-stage roll coater, etc. for thin film coating The coating method is applied to a substrate such as a plastic film.

The coating amount of the base material of the compositions 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. Each method described above, the composition the coated substrate of the present invention allowed forming a cured coating on a substrate surface by heating from 60 to 5 seconds at 80 to 150 ° C., can be obtained release film.

式中、Ｒ¹³は水酸基、Ｒ¹⁴は上記Ｒ¹¹と同じ一価炭化水素基を示すが、脂肪族不飽和結合を含有してもよい。Ｘ²は以下の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℃の粘度が０．１Ｐａ・ｓ以上、３０％トルエン溶液での２５℃の粘度が７０Ｐａ・ｓ以下を満たす正数から選ばれ、ｂ２、ｃ２、ｄ２、ｅ２は０であってもよい。γ及びδは０または１の整数である。 Next, a silicone composition that cures by a condensation reaction will be described. The composition has a structure represented by the following general formula (2) in which (A) an organopolysiloxane has (A2) at least two hydroxyl groups in one molecule.

In the formula, R ¹³ represents a hydroxyl group, and R ¹⁴ represents the same monovalent hydrocarbon group as R ¹¹ described above, but may contain an aliphatic unsaturated bond. X ² is a group represented by the following formula.

a2, b2, c2, d2, and e2 are selected from positive numbers satisfying a viscosity of 25 ° C. of the organopolysiloxane of 0.1 Pa · s or more and a viscosity of 25 ° C. in a 30% toluene solution of 70 Pa · s or less. , C2, d2, and e2 may be zero. γ and δ are integers of 0 or 1.

In the above formula, R ¹⁴ may be an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group, or a propenyl group, in addition to the groups described for R ¹¹ above. Like R ¹¹ above, (A2) R ¹⁴ contained in the entire organopolysiloxane is preferably at least 80% methyl in terms of characteristics.

(A2) One molecule of organopolysiloxane has 2 or more hydroxyl groups, and preferably (A2) 0.0001 to 0.1 mol as a content per 100 g. 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. The a2, b2, c2, d2, and e2 of the corresponding formula (2) and substituent X ² are selected so that the number of hydroxyl groups c2 + b2 × (e2 + δ) + 2γ of one molecule is in the range of 2 to 150.

  (A2) The range of the viscosity of the organopolysiloxane at 25 ° C. is 0.1 Pa · s or more and 70 Pa · s or less in a 30% by mass toluene solution. When the viscosity is less than the lower limit, coating of the composition becomes difficult, and when the viscosity exceeds the upper limit, workability decreases. The a2, b2, c2, d2, and e2 of the formula (2) and the substituent X2 are selected so that the polymerization degree a2 + c2 + b2 × (d2 + e2 + 1) +2 is in the range of 50 to 20,000.

  (A2) The main chain structure of the organopolysiloxane may be linear or may include a branched chain structure corresponding to the case where b2 is not 0.

  (A2) The organopolysiloxane is subjected to a condensation reaction with (D2) an organopolysiloxane having at least three SiH or hydrolyzable groups in one molecule. In the case of an organopolysiloxane having a SiH group, the same as (D1) can be used. (D2) is used in such an amount that the number of moles of the SiH group or hydrolyzable group contained is 5 to 200 times the number of moles of the hydroxyl group contained in (A2). In the case of a typical organopolysiloxane, the amount is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of (A2). When the number of moles of SiH groups and the like contained in (D2) is less than the lower limit, the amount of cross-linking due to a chemical reaction between a hydroxyl group and SiH or the like is not sufficient, and the peelability tends to decrease. On the other hand, even if blended in excess of the above upper limit, there is no significant increase in the effect of improving peelability, but there is a tendency to reduce the pot life of the composition.

As (D2) organopolysiloxane having a hydrolyzable group, those represented by the following composition formula can be used.
R ¹¹ _f W _g SiO _{(4-fg) / 2}
(Wherein R ¹¹ is the same as R ¹¹ described above, W represents a hydrolyzable group, f is 0 ≦ f ≦ 3, g is 0 <g ≦ 3, and f + g is a number 1 ≦ f + g <3. .)

  The molecular structure of (D2) may be linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s.

  Examples of the hydrolyzable group W include 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 silicon, an acyloxy group such as an acetoxy group, and an amino group such as an ethylamino group. , An oxime group such as an amide group and an ethylmethylbutanoxime group, and a halogen atom such as chlorine and bromine. For example, the following polyorganosiloxane can be used.

上式でＷは、ＣＨ₃ＣＯＯ−，ＣＨ₃（Ｃ₂Ｈ₅）Ｃ＝ＮＯ−，（Ｃ₂Ｈ₅）₂Ｎ−，ＣＨ₃ＣＯ（Ｃ₂Ｈ₅）Ｎ−，ＣＨ₂＝（ＣＨ₃）ＣＯ−などの加水分解性基を示し、ｘ、ｙ、ｚは０〜５００の範囲の整数である。

In the above 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 = ( CH ₃ ) represents a hydrolyzable group such as CO—, and x, y and z are integers in the range of 0 to 500.

  (D2) The organopolysiloxane having a hydrolyzable group is also used in the same amount as that having the SiH group. Moreover, you may use what has both a hydrolysable group and SiH group on 1 molecule.

  The (E2) condensation catalyst used when (A2) and (D2) are reacted is used to accelerate the condensation reaction to crosslink and increase the peelability and durability of the cured film. Such (E2) condensation catalysts include acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, maleic acid, trifluoroacetic acid, 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.

  (E2) The condensation catalyst is usually blended in an amount of 0.1 to 5% (mass ratio) as an active component with respect to the total mass of (A2), (B), (C) and (D2). The amount can be appropriately increased or decreased depending on the reactivity of or the desired curing rate.

   Also in the condensation type silicone composition, the point that (F) an organic solvent and an optional component can be blended, the production method, and the coating method are the same as those of the addition type composition.

付加物１

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.
[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 (13), 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 (14).

Addendum 1

[Synthesis Example 2]
Except using 1 mol of trimethoxysilane 2 mode allyl ether compound represented by the formula (13), in the same manner as in Synthesis Example 1 to obtain the adduct 2 represented by the following formula (15).
Addendum 2

（Ｂ）として合成例２で得られた反応物２を２質量部、
（Ｃ）として以下の構造のイソシアヌレートを１質量部、

（Ｄ１）として以下の式で示されるメチルハイドロジエンポリシロキサン（２５℃での粘度が２５ｍＰａ・ｓ、Ｈ含有量＝１．５モル／１００ｇ）を５質量部（Ａ１成分とＢ成分のアルケニル基モル数の２倍に相当するＳｉＨを含有）、

（Ｅ１）触媒として白金-ビニルシロキサン錯体を白金として、（Ａ１）、（Ｂ）、（Ｃ）、（Ｄ１）の合計質量に対して １００ｐｐｍ、及び
（Ｆ）成分としてトルエンを２０５２質量部
を均一に混合して組成物を得た。 Example 1
100 parts by mass of polyorganosiloxane represented by the following formula (A1) (viscosity of 30% toluene solution at 25 ° C. is 10 Pa · s, vinyl group content is 0.03 mol / 100 g),

(B) 2 parts by mass of the reactant 2 obtained in Synthesis Example 2;
(C) 1 part by mass of isocyanurate having the following structure:

(D1) 5 parts by weight (alkenyl group of component A1 and component B) of methylhydropolysiloxane represented by the following formula (viscosity at 25 ° C. is 25 mPa · s, H content = 1.5 mol / 100 g) SiH corresponding to twice the number of moles)

(E1) Platinum-vinylsiloxane complex as a catalyst as platinum, 100 ppm with respect to the total mass of (A1), (B), (C), and (D1), and 2052 parts by mass of toluene as the component (F) To obtain a composition.

（Ｂ）として合成例１で得られた付加物１を２質量部、
（Ｃ）として実施例１で使用したのと同様のイソシアヌレートを１質量部、
（Ｄ２）として以下の式で示されるメチルハイドロジエンポリシロキサン（２５℃での粘度が２５ｍＰａ・ｓ、Ｈ含有量＝１．５モル／１００ｇ）を１質量部（Ａ２成分の水酸基モル数の３０倍に相当するＳｉＨを含有）、

（Ｅ２）触媒としてジオクチル錫ジオクテートを５質量部、及び
（Ｆ）トルエンを２０７１質量部
を均一に混合して組成物を得た。 Example 2
100 parts by mass of polyorganosiloxane represented by the following formula as (A2) (viscosity of 30% toluene solution at 25 ° C. is 10 Pa · s, silanol group content = 0.0005 mol / 100 g),

(B) 2 parts by mass of the adduct 1 obtained in Synthesis Example 1;
(C) 1 part by mass of the same isocyanurate used in Example 1 as
As (D2), 1 part by mass (30 moles of hydroxyl groups of the component A2) of methylhydropolyenepolysiloxane represented by the following formula (viscosity at 25 ° C. is 25 mPa · s, H content = 1.5 mol / 100 g) Double the equivalent SiH),

(E2) As a catalyst, 5 parts by mass of dioctyltin dioctate and (F) 2071 parts by mass of toluene were uniformly mixed to obtain a composition.

Comparative Example 1
A composition was prepared in the same manner as in Example 1 except that (B) and (C) were not blended.

Comparative Example 2
A composition was prepared in the same manner as in Example 2 except that (B) and (C) were not blended.
Comparative Example 3
A composition was prepared in the same manner as in Example 1 except that (B) was not blended and 3 parts by mass of (C) was added.
Comparative Example 4
A composition was prepared in the same manner as in Example 1 except that (C) was not blended and 3 parts by mass of (B) was added.

Evaluation method The composition 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 heated at 80 ° C. The time until the cured film was completely formed by heat treatment with a dryer 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 cured by heating for 30 seconds in a 100 ° C. hot air circulating dryer. A film was formed to produce a separator for evaluation.
After leaving the prepared separator at 25 ° C. and 50% RH for 1 day, an acrylic solvent adhesive (Olivein BPS-5127, manufactured by Toyo Ink Mfg. Co., Ltd.) is 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 prepared in the same manner as in 2) and a separator prepared in the same manner as in 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 at 25 ° C. and 50% RH, and the number of days until the film surface was clouded and dropped off was examined.

表１から分かるように、本発明の組成物から得られる硬化膜は、顕著に優れた密着性を有する。該密着性は（Ｂ）付加物と（Ｃ）イソシアヌレートとを、夫々、多く含むことによっても得ることはできず（比較例４及び３）、（Ｂ）付加物と（Ｃ）イソシアヌレートとの相乗的な効果であることが分かる。

As can be seen from Table 1, the cured film obtained from the composition of the present invention has remarkably excellent adhesion. The adhesion cannot be obtained by including a large amount of (B) adduct and (C) isocyanurate (Comparative Examples 4 and 3), and (B) adduct and (C) isocyanurate. It can be seen that this is a synergistic effect.

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

Claims (5)

In the silicone composition for release film mainly composed of organopolysiloxane,
For 100 parts by mass of (A) organopolysiloxane,
(B) at least one diphenylalkane derivative selected from the group consisting of diphenylmethane, diphenylethane and diphenylpropane, the diphenylalkane derivative having an unsaturated substituent in at least one phenyl group, and at least one organooxy An adduct with an organopolysiloxane derivative having a group, SiH or SH group , and (C) isocyanurate, wherein at least one of the substituents bonded to the nitrogen atom is A silicone composition comprising 0.1 to 2 parts by mass of isocyanurate having an epoxy group or a trialkoxysilyl group. (A) the organopolysiloxane is (A1) an organopolysiloxane having at least two alkenyl groups in one molecule;
The silicone composition is
(D1) An organohydrogenpolysiloxane having at least three SiH groups in one molecule is such that the total number of moles of SiH groups is 1 to 5 times the total number of moles of alkenyl groups contained in (A1), And (E1) a catalytic amount of a platinum group metal catalyst,
The silicone composition of claim 1 further comprising: (A) the organopolysiloxane is (A2) an organopolysiloxane having at least two hydroxyl groups in one molecule;
The silicone composition is
(D2) In an organopolysiloxane having at least three SiH groups or hydrolyzable groups in one molecule, the total number of moles of SiH groups and hydrolyzable groups is 5 of the total number of moles of hydroxyl groups contained in (A2). The silicone composition according to claim 1, further comprising an amount equivalent to ˜200 times and (E2) a catalytic amount of a condensation catalyst. (B) The silicone composition according to any one of claims 1 to 3, wherein the adduct contains a compound represented by the following formula (I) or (II).

(In the formulas (I) and (II), R ⁴ is independently a hydrogen atom or a methyl group, A is independently a group represented by the formula (i) or (ii), and R ⁵ is a group selected from the group consisting of hydroxyl and methyl groups, a is an integer of 0 to 2, R ⁶ is optionally substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁷ carbon the number 1 to 8 of the optionally substituted monovalent hydrocarbon group, b is an integer from 1 to 3, c is 0 or 1, provided that b + c is 2 or 3, and x is 1 to 8 (It is an integer.) (C) Isocyanurate is represented by following formula (7), The silicone composition of any one of Claims 1-4.

Wherein at least one T is a group represented by the following formula (iii):

(R ¹ O) ₃ Si—R ² − (iii)
[In Formula (iii), 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]

Or a group represented by the following formula (iv):

Q-R ³ - (iv)
[In the formula (iv), Q is an epoxy group, and R ³ is an alkylene group having 1 to ³ carbon atoms]

Other T's are each independently an alkyl group, an aryl group, an aralkyl group, or a monofunctional alkenyl group having 1 to 8 carbon atoms.
The silicone composition according to any one of claims 1 to 4.