TWI665271B - Silicone composition for release paper or release film, release paper and release film - Google Patents

Abstract

To provide a migration inhibiting agent, Addition reaction hardening type peeling paper or release film with no adverse effect on peeling force and peeling force resistance, and a silicone composition for release paper or release film, and providing peeling of cured film formed with the composition Paper and release film.

In addition reaction hardening type polysiloxane composition, A specific amount of one or more compounds selected from the group consisting of olefins and diolefins having an unsaturated bond at the terminal, silanes and disiloxanes having an unsaturated bond at the terminal are prepared.

Description

Silicone composition for release paper or release film, release paper and release film

The present invention relates to a polysiloxane composition, which is suitable for producing a release paper and a release film excellent in the effect of suppressing the phenomenon of re-peeling due to exposure to the atmosphere (hereinafter referred to as "exposure resistance"). The silicone coating paper and the coating surface of the silicone coating film produced by coating the composition can maintain good peeling properties even when exposed to the atmosphere, and a silicone coating composition having a hardened film formed with the composition Release paper and release film.

A release film or release paper is coated with a silicone-based release agent on the surface of a substrate such as a plastic film or paper, and a cured film is formed by a crosslinking reaction. It is widely used as a release agent film for adhesive to adhesive substances. use.

As such a curable organic polysiloxane composition, it is well-known that an organic polysiloxane containing a vinyl group and an organic hydrogen polysiloxane containing a hydrogen atom bonded to a silicon atom are used as a main component. Addition reaction hardening type peeling composition hardened by the silylation reaction has the advantages of fast curing speed and various peeling characteristics, etc. The composition for peeling is widely used. However, the peeling composition of the addition reaction-hardening type peeling composition becomes abnormally heavy when the cured film is exposed to the outside air, and it has been blamed for the phenomenon that it cannot be peeled depending on the circumstances. Therefore, in the process of producing labels or adhesive tapes by using release paper or release film formed of a release agent film with an addition reaction-hardening type release composition, it becomes impossible to expose the silicone-coated film to the atmosphere. Maintaining the releasability required for these products causes poor peeling and severely degrades the quality.

In order to solve this problem, a method of blending an alcohol-modified organic polysiloxane or a polyether-modified organic polysiloxane in an addition reaction-hardening type peeling composition has been reported (Japanese Patent Laid-Open No. 55-3460). Gazette: Patent Document 1) and a method for preparing a silicon atom having only one terminal having a hydrosilyl group as part of the organohydrogenpolysiloxane (Japanese Patent Application Laid-Open No. 1-217068: Patent Document 2). However, although the effects of these methods to suppress the phenomenon of re-peeling due to exposure to the atmosphere have been confirmed, they are not sufficient. It also has the disadvantage of reducing the residual adhesive force of the adhesive layer.

Japanese Patent No. 2934118 (Patent Document 3) discloses a method for limiting the structure of a cross-linking agent. Although the reduction of the residual adhesive force is improved, other influences on the peeling characteristics such as a heavy peeling force are increased.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 55-3460

[Patent Document 2] Japanese Unexamined Patent Publication No. 1-217068

[Patent Document 3] Japanese Patent No. 2934118

The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide an addition reaction-hardening type peeling of a peeling agent film that imparts migration resistance to a peeling agent, has no adverse effect on residual adhesion or peeling force, and has resistance to exposure. A polysiloxane composition for paper or a release film, and a release paper and a release film provided with a hardened film formed of the composition.

As a result of intensive research in order to achieve the above-mentioned object, the inventors have found that, by adding an addition reaction-hardening type polysiloxane composition, a specific amount is selected from olefins and diolefins having unsaturated bonds at the ends, One or more compounds of saturated bond alkenyl silanes and disilanes are provided with a release agent film that suppresses the migration of the release agent, has no adverse effect on the residual adhesive force or the release force, and has an exposure resistance. Polysiloxane composition for paper or release film. The release paper and release film formed from the cured film of the composition are excellent in exposure resistance and release property. Even if the cured film formed on the release paper and release film is exposed for a long time, In the air, the peelability before exposure can be almost maintained, and the present invention has been completed.

Accordingly, the present invention provides the following silicone composition for release paper or release film, release paper, and release film.

〔1〕

An addition reaction-hardening type polysiloxane composition for release paper or release film, which comprises the following (A) to (E): (A) is represented by the following general formula (1), and has at least 2 in one molecule. Alkenyl organic polysiloxane: 100 parts by mass,

(In the formula, R ^{1 is} independently an alkenyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, and X ^{1 is} independently the following general formula (2-1) X ^{2 is} independently the following general formula (2-2), X ^{3 is} independently the following general formula (2-3)

In the base shown, X ^{4 is} each independently the following general formula (3-1), X ^{5 is} each independently the following general formula (3-2), and X ^{6 is} each independently the following general formula (3-3)

The base shown. R ¹ and R ^{2 are} as described above, and a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3. a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, and a63 are 0 or positive numbers. These are the viscosity of organic polysiloxane Choose from a range of 0.05 Pa · s or more, 30% by mass toluene dilution viscosity of 70 Pa · s or less), and (B) selected from the number of carbons with unsaturated bonds at the ends shown in the following general formula (4): 8 to 30 Olefins, diolefins having 10 to 32 carbon atoms having unsaturated bonds at both ends shown in the following general formula (5), and 1-4 having unsaturated bonds having 1 to 4 ends shown in the following general formula (6) One of the alkenyl silanes having 8 to 30 carbon atoms, and one of the disiloxanes having 8 to 30 carbon alkenyl groups having 2 to 6 terminals having unsaturated bonds as shown in the following general formula (7) Compounds above: 5-20 parts by mass, CH ₂ = CH-R ³ -H (4)

CH ₂ = CH-R ³ -CH = CH ₂ (5)

(CH ₂ = CH-R ³ ) _b1 SiR ⁴ _4-b1 (6)

(In the formula, R ^{3 is} each independently a bivalent hydrocarbon group having 6 to 28 carbon atoms, R ^{4 is} independently a monovalent hydrocarbon group or alkoxy group having 1 to 10 carbon atoms, b1 is an integer of 1 to 4 and b2 is independently 1 to 4 An integer of 3), (C) As shown in the following average composition formula (8), an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: (C) The component is bonded to The mole number of the hydrogen atom of the silicon atom is an amount equivalent to 1 to 20 times the total mole number of the alkenyl group and the unsaturated group in the components (A) and (B). R ² _c1 H _c2 SiO _{(4-c1 -c2) / 2} (8)

(In the formula, R ^{2 is} independently an unsubstituted or halogen atom or cyano substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, c1 is a positive number of 0.1 to 2, c2 is a positive number of 0.01 to 2, and c1 + c2 is Positive numbers below 3, with more than two SiH groups in one molecule, selected at a viscosity of 25 ° C in the range of 0.005 ~ 10Pa · s), (D) platinum group metal catalyst with catalyst amount, (E ) Organic solvents: 0 to 100,000 parts by mass.

〔2〕

The polysiloxane composition for release paper or release film according to [1], wherein the component (C) is an organic hydrogen polysiloxane represented by the following general formula (9) and / or the following general formula (10):

(In the formula, Me is a methyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ^{5 is} each independently a hydrogen atom or contains no aliphatic unsaturated bond. Unsubstituted or halogen atom or cyano-substituted monovalent hydrocarbon group, R ⁶ and R ⁷ are each independently unsubstituted or halogen atom or cyano-substituted monovalent hydrocarbon group other than Me without aliphatic unsaturated bond, Y ³ Each is independently the following general formula (11-1), Y ^{4 is} each independently the following general formula (11-2), and Y ^{5 is} each independently the following general formula (11-3)

In the base shown, Y ^{6 is} each independently the following general formula (12-1), Y ^{7 is} each independently the following general formula (12-2), and Y ^{8 is} each independently the following general formula (12-3)

As shown above, R ⁵ , R ⁶ , and R ^{7 are} as described above, c11, c12, c31, c41, c51, c61, c71, and c81 are each independently an integer of 0 to 3, c23 is an integer of 2 or more, and c13 to c19 , C24 ~ c29, c32 ~ c38, c42 ~ c48, c52 ~ c58, c62 ~ c66, c72 ~ c76, c82 ~ c86 are integers of 0 or more, c23 + c24 + c25 + c26 + c27 + c28 + c29 is 3 or more Integer, there are 2 or more hydrogen atoms bonded to silicon atoms in a molecule, and the viscosity is selected in the range of 0.005 ~ 10Pa · s at a viscosity of 25 ° C).

[3]

The polysiloxane composition for release paper or release film as in [1] or [2], in which the component (C) is 2 or more R ² ₂ HSiO _1/2 units in one molecule (R ² is free of fat) (Unsubstituted or halogen atom or cyano-substituted monovalent hydrocarbon group) organic hydrogen polysiloxane, or a mixture containing a part of the organic hydrogen polysiloxane.

[4]

The polysiloxane composition for release paper or release film according to any one of [1] to [3], wherein the component (C) is (C1) an organic hydrogen polysiloxane containing no aromatic substituent and (C2 ) A mixture of organohydrogenpolysiloxanes containing aromatic substituents. The mass ratio (C1) / (C2) of these (C1) and (C2) components is 1/9 to 9/1.

[5]

The silicone composition for release paper or release film according to any one of [1] to [4], which further contains the following general formula (13) as a component (F) with respect to 100 parts by mass of the component (A). 0.1 to 30 parts by mass of organic polysiloxane,

(In the formula, Me is methyl, R ^{8 is} independently hydroxy, alkoxy, or alkoxyalkyl, and R ^{9 is} independently hydroxy, alkoxy, alkoxyalkyl, and free of aliphatic unsaturated bonds. A substituted or halogen atom or a cyano-substituted monovalent hydrocarbon group. R ^{10 is} independently an unsubstituted or halogen atom or a cyano group other than hydroxyl, alkoxy, alkoxyalkyl, and Me containing no aliphatic unsaturated bond. Monovalent hydrocarbon group, f1 and f2 are integers of 1 ~ 3, f3 ~ f5 is the range where the viscosity of the organopolysiloxane at 25 ° C falls above 1Pa‧s, and the dilution viscosity of 30% by mass of toluene is below 100Pa‧s To choose).

[6]

The polysiloxane composition for a release paper or a release film according to any one of [1] to [5], which further contains an organic polysiloxane 10 as a (G) component with respect to 100 parts by mass of the (A) component. ~ 100 parts by mass, the organic polysiloxane has at least two alkenyl groups, with R ² _(3-g1) R ¹ _g1 SiO _1/2 siloxane units (M ^R1R2 units), R ² SiO _3/2 Siloxane units (T ^R2 units) (wherein R ^{1 is} independently an alkenyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, and g1 is 1 ~ Integer of 3) As a necessary unit, the molar ratio of M ^R1R2 units / T ^R2 units satisfies 2/8 ~ 8/2, the viscosity at 25 ° C has a range of 0.001 ~ 1Pa‧s, and the molecular ends are M ^R1R2 units, Or M ^R1R2 units and part is silanol or alkoxy.

[7]

The silicone composition for release paper or release film according to any one of [1] to [6], which further contains at least one ring as a component (H) per 100 parts by mass of the component (A). 0.1 to 10 parts by mass of an organic silane and an alkoxysilyl group represented by the following general formula (14) and / or a partially hydrolyzed (co) condensed siloxane represented by the following average composition formula (15) , R ¹¹ _h1 (OR ¹² ) _h2 Si (R ¹³ ) _(4-h1-h2) (14)

R ¹¹ _h3 (OR ¹² ) _h4 (R ¹³ ) _h5 SiO _{(4-h3-h4-h5) / 2} (15)

(In the formula, R ¹¹ is a monovalent organic group containing an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms, which may include an ether bond, and a part thereof may be hydrolyzed to a hydroxyl group. R ¹³ is unsubstituted or halogen An atom or a cyano-substituted monovalent hydrocarbon group. H1 and h2 are integers and satisfy 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, h3 ~ h5 are positive numbers and satisfy 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, selected by the positive number of the partially hydrolyzed (co) condensed siloxane at 25 ° C to be in the range of 0.001 ~ 1Pa · s).

〔8〕

The silicone composition for release paper or release film according to any one of [1] to [7], which further contains the following general formula (16) as a component (I) with respect to 100 parts by mass of the component (A). The siloxane unit (M unit) shown by) and the siloxane unit (Q unit) shown by the following formula (17) are 2/8 to 8/2 in molar ratio (M unit / Q unit). 1 ~ 100 parts by mass of MQ resin, R ² _(3-i1) R ¹ _i1 SiO _1/2 (16)

SiO _4/2 (17)

(In the formula, R ^{1 is} independently an alkenyl group, and R ^{2 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and i1 is an integer of 0 to 3).

〔9〕

The silicone composition for release paper or release film according to any one of [1] to [8], which further contains a nonionic surfactant as a component (J) with respect to 100 parts by mass of the component (A). 0.1 to 5 parts by mass.

[10]

A release paper or release film having a cured film of a polysiloxane composition for release paper or release film according to any one of [1] to [9].

Exposure resistance and peeling of the release agent and release film of the present invention Excellent sex. The hardened release paper and release film are coated with the silicone composition of the release paper or release film of the present invention, and even if the silicone-coated surface is exposed to air for a long time, the release property before exposure can be almost maintained.

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

[Polysiloxane composition for release paper or release film]

The polysiloxane composition for a release paper or a release film of the present invention contains the following (A) to (D) components, and an addition reaction-hardening type polysiloxane composition containing the (E) to (J) components as necessary Substance, which hardens by addition reaction.

(A) Ingredient

The organopolysiloxane which constitutes the component (A) of the addition reaction-hardening type polysiloxane composition of the present invention has a structure represented by the following general formula (1), and has at least two alkenyl groups in one molecule. By.

(In the formula, R ^{1 is} independently an alkenyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, and X ^{1 is} independently the following general formula (2-1) , X ^{2 is} independently the following general formula (2-2), X ^{3 is} independently the following general formula (2-3)

In the base shown, X ^{4 is} each independently the following general formula (3-1), X ^{5 is} each independently the following general formula (3-2), and X ^{6 is} each independently the following general formula (3-3)

The base shown. R ¹ and R ^{2 are} as described above, and a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3. a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, and a63 are 0 or positive numbers. These are based on the viscosity of organic polysiloxane at 25 ° C. (Select from the range of 0.05 Pa · s or more and 30% by mass toluene dilution viscosity of 70 Pa · s or less).

In the above formula (1), R ¹ is the same or different vinyl, allyl, propenyl, etc., preferably alkenyl having 2 to 10 carbon atoms, more preferably 2 to 8, and R ¹ is vinyl Good for industrial.

R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl, and cycloalkyl groups such as cyclohexyl Aryl groups such as phenyl, tolyl, etc., or some or all of the hydrogen atoms of carbon atoms bonded to these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, etc., and cyano as substituents Chloromethyl, trifluoropropyl, cyanoethyl, etc. are preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and are unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, etc. . R ^{2 is} more than 80 mole% methyl, and phenyl is better in manufacturing and characteristics. Furthermore, R ² is more than 40 mole%, especially more than 50 mole% is methyl, and less than 40 mole% is Phenyl is preferred.

The (A) component of the organopolysiloxane has two or more alkenyl groups in one molecule, and it is not suitable because less than two uncrosslinked molecules may remain after curing and the hardenability is reduced. The alkenyl content per 100 g of the organic polysiloxane is preferably 0.001 to 0.5 mol, and more preferably 0.002 to 0.45 mol. If the content is less than 0.001 mol, there may be a decrease in sclerosis, and if it exceeds 0.5 mol, the pot life may be shortened and the operation may be difficult.

In addition, in the above formula (1), the number of alkenyl groups in one molecule is 2 to 300, and it is particularly preferable to select a range of 3 to 280. At this time, the number of alkenyl groups is [a1 + a2 + a4 + a5 × {a11 + a13 + a14 × (a41 + a43) + a15 × (a51 + a53 + a61 + a63)} + a6 × {a21 + a23 + a31 + a33 + (a24 + a34) × (a41 + a43) + (a25 + a35) × (a51 + a53 + a61 + a63)}].

In the above formula (1), a1, a2, a11, a21, a31, a41, a51, and a61 are each independently an integer of 0 to 3.

Furthermore, in the above formula (1), a3 is a positive number, a4 to a6, a12 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62, a63 are 0 or a positive number. Positive viscosity.

(A) The viscosity of the organopolysiloxane at 25 ° C is Above 0.05 Pa‧s, the dilution viscosity of 30% by mass of toluene is within the range of 70Pa‧s, preferably within the range of 0.1Pa‧s, and the dilution viscosity of 30% by mass of toluene is below 60Pa‧s. When the viscosity is less than 0.05Pa‧s, the mold release property is insufficient, and the dilution viscosity of 30% by mass of toluene exceeding 70Pa‧s decreases the workability. Here, the viscosity can be measured by a rotary viscometer (the same applies hereinafter).

In addition, in the above formula (1), the degree of polymerization is preferably 50 to 20,000, and is particularly preferably selected within a range of 55 to 19,000. At this time, the degree of polymerization is from [2 + a3 + a4 + a5 × {2 + a12 + a13 + a14 × (2 + a42 + a43) + a15 × (3 + a52 + a53 + a62 + a63)} + a6 × { 3 + a22 + a23 + a32 + a33 + (a24 + a34) × (2 + a42 + a43) + (a25 + a35) × (3 + a52 + a53 + a62 + a63)}].

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

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

_{Me 2 ViSiO- (Me 2 SiO)} 1000 -SiViMe 2 MeVi 2 SiO- (Me 2 SiO) 500 -SiVi 2 Me Vi 3 SiO- (Me 2 SiO) 2000 -SiVi 3 Me 2 ViSiO- (Me 2 SiO) 9900 (MeViSiO) ₁₀₀ -SiViMe ₂

(B) Ingredient

The component (B) of the present invention is formulated as one of the components for improving the resistance to exposure, and is selected from the group consisting of olefins having 8 to 30 carbon atoms having an unsaturated bond at the terminal represented by the following general formula (4). The diolefins having 10 to 32 carbon atoms having unsaturated bonds at both ends shown in the general formula (5) are described, and the number of 1-4 is shown in the following general formula (6), especially 1 to 3 ends. Do not Alkanyl silanes having 8 to 30 carbon atoms in saturated bonds, and 8 to 30 carbon atoms having 2 to 6 carbon atoms, especially 2 to 4 terminals having unsaturated bonds, as shown in the following general formula (7). One or more compounds of alkenyl disiloxane.

CH ₂ = CH-R ³ -H (4)

CH ₂ = CH-R ³ -CH = CH ₂ (5)

(CH ₂ = CH-R ³ ) _b1 SiR ⁴ _4-b1 (6)

(In the formula, R ^{3 is} each independently a bivalent hydrocarbon group having 6 to 28 carbon atoms, R ^{4 is} independently a monovalent hydrocarbon group or alkoxy group having 1 to 10 carbon atoms, b1 is an integer of 1 to 4 and b2 is independently 1 to 4 An integer of 3).

In the above formulae (4) to (7), R ³ is a divalent hydrocarbon group having 6 to 28 carbon atoms, and preferably 6 to 24 carbon atoms. Examples include hexamethylene, heptamethylene, octamethylene, and nine methylene. Methyl, decamethylene, undecymethylene, dodecylmethylene, tridecylmethylene, tetradecylmethylene, pentamethylene, hexamethylene, heptamethylene, ten Cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, etc. Rings of heptyl, octyl, octyl nonyl, octyl decyl, octyl 12, octyl 14, octyl 16, octyl 18, octyl 20 Alkyl, phenylene, benzylidene, stubyl, trimethyl phenylene, naphthyl, phenylene, etc. aryl, methylene phenylene, methylene phenylene Methylene and other aralkyl groups.

R ⁴ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. As a monovalent hydrocarbon group, it does not contain aliphatic unsaturation. The bond is preferably, for example, an alkyl group such as methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, or cyclohexyl. Alkyl groups, aryl groups such as phenyl, tolyl, xylyl, naphthyl, aralkyl groups such as benzyl, phenylethyl, phenylpropyl, etc., and examples of the hydrocarbonoxy group include methyl Oxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, Methoxyethyl, methoxybutyl, ethoxyethyl, ethoxybutyl, ethoxyhexyl, propoxybutyl, butoxybutyl and the like.

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

Specific examples of the olefin represented by the formula (4) include 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1 -Tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, 1-docosaene, 1-tetracosene, 1-hexadecene, 1-octacosene , 1-tridecene, etc.

Specific examples of the diene represented by the formula (5) include 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, and 1,13-tetradecane. Diene, 1,15-hexadecadiene, 1,17-octadecadiene, 1,19-icosanediene, 1,21-icosadiene, 1,23-icosadiene Tetradiene, 1,25-hexadecanediene, 1,27-octadecanediene, 1,29-triacontadiene, and the like.

Specific examples of the silane represented by formula (6) include CH ₂ = CH- (CH ₂ ) ₆ -Si (CH ₃ ) ₃ and CH ₂ = CH- (CH ₂ ) ₈ -Si (CH ₃ ) ₃ , CH ₂ = CH- (CH ₂ ) ₆ -Si (C ₃ H ₇ ) ₃ , CH ₂ = CH- (CH ₂ ) ₆ -Si (CH ₃ ) ₂ OCH ₃ , CH ₂ = CH- (CH ₂ ) ₆ -Si (CH ₃ ) (OCH ₃ ) ₂ , [CH ₂ = CH- (CH ₂ ) ₆ ] ₂ Si (CH ₃ ) ₂ , CH ₂ = CH- (CH ₂ ) ₁₂ -Si (CH ₃ ) ₃ etc.

As the disiloxane represented by the formula (7), specifically, for example, Wait.

The structure of the alkenyl compound of the component (B) with little or no Si content is presumed to suppress the volatility by using a relatively high molecular weight compound, so that most of them can form a chemical bond in the hardened film, and at the same time, In the hardened film formed by the cross-linking of the component (A), the dispersion state of the component (B) is unevenly formed, for example, it shows the influence of the tendency of the density separation between the surface and the inside of the film. It is considered that the effect of improving the exposure resistance may be exhibited by forming a portion having a high hydrocarbon group concentration. In addition, the preparation of these alkenyl compounds has almost no effect on the peeling properties, and is suitable as a method for preventing re-peeling, reduction of residual adhesion, and performance of migration properties.

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

(C) Ingredient

The organohydrogenpolysiloxane based on the component (C) of the present invention has at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and is represented by the following average composition formula (8).

R ² _c1 H _c2 SiO _{(4-c1-c2) / 2} (8)

(In the formula, R ² is the same as above, c1 is a positive number of 0.1 ~ 2, c2 is a positive number of 0.01 ~ 2, c1 + c2 is a positive number of 3 or less, there are two or more SiH groups in one molecule, and the temperature is 25 ° C. The viscosity falls within the range of 0.005 ~ 10Pa‧s to choose).

In the above formula (8), R ² can be exemplified by the same monovalent hydrocarbon group without aliphatic unsaturated bond as R ^{2 in the} above formula (1). Among them, methyl, ethyl, propyl, and butyl Alkyl groups such as cycloalkyl, cycloalkyl groups such as cyclohexyl, and aryl groups such as phenyl are preferred.

In addition, c1 is a positive number of 0.1 ~ 2, preferably 0.2 ~ 2, c2 is 0.01 ~ 2, preferably 0.04 ~ 1.5, more preferably a positive number of 0.1 ~ 1, c1 + c2 is 3 or less, preferably 0.5 ~ 3, more preferably a positive number of 1 ~ 3, with more than two SiH groups in one molecule, viscosity at 25 ° C to be in the range of 0.005 ~ 10Pa‧s, preferably in the range of 0.01 ~ 10Pa‧s . Outside this viscosity range, the hardenability is reduced.

In the organohydrogen polysiloxane containing the component (C), the number of hydrogen atoms bonded to the silicon atom in one molecule is two or more, preferably 3 to 1,000. When less than two, the sclerosis is insufficient. The SiH group content per 100 g of organic hydrogen polysiloxane is preferably 0.1 to 1.7 moles, preferably 0.2 to 1.7 moles, and more preferably 0.3 to 1.7 moles. If the content is too small, the hardenability may be insufficient, and if it is too large, the storage stability may be reduced.

The viscosity of the organic hydrogen polysiloxane of the component (C) at 25 ° C is preferably in the range of 0.005 to 10 Pa · s, and more preferably in the range of 0.005 to 5 Pa · s. If the viscosity is too small, there is a case where the hardening property is insufficient, and if it is too high, there is a case where the storage stability is insufficient.

In addition, the molecular structure of the component (C) may be one of linear, branched, or cyclic, and may also be a structure of these combinations, and a plurality of these may be used in combination.

Specific examples of the compound represented by the formula (8) include straight-chain methylhydrosiloxane, which is composed of Me ₃ SiO _1/2 and Me (H) SiO _2/2 siloxane units. Polymer; linear methyl hydrosiloxane, which is a polymerization of Me ₂ (H) SiO _1/2 , Me (H) SiO _2/2 and Me ₂ SiO _2/2 units Substance; linear methylphenylhydrosiloxane, which is a polymer made of Me ₃ SiO _1/2 , Me (H) SiO _2/2, and MePhSiO _2/2 ; linear methylphenyl Hydrosiloxanes are polymers composed of Me ₂ (H) SiO _1/2 , Me (H) SiO _2/2, and Ph ₂ SiO _2/2 siloxane units; branched methyl hydrosiloxane Alkoxysilane, which is a polymer formed from Me ₃ SiO _1/2 , Me (H) SiO _2/2, and MeSiO _3/2 siloxane units; branched methylphenylhydrosiloxane, which Based on Me ₂ (H) SiO _1/2 , Me (H) SiO _2/2 , Ph ₂ SiO _2/2, and PhSiO _3/2 siloxane units; cyclic methylhydrogen siloxane Alkane, which is a polymer made of Me (H) SiO _2/2 siloxane units only; cyclic methylhydrosiloxane, which consists of Me ₂ SiO _2/2 and Me (H) SiO ₂ polymer _{/ 2} siloxane units made of silicon; the cyclic hydrogen-methylphenyl silicone Alkyl, which is based a MePhSiO _2/2 and Me (H) SiO _2/2 siloxane units made of silicon polymers.

The component (C) is more preferably an organohydrogenpolysiloxane having a linear structure or a branched structure represented by the following general formula (9) and / or a cyclic structure represented by the following general formula (10) The organohydrogenpolysiloxane may also be an organohydrogenpolysiloxane containing both a linear structure and a cyclic structure in one molecule.

(Wherein R ² is the same as above, R ^{5 is} each independently a hydrogen atom or an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and R ⁶ and R ⁷ are each independently free Y ^{3 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group other than Me of an aliphatic unsaturated bond, and Y ^{4 is} each independently of the following general formula (11- 2), Y ⁵ are each independently the following general formula (11-3)

In the base shown, Y ^{6 is} each independently the following general formula (12-1), Y ^{7 is} each independently the following general formula (12-2), and Y ^{8 is} each independently the following general formula (12-3)

As shown above, R ⁵ , R ⁶ , and R ^{7 are} as described above, c11, c12, c31, c41, c51, c61, c71, and c81 are each independently an integer of 0 to 3, c23 is an integer of 2 or more, and c13 to c19 , C24 ~ c29, c32 ~ c38, c42 ~ c48, c52 ~ c58, c62 ~ c66, c72 ~ c76, c82 ~ c86 are integers of 0 or more, c23 + c24 + c25 + c26 + c27 + c28 + c29 is 3 or more Integer, there are two or more, especially three or more SiH groups in one molecule, and the viscosity is selected in the range of 0.005 ~ 10Pa · s at 25 ° C).

In the above formulae (9) and (10), R ² may be exemplified by the same monovalent hydrocarbon group containing no aliphatic unsaturated bond as R ^{2 in the} above formula (1). Among them, methyl, ethyl, and propyl Alkyl groups such as alkyl and butyl, cycloalkyl groups such as cyclohexyl, and aryl groups such as phenyl are preferred.

R ^{5 is} each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and examples thereof include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. Cycloalkyl groups, aryl groups such as phenyl, tolyl, etc., or some or all of the hydrogen atoms of carbon atoms bonded to these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, etc., and cyano as substituents The substituted chloromethyl, trifluoropropyl, cyanoethyl, etc. are preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, which are unsubstituted or substituted without aliphatic unsaturated bonds. Valence hydrocarbon groups and the like include hydrogen atoms, methyl, ethyl, propyl, butyl and other alkyl groups, cyclohexyl and other cycloalkyl groups, and aryl and other aryl groups.

R ⁶ and R ⁷ are each independently an unsubstituted or substituted monovalent hydrocarbon group other than Me containing no aliphatic unsaturated bond, and examples thereof include an alkyl group such as ethyl, propyl, and butyl, and a ring such as cyclohexyl. An alkyl group, an aryl group such as phenyl, tolyl, or the hydrogen atom of a carbon atom bonded to these groups is partially or wholly substituted with a halogen atom such as fluorine, chlorine, bromine, etc., and a cyano group as a substituent. The substituted chloromethyl, trifluoropropyl, cyanoethyl, etc. are preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and are unsubstituted or substituted monovalent without aliphatic unsaturated bonds. Hydrocarbyl, etc.

Among these, R ^{6 is} preferably an alkyl group, and as a substituent for changing the carbon number, an effect of changing the properties of the cured film can be obtained. However, if the carbon number becomes too large, the hardenability tends to decrease, so it is better to select from a carbon number of 4 or less, and ethyl and propyl are more industrially preferable. An ethyl group having a carbon number of 2 is more suitable for the extraction. As R ⁷ , an alkyl group such as ethyl, propyl, or butyl, or a cycloalkyl group such as cyclohexyl is preferred.

(C) Substituents contained in one molecule of the component may be mutually However, it is preferably more than 50 mole%, and more preferably more than 80 mole%. In the release film, there are many applications in which high transparency of the hardened film or adhesion to the substrate is pursued. In this case, the substituents of the component (C) are changed to have a higher number than the number of methyl carbons. Volume substituents or aromatic substituents can promote the wetting or interaction of the surface of the film substrate. The component (C) without an aromatic substituent is referred to as the (C1) component, and the component (C) with an aromatic substituent is referred to as the (C2) component, and the ratio by mass of (C1) / (C2) = 1/9 ~ 9/1, especially 2/8 ~ 9/1 organic hydrogen polysiloxane mixture is suitable, and it is easy to balance with other characteristics such as peeling force of hardened film.

Here, as the component (C1), in the general formula (9) and / or the general formula (10), R ² is a monovalent hydrocarbon group other than an aromatic group containing no aliphatic unsaturated bond, and R ⁵ is The structure of a monovalent hydrocarbon group other than a hydrogen atom or an aromatic group containing no aliphatic unsaturated bond, and R ⁶ and R ⁷ being a monovalent hydrocarbon group other than the aromatic group containing no aliphatic unsaturated bond is preferred.

In addition, as the component (C2), in the general formula (9) and / or the general formula (10), at least one of R ² and R ⁵ to R ⁷ is a monovalent hydrocarbon group having an aromatic group. good.

In the above formulae (9) and (10), c11, c12, c31, c41, c51, c61, c71, and c81 are each independently an integer of 0 to 3, preferably 0 or 1.

(C) The organohydrogenpolysiloxane is an organohydrogenpolysiloxane having 2 or more R ² ₂ HSiO _1/2 units (R ² is the same as the above) in one molecule, or a part containing the organic Mixtures of hydrogen polysiloxanes are preferred.

In the above formulae (9) and (10), c23 is an integer of 2 or more, c13 to c19, c24 to c29, c32 to c38, c42 to c48, c52 to c58, c62 to c66, c72 to c76, c82 to c86 is an integer of 0 or more, has 2 or more, especially 3 or more SiH groups in one molecule, and satisfies the positive number of the viscosity of the component (C).

In the above formula (10), c23 + c24 + c25 + c26 + c27 + c28 + c29 is an integer of 3 or more.

The number of SiH groups in the organohydrogenpolysiloxane represented by the above formulas (9) and (10) is two or more, especially three or more. When less than two, the time required for hardening may be long and the production efficiency may decrease. .

In addition, in the above formula (9), the number of SiH groups in one molecule is preferably selected in a range of 2 to 1,000, especially 3 to 1,000, and particularly 3 to 500. At this time, the base number of SiH in a molecule is [c11 + c12 + c13 + c14 + c15 × {c31 + c32 + c33 + c34 × (c61 + c62 + c63)} + c16 × {c41 + c42 + c43 + c51 + c52 + c53 + (c44 + c54) × (c61 + c62 + c63) + (c45 + c55) × (c71 + c72 + c73 + c81 + c82 + c83)}].

In the above formula (10), the number of SiH groups in one molecule is preferably selected in a range of 2 to 100, especially 3 to 100, and particularly 4 to 50. At this time, the base number of SiH in one molecule is [c23 + c24 + c25 × {c31 + c32 + c33 + c34 × (c61 + c62 + c63)} + c26 × {c41 + c42 + c43 + c51 + c52 + c53 + ( c44 + c54) × (c61 + c62 + c63) + (c45 + c55) × (c71 + c72 + c73 + c81 + c82 + c83)}].

In addition, in the above formula (9), the degree of polymerization is preferably selected in a range of 3 to 1,000, particularly 3 to 500. At this time, the degree of aggregation is from [2 + c13 + c14 + c15 × {2 + c32 ++ c33 + c34 × (2 + c62 + c63 + c64 + c65 + c66) + c35 × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86) + c36 + c37 + c38} + c16 × {3 + c42 + c43 + c46 + c47 + c48 + c52 + c53 + c56 + c57 + c58 + (c44 + c54 ) × (2 + c62 + c63 + c64 + c65 + c66) + (c45 + c55) × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86)) + c17 + c18) + c19] to calculate.

In the above formula (10), the degree of polymerization is preferably selected in a range of 3 to 100, particularly 4 to 50. At this time, the degree of aggregation is from [c23 + c24 + c25 × {2 + c32 ++ c33 + c34 × (2 + c62 + c63 + c64 + c65 + c66) + c35 × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86) + c36 + c37 + c38} + c26 × {3 + c42 + c43 + c46 + c47 + c48 + c52 + c53 + c56 + c57 + c58 + (c44 + c54) × (2 + c62 + c63 + c64 + c65 + c66) + (c45 + c55) × (3 + c72 + c73 + c74 + c75 + c76 + c82 + c83 + c84 + c85 + c86)) + c27 + c28 + c29 ] To calculate.

Specific examples of the organohydrogenpolysiloxane represented by the formulae (9) and (10) include the following.

Me ₃ SiO- (Me (H) SiO) ₁₀₀ -SiMe ₃ Me ₂ (H) SiO- (Me (H) SiO) _50- (Me ₂ SiO) ₅₀ -Si (H) Me ₂

In addition, as an organohydrogenpolysiloxane containing both a linear structure and a cyclic structure in one molecule, for example, the organohydrogenpolysiloxane represented by the above formula (9) and the one represented by the above formula (10) can be exemplified. In the organohydrogenpolysiloxane, one of the SiH groups at the end of the molecular chain of the formula (9) and one of the SiH groups of the formula (10) are crosslinked, and the Si atoms pass through the divalent organic group (-CH _2- An organohydrogenpolysiloxane having two types of structures: a linear structure and a cyclic structure, such as a CH ₂ -etc.) Or an oxygen atom (-O-).

In the linear structure, the branched structure, and the ring structure, the crosslinked state of the hardened film can be different, so the peeling characteristics can be controlled by selection. The ring structure is effective for making the hardened film harder and reducing the speed dependency of the peeling force. The linear structure reduces the peeling force of the hardened film. effective. The branched structure is effective in improving the hardenability of the composition at the point that many terminal SiH functional groups that are favorable to the hardening reaction can be introduced.

As an example of a branched organic hydrogen polysiloxane having a special structure among the branched organic hydrogen polysiloxanes represented by the above formula (9), monofunctional R ² ₂ HSiO _1/2 silicone can be exemplified. Unit (R ² is the same as above (hereinafter the same), and is hereinafter referred to as M ^H unit) and / or R ² ₃ SiO _1/2 siloxane unit (hereinafter referred to as M unit) and trifunctional R ² SiO ₃ Siloxane units (hereafter referred to as T units) made of _{/ 2} siloxane units (hereinafter referred to as HMT siloxane units), which are composed of M ^H units or M units and tetrafunctional SiO _4/2 siloxane units ( It is referred to as a Q unit hereinafter (hereinafter referred to as HMQ siloxane).

Any of the radicals represented by R ^{2 of the} siloxane is preferably Me-based or Ph-based for industrial use.

The molar ratio of (M ^H unit + M unit) / T unit in HMT siloxane is preferably 2/8 ~ 8/2, especially 3/7 ~ 7/3. Mo unit / M ^H unit The ear ratio is preferably from 0/10 to 9/1, especially from 0/10 to 8/2. In addition, it is preferable that M ^H units or M units are bonded to the molecular ends, but a part may be formed with a silanol group or an alkoxy group to form a terminal.

The same is true for HMQ siloxane, the molar ratio of (M ^H unit + M unit) / Q unit is 2/8 ~ 8/2, especially 3/7 ~ 7/3, M unit / M ^H unit The molar ratio is preferably from 0/10 to 9/1, especially from 0/10 to 8/2. It is advisable to have M ^H units or M units bonded to the molecular ends, but some of them are silanol groups or alkoxy groups. The base may form a terminal.

As the specifics of these HMT siloxanes and HMQ siloxanes Examples include the following.

These HMT siloxane and HMQ siloxane show the effect of improving the exposure resistance, and even if used alone, a certain degree of effect can be expected, but the combination with (B) component can further improve the exposure resistance. . It is presumed that the organohydrogenpolysiloxane having a branched structure is easy to gather on the surface of the hardened film due to its structural characteristics, and forms a surface that is not easily exposed.

In addition, in HMQ siloxane, it is preferable to increase the molar ratio (M ^H unit + M unit) / Q unit or reduce the degree of polymerization in order to suppress re-peeling. The use of HMQ siloxane as a heavy peel control agent has been known in the past, but in particular, increasing the molar ratio (M ^H unit + M unit) / Q unit or reducing the degree of polymerization can effectively suppress heavy peeling. The same effect can be expected for HMDQ siloxanes containing difunctional (R ² ) ₂ SiO _2/2 siloxane units (hereinafter referred to as D units). For HMT siloxane, the same method can be used to improve it.

(C) The organohydrogenpolysiloxane can be used alone or in combination of two or more.

The compounding amount of the organohydrogenpolysiloxane in the component (C) is equivalent to the molar number of the hydrogen atom (SiH group) bonded to the silicon atom in the component (C) being components (A) and (B). An amount of 1 to 20 times, preferably 1.1 to 15 times, the total mole number of the alkenyl group (unsaturated group) in (or this and any of the components described later). (C) When the MoH number of the SiH group in the component is less than 1 time of the total Mohr number of the alkenyl group (unsaturated group), the hardening property is insufficient, and on the other hand, no exposure resistance is seen even if it is blended more than 20 times The effect is significantly increased, but it is economically unfavorable because of changes over time. In addition, as a general organohydrogenpolysiloxane compounding amount, it can be in a range of 0.1 to 30 parts by mass based on 100 parts by mass of the organopolysiloxane of the component (A).

(D) Ingredient

The platinum group metal catalyst (addition reaction catalyst) of the component (D) of the present invention promotes the intersection of the components (A) and (B) (or any component containing an alkenyl group described later) with the component (C) This reaction is used to form a hardened film. Examples of the addition reaction catalyst include platinum rhenium, chloroplatinic acid, Chloroplatinic acid-olefin complexes, chloroplatinic acid-alcohol complexes, platinum vinyl-containing siloxane complexes, rhodium, rhodium-olefin complexes, and the like.

The amount of the above-mentioned addition reaction catalyst is the amount of the catalyst. Although it can be appropriately increased or decreased according to the reactivity of the aforementioned components or the desired curing rate, the platinum is relative to the total mass of the components (A) to (C). It is preferable to mix 5 to 1,000 ppm (mass ratio) of the amount or the amount of rhodium to form a sufficient hardened film.

(E) Ingredient

The organic solvent of the component (E) of the present invention can be prepared as needed for the purpose of improving the stability of the treatment bath and the applicability to various substrates, and adjusting the coating amount and viscosity. In particular, it is advantageous for imparting a desired effect that the polysiloxane composition for a release film can be thin-film coated and that the surface smoothness of the cured film is improved. As the organic solvent, for example, a composition capable of uniformly dissolving a composition such as toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, hexane, and 2-butanone can be used.

In addition, the (E) component is an optional component, and it may not be blended due to the deterioration of the danger or safety of the organic solvent, and it is also possible to use it as a silicone composition for a solventless release paper or a release film. .

(E) The organic solvent of a component may be used individually by 1 type, and may use 2 or more types together.

The amount of the component (E) to be used is preferably 10 to 100,000 parts by mass with respect to 100 parts by mass of the component (A), and particularly preferably in a range of 10 to 10,000 parts by mass. If the blending amount is too large, it may become difficult to control the coating amount. In some cases, if it is too small, the effect of blending the solvent, the coating property, or the improvement of the pot life may not be seen.

Although the polysiloxane composition of the present invention can be easily manufactured by uniformly mixing the aforementioned components (A), (B), (C), (D) and, if necessary, the (E) component, in order to ensure sufficient application It is preferable that the component (C) or the component (D) is added and mixed before coating. When an organic solvent of the component (E) is used, it is advantageous that the component (A) is uniformly dissolved in the component (E) and then the components (B), (C), or (B) and (D) are mixed.

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

(F) Ingredient

The (F) component is an organic polysiloxane represented by the following general formula (13). The component (F) is different from the component (A) in that it does not contain an alkenyl group as a functional group.

(Wherein R ^{8 is} independently a hydroxyl group, an alkoxy group, or an alkoxyalkyl group, and R ^{9 is} independently a hydroxyl group, an alkoxy group, an alkoxyalkyl group, and an unsubstituted or halogen atom having no aliphatic unsaturated bond or A cyano-substituted monovalent hydrocarbon group, R ^{10 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group other than hydroxyl, alkoxy, alkoxyalkyl, and Me without aliphatic unsaturated bonds, f1 , F2 is an integer of 1 ~ 3, f3 ~ f5 is selected according to the range of the viscosity of the organic polysiloxane at 25 ° C falling above 1 Pa · s and the dilution viscosity of 30% by mass of toluene being below 100 Pa · s).

In the formula (13), R ^{8 is} independently a hydroxyl group, an alkoxy group, or an alkoxyalkyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and n-butane. 1 to 6 carbons such as oxy, sec-butoxy, and tert-butoxy. Examples of the alkoxyalkyl group include methoxyethyl, ethoxyethyl, methoxypropyl, Ethoxypropyl, methoxybutyl, ethoxybutyl, etc. have 1 to 6 carbon atoms.

R ^{9 is} independently a hydroxy group, an alkoxy group, an alkoxyalkyl group, and an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond. Specifically, examples thereof include methyl, ethyl, propyl, and butyl. Some alkyl groups, cyclohexyl groups, cycloalkyl groups, phenyl groups, tolyl groups, aryl groups, etc., or some or all of the hydrogen atoms of carbon atoms bonded to these groups are fluorine, chlorine, bromine, etc. The chloromethyl, trifluoropropyl, cyanoethyl, etc. substituted by a halogen atom or a cyano group as a substituent are preferably 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms. Valence hydrocarbon groups and the like are preferably hydroxy, alkoxy and unsubstituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and alkyl groups such as methyl, ethyl, propyl, butyl, and cyclohexyl are used. Aryl groups such as alkyl, phenyl and tolyl are more preferred.

R ^{10 is} independently an unsubstituted or substituted monovalent hydrocarbon group other than hydroxyl, alkoxy, alkoxyalkyl, and Me without aliphatic unsaturated bonds. Specifically, examples thereof include ethyl, propyl, and butyl. Some alkyl groups, cyclohexyl groups, cycloalkyl groups, phenyl groups, tolyl groups, aryl groups, etc., or some or all of the hydrogen atoms of carbon atoms bonded to these groups are fluorine, chlorine, bromine, etc. The chloromethyl, trifluoropropyl, cyanoethyl, etc. substituted by a halogen atom or a cyano group as a substituent are preferably 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms. Valence hydrocarbon groups and the like are preferably hydroxy, alkoxy and unsubstituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and alkyl groups such as ethyl, propyl, butyl, and cycloalkyl groups such as cyclohexyl, Aryl groups such as phenyl and tolyl are more preferred.

f1 and f2 are integers of 1 to 3, preferably 1 or 2, and f3 to f5 are integers that satisfy the viscosity described later.

(F) The organopolysiloxane has a viscosity at 25 ° C of 1 Pa · s or more, 30% by mass toluene dilution viscosity in the range of 100Pa · s or less, and especially 10Pa‧s ~ 30% by mass toluene dilution viscosity of 50Pa. The range of ‧s is better. If the viscosity is too low, the smoothness of the hardened film may be insufficient, and if it is too high, the industrial operation may become difficult.

In such a linear polymer, a siloxane having no functional group in a side lock is effective for imparting smoothness to a cured film, and the effect of reducing the peeling force without reducing the residual adhesive force can also be expected. The peeling film also exhibits the effect of preventing peeling due to its smooth effect.

Specific examples of the (F) component include the following polysiloxanes.

(HO) Me ₂ SiO- (Me ₂ SiO) ₁₀₀₀₀ -SiMe ₂ (OH) (MeO) Me ₂ SiO- (Me ₂ SiO) ₂₀₀₀ -SiMe ₂ (OMe) (EtO) Me ₂ SiO- (Me ₂ SiO) _500- (Ph ₂ SiO) ₃₀ -SiMe ₂ (OEt) (HO) Me ₂ SiO- (Me ₂ SiO) _500- (Ph ₂ SiO) ₁₀ -SiMe ₂ (OH)

The blending amount when blending (F) ingredients is relative to (A) It is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass. If it is less than 0.1 parts by mass, the effect of imparting smoothness may not be obtained, and if it exceeds 30 parts by mass, a decrease in residual adhesion may be found.

(G) Ingredient

As (G) component, the component which improves the adhesiveness of a base material can be mix | blended. (G) The component is an organic polysiloxane having at least two alkenyl groups, and is a functional R ² _(3-g1) R ¹ _g1 SiO _1/2 silicone unit (wherein R ¹ and R ² The same as above (the same below), g1 is an integer of 1 to 3. The following is referred to as the M ^R1R2 unit), and the trifunctional R ² SiO _3/2 siloxane unit (hereinafter referred to as the T ^R2 unit) is required. The molar ratio of the M ^R1R2 unit / T ^R2 unit satisfies 2/8 ~ 8/2 of the organic polysiloxane, and the viscosity at 25 ° C is preferably in the range of 0.001 ~ 1Pa‧s. The M ^R1R2 unit is preferably bonded to the molecular terminal, but a part may be a silanol group or an alkoxy group to form a terminal.

In the above formula, R ¹ may be exemplified by the same alkenyl group as R ^{1 in the} above formula (1), and among these, vinyl is more industrially preferable. R ² can be exemplified by the same monovalent hydrocarbon group containing no aliphatic unsaturated bond as R ^{2 in} the formula (1). Among these, methyl and phenyl are preferred for industrial use. g1 is an integer from 1 to 3, preferably 1 or 2.

(G) The component is an ^{organopolysiloxane} in which the molar ratio of the above-mentioned M ^R1R2 unit / T ^R2 unit satisfies ^{2/8 to 8/2} , and preferably 3/7 to 7/3. When the Mohr ratio is less than 2/8, the effect of improving the adhesion may become small, and if it exceeds 8/2, it will become difficult for industrial production.

In addition, as long as the effect of the (G) component is not degraded, difunctional R ² _(2-g2) R ¹ _g2 SiO _2/2 siloxane units may be included (wherein g2 is 0, 1, or 2. Recorded as D ^R1R2 units), tetrafunctional SiO _4/2 siloxane units (Q units), especially in release films, when stronger adhesion is required, these M ^R1R2 units / Siloxane with a mole ratio of 2/8 ~ 8/2 is suitable for T ^R2 units. When D ^R1R2 units or Q units are included, they must be used in a small amount relative to either the M ^R1R2 unit or the T ^R2 unit.

In addition, the (G) component is different from the (A) component in that there are more T ^R2 units than D ^R1R2 units.

(G) The amount of alkenyl groups of the organopolysiloxane is preferably 0.01 to 2.5 moles, more preferably 0.03 to 2.0 moles, and even more preferably 0.05 as the alkenyl content per 100g of the organic polysiloxane. ~ 1.5 Mor. If the content is too small, the effect of improving the adhesion may become small, and if it is too large, the application period may become short.

(G) The organopolysiloxane has a viscosity at 25 ° C of 0.001 ~ 1Pa‧s, especially 0.005 ~ 0.5Pa‧s, more preferably 0.01 ~ 0.1Pa‧s, and more A range of 0.01 to 0.05 Pa · s is preferred, and a degree of polymerization that has this viscosity range is better. When the viscosity is less than 0.001 Pa · s, the adhesion improving effect may be small. If it exceeds 1 Pa · s, the solubility or dispersibility of the composition may be reduced.

In addition, the (G) component can be expected to have a large change in the effect of improving the exposure resistance by using it in combination with the branched organic hydrogen polysiloxane in the (C) component. It is presumed to be carried out with branched organic hydrogen polysiloxane The bond of the addition reaction becomes a strong feature of the branch structure.

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

The amount of the (G) component to be blended is preferably 10 to 100 parts by mass, more preferably 15 to 100 parts by mass, relative to 100 parts by mass of the (A) component. If it is less than 10 parts by mass, the effect of improving the adhesiveness of the substrate may be small, and if it exceeds 100 parts by mass, heavy peeling may become large.

In addition, when the (G) component is formulated, the ratio of the SiH-based molar number (SiH group / alkenyl group) in the (C) component to the alkenyl-mol number in the (G) component is 1 or more, and especially added (C) component is mix | blended in the quantity of 1-3, It is suitable from the point which can prevent reduction of hardenability.

(H) component

As another component that improves the adhesion of the substrate, the following general formula having at least an epoxy group and an alkoxysilyl group in (H) 1 molecule can be used Partial hydrolysis (co) condensation of the organosilanes represented by (14) and / or the organosilanes represented by the following average composition formula (15) (14):

R ¹¹ _h1 (OR ¹² ) _h2 Si (R ¹³ ) _(4-h1-h2) (14)

R ¹¹ _h3 (OR ¹² ) _h4 (R ¹³ ) _h5 SiO _{(4-h3-h4-h5) / 2} (15)

(In the formula, R ¹¹ is a monovalent organic group containing an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms, which may include an ether bond, and a part thereof may be hydrolyzed to a hydroxyl group. R ¹³ is unsubstituted or halogen An atom or a cyano-substituted monovalent hydrocarbon group. H1 and h2 are integers and satisfy 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, h3 ~ h5 are positive numbers and satisfy 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, which is selected by the viscosity of the partially hydrolyzed (co) condensed siloxane at 25 ° C being a positive number in the range of 0.001 ~ 1Pa · s).

In addition, the partially hydrolyzed (co) condensed siloxane represented by the formula (15) of the (H) component is different from the (A) component and the (F) component in that it has an epoxy group.

In the formulae (14) and (15), as examples of the monovalent organic group containing an epoxy group of R ¹¹ , 3-glycidoxyalkyl groups such as 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) propyl and the like 2- (3,4-epoxycyclohexyl) alkyl and the like.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, and hexyl. Examples of the ether bond include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, and propoxyethyl. Alkyl, butoxyethyl, methoxypropyl, ethoxypropyl, methoxybutyl, ethoxybutyl, etc. alkoxyalkyl groups having 1 to 6 carbon atoms, such as methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl And ethoxyethyl are preferred. Examples of the OR ¹² group include methoxy, ethoxy, propoxy, butoxy, methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethyl. Oxygen, etc.

R ¹³ is an unsubstituted or substituted monovalent hydrocarbon group. Specific examples include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, phenyl, tolyl, and the like An aryl group, or a hydrogen atom of a carbon atom bonded to such a group, a chloromethyl group, a trifluoropropyl group substituted with a halogen atom such as fluorine, chlorine, bromine, etc., as a substituent And cyanoethyl are preferably 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms. They are non-substituted or substituted monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds, and do not contain aliphatic unsaturated bonds. Of these, methyl, ethyl, propyl, butyl, cyclohexyl, and phenyl are more preferred.

In addition, h1 and h2 are integers and satisfy 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, h3 ~ h5 are positive numbers and satisfy 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, which is a positive number that satisfies the viscosity described later.

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

The partially hydrolyzed (co) condensed siloxane represented by formula (15) can be obtained by adding water to the silane represented by formula (14), Acid, acetic acid, oxalic acid, maleic acid, osmic acid, p-toluenesulfonic acid and other catalysts are reacted in the presence of catalysts to obtain distilled alcohol. Further, the silane represented by formula (14) may be mixed with other alkoxysilanes and reacted to form a partially hydrolyzed co-condensed silane.

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

The amount of the (H) component to be blended is preferably 0.1 to 10 parts by mass, and more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the (A) component. When the content is less than 0.1 parts by mass, the effect of improving adhesion may not be obtained, and when it exceeds 10 parts by mass, the residual adhesion may be reduced.

In the present invention, in order to further promote the adhesion improvement effect of the (H) component, a catalyst amount of an acid, an alkali, and a metal compound may be added. Examples of the acid include formic acid, acetic acid, lactic acid, oxalic acid, maleic acid, and malonic acid. Acids, benzoic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, ammonium chloride, ammonium sulfate, and the like. Examples of the base include ammonia, sodium acetate, sodium carbonate, sodium hydroxide, ammonium hydroxide, and the like as metal compounds. For example, aluminum chloride, acetoacetone aluminum, iron octoate, acetoacetone iron, acetoacetone zirconium, and the like can be exemplified.

These are used to activate the functional group of the (G) component, and it is better to control the addition amount in a range that does not affect the hardenability, shelf life, and storage stability of the composition. Compared to the (A) component 100 parts by mass is preferably 0.0001 to 0.01 parts by mass.

(I) Ingredient

Furthermore, as the component (I), a siloxane unit (M ^R1R2 unit) represented by the following general formula (16) and a siloxane unit (Q unit) represented by the following formula (17) can be used. The ratio (M ^R1R2 unit / Q unit) is ^2/8 ~ 8/2 of MQ resin.

R ² _(3-i1) R ¹ _i1 SiO _1/2 (16)

SiO _4/2 (17)

(In the formula, R ¹ and R ² are the same as above, and i1 is an integer of 0 to 3).

In the above formula, R ¹ may be exemplified by the same alkenyl group as R ^{1 in the} above formula (1), and among these, an alkenyl group such as a vinyl group, an allyl group, and a propenyl group is preferred. Further, R ² may be exemplified by the same monovalent hydrocarbon group containing no aliphatic unsaturated bond as R ^{2 in} the formula (1). Among them, methyl, ethyl, propyl, isopropyl, butyl, Amyl, phenyl and cyclohexyl are preferred. i1 is an integer from 0 to 3, preferably 0, 1, or 2.

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

In addition, as long as the effect of the present invention is not impaired, a difunctional R ² _(2-i2) R ¹ _i2 SiO _2/2 siloxane unit may be included (wherein i2 is 0, 1, or 2. D. ^R1R2 units), trifunctional R ² SiO _3/2 siloxane units (T ^R2 units) or R ¹ SiO _3/2 siloxane units (T ^R1 units). In addition, the ratio of the D ^R1R2 unit and the T ^R2 unit is smaller than any one of the M ^R1R2 unit and the Q unit. Therefore, the ratio is a structure different from the (G) component, and therefore its effect is also different.

The (I) component is different from the (A) component in that it contains more Q units than the D ^R1R2 unit, and is different from the (G) component in that it contains more Q units than the T ^R2 unit.

Although this component is generally used as a peeling force control agent, the effect of improving the exposure resistance can be obtained even if a small amount of the control effect is not formulated. Among the siloxane units represented by the formula (16), the MQ resin composed of only i1 = 0 has the advantage of obtaining stability and improving the resistance to exposure without depending on the application method such as coating conditions. On the other hand, the MQ resin having an alkenyl group other than i1 has a large variation in the effect of improving the resistance to exposure. It is difficult to use it. However, it can be used in combination with the branched organic hydrogen polysiloxane in the component (C). Stability and greater lead to improved exposure resistance. Presumably by addition reaction with branched organopolysiloxane And the bond becomes the person who draws out the branch structure feature more strongly.

(I) The amount of alkenyl groups of the MQ resin of the component, the content of alkenyl groups per 100 g of organopolysiloxane is preferably 0 to 2.4 moles, more preferably 0 to 2.0 moles, and even more preferably 0 to 1.5 moles. . If this content is too small, the effect of heavy peeling may decrease with time, and if it is too large, the pot life may be shortened.

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

The amount of the component (I) to be blended is preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the component (A). If it is less than 1 part by mass, the effect of improving the resistance to exposure may be reduced, and if it exceeds 100 parts by mass, the heavy peeling may be increased.

In addition, when the (I) component to be formulated contains alkenyl groups, the molar ratio (SiH group / alkenyl group) of the SiH group in the (C) component to the molar number of the alkenyl group in the (I) component is additionally prepared as The component (C) in an amount of 1 or more, particularly in an amount of 1 to 10, is preferred from the viewpoint of preventing reduction in hardenability.

(J) Ingredient

Further, as the component (J), a nonionic surfactant having little effect on the addition reaction may be added. Specific examples of the component (J) include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, and polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene polyoxypropylene octadecyl ether.

The (J) component is also expected to make it hydrophobic with other conductive components such as the conductive agent component of the conductive polymer composition described later as other adjustable components. The effect of improving the compatibility of the ingredients. In addition, by improving flatness due to the (J) nonionic surfactant, improvement in transparency or smoothness of the cured film can also be expected.

The addition of the component (J) is expected to improve the exposure resistance due to the antistatic effect. Therefore, it is preferable that the content of the component (A) is 0.1 to 5 parts by mass, especially 0.2 to 4 parts by mass. When the amount is too large, the hardenability of the composition may be reduced.

Other ingredients

In the polysiloxane composition of the present invention, about 0.01 to 1 part by mass of 3-methyl-1-butyn-3-ol, ethynylcyclohexanol, and ethynyl can be blended with respect to 100 parts by mass of the component (A). Cyclohexene and other bath life extension agents.

The polysiloxane composition of the present invention may also contain other organic resins. Organic resin is a component formulated for the purpose of stability of the processing bath, improvement of coating properties to various substrates, improvement of film formation, adjustment of peeling characteristics, adjustment of coating amount and viscosity, and for example, polyethylene can be used. Organic resins such as base alcohols, poly (meth) acrylates, polyesters, celluloses, and derivatives thereof may contain 2 to 400 parts by mass, based on 100 parts by mass of the component (A), but they have a If the electrostatic characteristics have an influence, it is not necessary to mix them.

Specific examples of the above-mentioned derivatives include those in which a part of the hydroxyl groups of cellulose is etherified with an alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, and butyl, and ethyl is preferred.

In the polysiloxane composition of the present invention, antistatic or A conductive polymer composition may be blended for the purpose of conductivity and / or for the purpose of improving atmospheric exposure. The conductive polymer composition contains (a) a π-conjugated conductive polymer, and (b) a polyanion doped with the above (a) π-conjugated conductive polymer, and (c) a solubilizing agent, etc. It is better to disperse the composition which is soluble in the solvent mainly composed of organic solvent. The amount of the conductive polymer composition to be prepared is preferably 5 to 50 parts by mass relative to 100 parts by mass of the component (A).

[Release paper or release film]

The release paper or release film in the second aspect of the present invention includes a substrate made of paper or a plastic film, and a release agent layer formed on at least one side of the substrate.

The release agent layer constituting the release paper or release film of the present invention is a layer formed of the hardened film of the polysiloxane composition.

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

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

Examples of the resin material constituting the plastic film include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, and poly Naphthalenedicarboxylic acid Ethylene glycol, polyacrylic acid, polycarbonate, polyfluorinated vinylidene, polyallyl ester, styrene-based elastomer, polyester-based elastomer, polyether 碸, polyether 醯 imine, polyetheretherketone, poly Polyphenylene sulfide, polyallyl ester, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Among these resin materials, polyethylene terephthalate is preferred from the viewpoints of transparency, flexibility, pollution resistance, and strength.

As the paper, high-quality paper, kraft paper, and coated paper can be used.

Examples of a method for producing a release paper or a release film include a method of applying the polysiloxane composition on at least one side of a paper or a plastic film, and drying to obtain a release paper or a release film.

As a coating method, for example, a method using a coater such as a bar coater, a gravure coater, an air knife coater, a roll coater, a wire rod, or the like is applied. Although the amount of coating is not particularly limited, it is usually in the range of 0.1 to 5.0 g / m ² as a solid content.

As a method of drying, a method of removing a volatile component or a solvent component by heating can be exemplified. Specifically, a hot-air dryer, an IR dryer, etc. can be mentioned. Or just place it at room temperature. The temperature during drying is preferably 50 to 200 ° C, and more preferably 70 to 180 ° C. The drying time is preferably 1 to 120 seconds, and more preferably 5 to 90 seconds.

In the second aspect of the present invention, the release paper or release film is provided with a release agent layer formed by the hardened film of the polysiloxane composition, which is excellent in both exposure resistance and release properties. Therefore, the release paper or release film of the present invention is suitable for use as an adhesive sheet for optical or electronic and electrical parts.

[Example]

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

[Example 1]

Put a 30% toluene solution (A) as a component in a flask and the viscosity at 25 ° C is 20Pa · s. The two ends of the molecular chain are shown as (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 . Dimethylvinylsilyl is blocked, except that the main skeleton at the end is a methylvinylsiloxane unit represented by (CH ₃ ) (CH ₂ = CH) SiO _2/2 with 0.7 mole% and (CH ₃ ) 100 parts of organopolysiloxane (A-1) (vinyl content = 0.01 mol / 100g) composed of 99.3 mol% of dimethylsiloxane units represented by ₂ SiO _2/2 , as (E) 1,140 parts of toluene (E-1) and 1,140 parts of 2-butanone (E-2) as ingredients were dissolved by stirring at 20 to 40 ° C.

In the obtained solution, 15 parts of 1-octadecene (B-1) (unsaturated group content = 0.4 mole / 100g) as the component (B) was prepared, and both ends of the molecular chain as the (C) component were ( The trimethylsilyl group shown in CH ₃ ) ₃ SiO _{1/2 is} blocked, containing 95 mol% of methyl hydrosiloxane units shown in (CH ₃ ) HSiO _2/2 , and the viscosity at 25 ° C is 0.03 5 parts of Pa‧s linear organic hydrogen polysiloxane (C-1) (SiH content = 1.5 mole / 100g) (the mole number of the hydrogen atom directly bonded to the silicon atom is relative to the (A) component (The total mole number of the unsaturated groups contained in component (B) is equivalent to 1.3 times), 1 part of 3-methyl-1-butyn-3-ol as a bath life extension agent, and stirred at 20 to 40 ° C Mix for 1 hour.

Prior to the application of the obtained solution, a catalyst equivalent to 0.02 parts (20 mg) of platinum-vinylsiloxane complex as a component (D) was added to form a coating composition.

[Example 2]

Put a 30% toluene solution (A) as a component in a flask and the viscosity at 25 ° C is 10Pa · s. The end of the molecular chain is shown as (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 . Methylvinylsilyl is blocked and contains methyl vinyl siloxane units of (CH ₃ ) (CH ₂ = CH) SiO _2/2 with 2.8 mole% and (CH ₃ ) ₂ SiO _2/2 . The dimethyl siloxane unit shown is 96.9 mol% and the methyl siloxane unit shown as (CH ₃ ) SiO _{3/2 is} 0.1 mol% of organic polysiloxane (A-2) (vinyl content = 0.04 mole / 100g) 100 parts, 1,102 parts of toluene (E-1) as a component (E) and 1,102 parts of 2-butanone (E-2), and dissolved by stirring at 20 to 40 ° C.

In the obtained solution, 5 parts of 1,7-octadiene (B-2) (unsaturated group content = 1.8 mole / 100 g) as the component (B) was prepared as the component (C) of Example 1 8 parts of linear organic hydrogen polysiloxane (C-1) (SiH content = 1.5 mol / 100g), and 100 mol units of methyl hydrosiloxane represented by (CH ₃ ) HSiO _2/2 %, And cyclic organic hydrogen polysiloxane (C-2) (SiH content = 1.7 mole / 100g) at 25 ° C with a viscosity of 0.005Pa‧s (direct bonding of (C) ingredients The total number of moles of hydrogen atoms in the silicon atom is equivalent to 1.3 times the total number of moles of unsaturated groups contained in the component (A) and (B)). 3-methyl- 1 part of 1-butyne-3-ol, stir and mix at 20-40 ° C for 1 hour.

Prior to the application of the obtained solution, a catalyst equivalent to 0.02 parts (20 mg) of platinum-vinylsiloxane complex as a component (D) was added to form a coating composition.

[Example 3]

Into a flask, 100 parts of the organopolysiloxane (A-1) (vinyl content = 0.01 mole / 100 g) as the component (A) and toluene (E-1) as the component (E) were placed. ) 1,121 parts and 1,121 parts of 2-butanone (E-2), dissolve by stirring at 20-40 ° C.

In the obtained solution, the following formula CH ₂ = CH-C ₈ H ₁₆ -Si (CH ₃ ) _{3 was} prepared as the component (B).

10 parts of silane (B-3) (unsaturated group content = 0.47 mol / 100g) shown as the linear organic hydrogen polysiloxane (C-1) (SiH) of Example 1 as component (C) (Content = 1.5 mol / 100g) 4 parts, and both ends of the molecular chain are closed with a dimethylhydrosilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , containing a formazan represented by (CH ₃ ) HSiO _2/2 Linear hydrosiloxane units of 70 mole%, dimethylsiloxane units of (CH ₃ ) ₂ SiO _2/2 shown as 25 mole% units, and linear viscosity at 25 ° C of 0.04Pa‧s Organic hydrogen polysiloxane (C-3) (SiH content = 1.2 mole / 100g) 4 parts (The total mole number of the hydrogen atom directly bonded to the silicon atom of the (C) component is relative to the (A) component and (B) The total number of moles of the unsaturated groups contained in the component is equivalent to 1.3 times.) 1 part of 3-methyl-1-butyn-3-ol as a bath life extension agent. Stir and mix at 20-40 ° C. 1 hour.

Prior to the application of the obtained solution, a catalyst equivalent to 0.02 parts (20 mg) of platinum-vinylsiloxane complex as a component (D) was added to form a coating composition.

[Example 4]

Put a 30% toluene solution (A) as a component in a flask, the viscosity at 25 ° C is 15Pa · s, and both ends of the molecular chain are shown as (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 The dimethylvinylsilyl group is blocked, except that the main skeleton of the terminal is represented by (CH ₃ ) (CH ₂ = CH) SiO _2/2 . The methyl vinyl siloxane unit is 1.5 mole% and (CH ₃ ) 100 parts of organopolysiloxane (A-3) (vinyl content = 0.02 mol / 100g) composed of 98.5 mol% of dimethylsiloxane units shown in ₂ SiO _2/2 , as (E) 1,121 parts of toluene (E-1) and 1,121 parts of 2-butanone (E-2) as ingredients were dissolved by stirring at 20 to 40 ° C.

In the obtained solution, the following formula as a component (B) is prepared

10 parts of the disiloxane (B-4) (unsaturated group content = 0.56 mole / 100g) shown as the linear organic hydrogen polysiloxane (C-1) of Example 1 as component (C) ) (SiH content = 1.5 mole / 100g) 4 parts, and 50 mole% of dimethylhydrosilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , (CH ₃ ) SiO _3/2 4 parts of branched organohydrogen polysiloxane (C-4) (SiH content = 0.75 mol / 100g) consisting of 50 mol% of methylsiloxane units and a viscosity of 0.01 Pa · s at 25 ° C (The total mole number of the hydrogen atom of the (C) component directly bonded to the silicon atom is 1.4 times the total mole number of the unsaturated groups contained in the (A) component and the (B) component). 1 part of 3-methyl-1-butyne-3-ol, which is a life extension agent, is stirred and mixed at 20 ~ 40 ° C for 1 hour.

Prior to the application of the obtained solution, a catalyst equivalent to 0.02 parts (20 mg) of platinum-vinylsiloxane complex as a component (D) was added to form a coating composition.

[Example 5]

Put a 30% toluene solution (A) as a component in a flask, the viscosity at 25 ° C is 15Pa · s, and both ends of the molecular chain are shown as (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 The dimethylvinylsilyl group is closed, except that the main skeleton of the terminal is represented by (CH ₃ ) (CH ₂ = CH) SiO _2/2 . The methyl vinyl siloxane unit is 4 mole% and (CH ₃ ) bis ₂ SiO _2/2 siloxane units shown methyl silicon 91 mole% and _{(C 6 H 5) 2 SiO} 2/2 of diphenyl siloxane unit shown silicon composed of 5 mole% organopolysiloxane 100 parts of siloxane (A-4) (vinyl content = 0.04 mole / 100g), 1,121 parts of toluene (E-1) as the (E) component, and 1,121 parts of 2-butanone (E-2), in Dissolve with stirring at 20 ~ 40 ℃.

In the obtained solution, 10 parts of the siloxane (B-4) of Example 4 as the component (B) (unsaturated group content = 0.56 mole / 100 g) was prepared, and Example 1 as the component (C) was prepared. 4 parts of linear organic hydrogen polysiloxane (C-1) (SiH content = 1.5 mole / 100g), and 45 dimethyl hydrosilyl group shown by (CH ₃ ) ₂ HSiO _1/2 It consists of 10 mol% of dimethyl siloxane units shown in (CH ₃ ) ₂ SiO _2/2 , and 45 mol% of siloxane units shown in SiO _4/2 . Branched organohydrogen polysiloxane (C-5) with a viscosity of 0.01 Pa · s (SiH content = 0.75 mol / 100g) 4 parts (Total of (C) component hydrogen atoms directly bonded to silicon atoms (The number of ears is equivalent to 1.4 times the total number of moles of the unsaturated groups contained in (A) component and (B) component), and 3-methyl-1-butyn-3-ol 1 as a bath life extension agent 1 Parts, stir and mix for 1 hour at 20-40 ° C.

Prior to the application of the obtained solution, a catalyst equivalent to 0.02 parts (20 mg) of platinum-vinylsiloxane complex as a component (D) was added to form a coating composition.

[Example 6]

Into a flask, 100 parts of the organopolysiloxane (A-1) (vinyl content = 0.01 mole / 100 g) as the component (A) and toluene (E-1) as the component (E) were placed. ) 1,168 parts and 1,168 parts of 2-butanone (E-2), dissolve by stirring at 20-40 ° C.

In the obtained solution, the following formula CH ₂ = CH-C ₁₄ H _{29 was} prepared as the component (B).

15 parts of 1-hexadecene (B-5) (unsaturated group content = 0.45 moles / 100g) shown as the linear organic organopolysiloxane (C- 1) (SiH content = 1.5 moles / 100g) 6 parts, and both ends of the molecular chain are closed with a dimethylhydrosilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , except that the main skeleton at the ends is (CH ₃ ) 60 mol% of methyl hydrosiloxane units shown in HSiO _2/2 and 20 mol% of dimethylsiloxane units shown in (CH ₃ ) ₃ SiO _1/2 and (C ₆ H ₅ ) A linear organic hydrogen polysiloxane (C-6) composed of 20 mol% of diphenylsiloxanes represented by ₂ SiO _2/2 and having a viscosity of 0.5 Pa · s at 25 ° C SiH content = 0.68 mol / 100g) 2 parts (The total mole number of the hydrogen atom directly bonded to the silicon atom of (C) component is relative to the total of the unsaturated groups contained in (A) component and (B) component. (Ear number is equivalent to 1.3 times), 1 part of 3-methyl-1-butyn-3-ol, which is a bath life extension agent, is stirred and mixed at 20-40 ° C for 1 hour.

Prior to the application of the obtained solution, a catalyst equivalent to 0.02 parts (20 mg) of platinum-vinylsiloxane complex as a component (D) was added to form a coating composition.

[Example 7]

In Example 1, a 30% toluene solution (F) component was additionally prepared to have a viscosity of 40 Pa · s at 25 ° C., and both ends of the molecular chain were closed with dimethylhydroxysilyl groups, except that the main skeleton of the ends was terminated with two One part of organopolysiloxane (F) (hydroxy content = 0.0002 mol / 100g) composed of 100 mol% of methylsiloxane units, and the component (C) was added to the linear organic compound of Example 1 5 parts of hydropolysiloxane (C-1) (SiH content = 1.5 mole / 100g), and both ends of the molecular chain are closed with a dimethylhydrosilyl group represented by (CH ₃ ) ₂ HSiO _1/2 , containing A linear organohydrogenpolysiloxane (C-7) with a dimethylsiloxane unit of 90 mol% as shown in (CH ₃ ) ₂ SiO _2/2 and a viscosity of 0.02 Pa · s at 25 ° C (SiH content = 0.1 mole / 100g) 5 parts (The total mole number of the hydrogen atom of (C) component directly bonded to the silicon atom is relative to that contained in (A) component, (B) component, and (F) component (The total mole number of unsaturated groups is equivalent to 1.3 times.) The component (E) was increased to 1,197 parts of toluene (E-1) and 1,197 parts of 2-butanone (E-2). Modulation composition.

[Example 8]

In Example 4, as a component (G), the viscosity at 25 ° C. was 0.03 Pa · s, and the end of the molecular chain was closed with dimethylvinylsilyl, except that the main skeleton of the end was (CH ₃ ) 20 parts of organopolysiloxane (G) (vinyl content = 0.6 mole / 100g) composed of ₂ CH ₂ = 50 mole% of CHSiO _1/2 unit and 50 mole% of CH ₃ SiO _3/2 unit, The component (C) was increased to 11 parts of the linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mole / 100g) of Example 1 and the branched organohydrogen polysiloxane of Example 4 Oxane (C-4) (SiH content = 0.75 mole / 100g) 11 parts (The total mole number of the hydrogen atom directly bonded to the silicon atom of the (C) component is relative to the (A) component and (B) component (The total mole number of unsaturated groups contained in the (G) component is equivalent to 1.3 times), and the (E) component is increased to 1,444 parts of toluene (E-1) and 1,444 parts of 2-butanone (E-2). The composition was prepared in the same manner as in Example 4.

[Example 9]

In Example 4, the following average composition formula (CH ₃ O) _a R ^Ep _b SiO _{(4-ab) / 2 was} additionally prepared as the (H) component.

(In the formula, R ^Ep is glycidoxypropyl, a is 1.7, and b is 1)

As shown, the average degree of polymerization is 3, and the viscosity of the epoxy siloxane oligomer (H) is 3 parts at a viscosity of 0.1 Pa · s at 25 ° C. The component (E) is increased to toluene (E-1). A composition was prepared in the same manner as in Example 4 except for 1,149 parts and 1,149 parts of 2-butanone (E-2).

[Example 10]

In Example 5, as the component (I), CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 unit 5 mole%, (CH ₃ ) ₃ SiO _1/2 unit 45 mole%, SiO ₄ of Example _1/2 units of from 50 mole%, average degree of polymerization of the organopolysiloxane of the silicone siloxane 100 (I-1) (vinyl content of 0.07 mole / 100g) 20 parts of the component (C) to increment 8 parts of linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mole / 100g), and branched organohydrogen polysiloxane (C-5) (SiH content = 0.75) of Example 5 Moore / 100g) 6 parts (The total mole number of the hydrogen atom directly bonded to the silicon atom of (C) component is relative to the total of unsaturated groups contained in (A) component, (B) component and (I) component The molar number is equivalent to 1.5 times.) The component was prepared in the same manner as in Example 5 except that the component (E) was increased to 1,368 parts of toluene (E-1) and 1,368 parts of 2-butanone (E-2).

[Example 11]

In Example 1, an organic polysiloxane having an average polymerization degree of 70 composed of (CH ₃ ) ₃ SiO _1/2 unit 55 mol% and SiO _4/2 unit 45 mol% was additionally prepared as the (I) component. The composition was prepared in the same manner as in Example 1 except that 2 parts of alkane (I-2) was added to (159) parts of toluene (E-1) and 1,159 parts of 2-butanone (E-2).

[Example 12]

In Example 1, 1 part of the nonionic surfactant (J) represented by polyoxyethylene dodecyl ether (the number of oxyethylene bonds 5 to 15) as an ingredient (J) was added, and (E) The components were increased to 1,149 parts of toluene (E-1) and 1,149 parts of 2-butanone (E-2), and the composition was prepared in the same manner as in Example 1.

[Example 13]

The viscosity of the compound (A) at 25 ° C is 0.5Pa‧s, and the end of the molecular chain is closed with dimethylvinylsilyl group, containing 97 mol% of dimethylsiloxane units, CH ₃ SiO ₃ Example of 100 parts of a branched organopolysiloxane (A-5) (vinyl content = 0.02 mol / 100g) of a methyl siloxane unit of 1 mol% shown in _{/ 2} as a component (B) 4bis Siloxane (B-4) (unsaturated group content = 0.56 mole / 100g) 10 parts, as the component (C), the linear organic hydrogen polysiloxane (C-1) of Example 1 (SiH content = 1.5 mole / 100g) 17 parts (The mole number of the hydrogen atom directly bonded to the silicon atom of (C) component is different from the content of (A) component, (B) component, and (G) component. (The total number of moles of the saturated group is equivalent to 1.3 times), (CH ₃ ) ₂ CH ₂ = CHSiO _1/2 unit 50 mole%, CH ₃ SiO _3/2 unit 50 as the component (G) 20 parts by mole% of organopolysiloxane (G) (vinyl content = 0.6 mole / 100g), 1 part of 3-methyl-1-butyne-3-ol as bath life extension agent Without mixing the (E) component, directly stir and mix at 20-40 ° C for 1 hour.

As a catalyst for the component (D), a platinum-vinylsiloxane complex compound having a content of 0.02 parts (20 mg) of platinum was added to prepare a composition.

[Comparative Example 1]

In Example 1, the component (B) was omitted, and the component (C) was reduced to 1 part of the linear organic hydrogen polysiloxane (C-1) (SiH content = 1.5 mol / 100g) in Example 1 (direct The mole number of the hydrogen atom bonded to the silicon atom is maintained at 1.3 times the total mole number of the unsaturated groups contained in the (A) component and the (B) component), so that the (E) component becomes toluene (E- 1) A composition was prepared in the same manner as in Example 1 except for 959 parts and 959 parts of 2-butanone (E-2).

<Evaluation> 〔Hardening property〕

The obtained composition (release agent) was applied to a PE laminated paper having a thickness of 100 μm with a # 14 bar coater, and heated in a hot air dryer at 120 ° C. for 1 minute to form a release agent layer. In addition, the composition of Example 12 was applied using an IR tester, and dried at 120 ° C. for 30 seconds to form a release agent layer. The coating amount was adjusted to a transfer amount of 0.8 g / m ² in terms of solid content. After this release agent layer was rubbed with a finger 10 times, the presence or absence of haze and peeling was visually observed, and evaluated by the following criteria.

A: No haze or peeling was seen.

B: Mist or peeling was seen.

[Adhesiveness]

The obtained product (release agent) was applied to a PET film having a thickness of 38 μm with a # 5 bar coater, and heated in a hot air dryer at 120 ° C. for 1 minute to form a release agent layer. In addition, the composition of Example 12 was applied using an IR tester, and dried at 120 ° C. for 30 seconds to form a release agent layer. The coating amount was adjusted to a transfer amount of 0.2 g / m ² in terms of solid content. The release agent layer was stored at 25 ° C and 50% RH for one week or at 60 ° C and 90% RH for one week. After this release agent layer was rubbed with a finger 10 times, the presence or absence of haze and peeling was visually observed, and evaluated by the following criteria.

A: Even after one week at 60 ° C and 90% RH, no haze or peeling was observed.

B: Although haze and peeling were seen after one week at 60 ° C and 90% RH, haze and peeling were not seen after one week at 25 ° C and 50% RH.

C: Fog or peeling was seen at 25 ° C and 50% RH for one week.

〔Peel force〕

A release agent layer was formed in the same manner as the above-mentioned hardenability evaluation. A 50-mm-wide polyester adhesive tape (Nitto 31B, trade name of Nitto Denko Corporation) was placed on the surface, and then a load of 1,976 Pa was placed on the adhesive tape and heat-treated at 70 ° C for 20 hours. On the release agent layer. Then, using a tensile tester, the polyester adhesive tape was peeled from the releasing agent layer at an angle of 180 ° (peeling speed 0.3 m / min), and the peeling force was measured.

[Residual Adhesion Rate]

The polyester adhesive tape was stuck to the release agent layer similarly to the measurement of the peeling force mentioned above. Thereafter, the polyester adhesive tape was peeled off from the release agent layer, and the polyester adhesive tape was affixed to a stainless steel plate. Next, using a tensile tester, the polyester adhesive tape was peeled from a stainless steel plate, and the peeling force X was measured.

Further, instead of the release agent layer, a polyester adhesive tape was attached to a tetrafluoroethylene plate, and the same treatment was performed, and the measured peeling force Y was measured.

Then, the residual adhesion rate was determined from the formula (peeling force X / peeling force Y) × 100 (%).

The higher the residual adhesion rate, the better the release property of the release agent layer, and the lower the adhesive force of the polyester adhesive tape caused by the release agent layer being suppressed.

〔Exposure resistance〕

A release agent layer was formed in the same manner as the above-mentioned evaluation of the hardenability, and the release agent layer was placed in a room at 25 ° C. and 50% RH for 8 hours and 1 day to expose the atmosphere. This release agent layer was measured after the same treatment as the above-mentioned release force. Peeling force after atmospheric exposure.

Claims (11)

An addition reaction hardening type polysiloxane composition is a polysiloxane composition for release paper or release film, and includes the following (A) to (E): (A) the following general formula (1) ), An organic polysiloxane having at least two alkenyl groups in one molecule: 100 parts by mass, (In the formula, R ^{1 is} independently an alkenyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, and X ^{1 is} independently the following general formula (2-1) X ^{2 is} independently the following general formula (2-2), X ^{3 is} independently the following general formula (2-3) In the base shown, X ^{4 is} each independently the following general formula (3-1), X ^{5 is} each independently the following general formula (3-2), and X ^{6 is} each independently the following general formula (3-3) The base shown; R ¹ and R ^{2 are} as described above, a1, a2, a11, a21, a31, a41, a51, a61 are each independently an integer of 0 to 3; a3 is a positive number, a4 to a6, a12 to a15, a22 ~ a25, a32 ~ a35, a42, a43, a52, a53, a62, a63 are 0 or positive numbers. These are diluted with toluene with an organopolysiloxane having a viscosity at 25 ° C of 0.05Pa‧s or more and 30% by mass of toluene. (The viscosity is selected in the range of 70 Pa · s or less), (B) is selected from olefins having 8 to 30 carbon atoms having an unsaturated bond at the terminal shown in the following general formula (4), and is shown in the following general formula (5) Diolefins having 10 to 32 carbon atoms at both ends of the unsaturated bond, silanes having 1 to 4 alkenyl groups having 8 to 30 carbon atoms at the end and having unsaturated bonds as shown in the following general formula (6), and One or more compounds of disiloxanes having an alkenyl group of 8 to 30 carbon atoms having 2 to 6 terminal unsaturated bonds and represented by the following general formula (7): 5 to 20 parts by mass, CH ₂ = CH-R ³ -H (4) CH ₂ = CH-R ³ -CH = CH ₂ (5) (CH ₂ = CH-R ³ ) _b1 SiR ⁴ _4-b1 (6) (In the formula, R ^{3 is} each independently a bivalent hydrocarbon group having 6 to 28 carbon atoms, R ^{4 is} independently a monovalent hydrocarbon group or alkoxy group having 1 to 10 carbon atoms, b1 is an integer of 1 to 4 and b2 is independently 1 to 4 An integer of 3), (C) As shown in the following average composition formula (8), an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: (C) The component is bonded to The mole number of the hydrogen atom of the silicon atom is an amount equivalent to 1 to 20 times the total mole number of the alkenyl group and the unsaturated group in the components (A) and (B). R ² _c1 H _c2 SiO _{(4-c1 -c2) / 2} (8) (wherein R ^{2 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, c1 is a positive number of 0.1 to 2, and c2 is 0.01 to A positive number of 2 and c1 + c2 is a positive number of 3 or less. There are more than 2 SiH groups in 1 molecule, and the viscosity is selected within the range of 0.005 ~ 10Pa‧s at 25 ° C.) (D) Platinum of catalyst amount Group metal catalyst, (E) organic solvent: 0 to 100,000 parts by mass. The polysiloxane composition according to claim 1, wherein the component (C) is an organohydrogenpolysiloxane represented by the following general formula (9) and / or the following general formula (10): (In the formula, Me is a methyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ^{5 is} each independently a hydrogen atom or contains no aliphatic unsaturated bond. Unsubstituted or halogen atom or cyano-substituted monovalent hydrocarbon group, R ⁶ and R ⁷ are each independently unsubstituted or halogen atom or cyano-substituted monovalent hydrocarbon group other than Me without aliphatic unsaturated bond, Y ³ Each is independently the following general formula (11-1), Y ^{4 is} each independently the following general formula (11-2), and Y ^{5 is} each independently the following general formula (11-3) In the base shown, Y ^{6 is} each independently the following general formula (12-1), Y ^{7 is} each independently the following general formula (12-2), and Y ^{8 is} each independently the following general formula (12-3) As shown above, R ⁵ , R ⁶ , and R ^{7 are} as described above, c11, c12, c31, c41, c51, c61, c71, and c81 are each independently an integer of 0 to 3, c23 is an integer of 2 or more, and c13 to c19 , C24 ~ c29, c32 ~ c38, c42 ~ c48, c52 ~ c58, c62 ~ c66, c72 ~ c76, c82 ~ c86 are integers of 0 or more, c23 + c24 + c25 + c26 + c27 + c28 + c29 is 3 or more Integer, there are 2 or more hydrogen atoms bonded to silicon atoms in a molecule, and the viscosity is selected in the range of 0.005 ~ 10Pa · s at a viscosity of 25 ° C). For example, the polysiloxane composition of claim 1 or 2, wherein the component (C) is 2 or more R ² ₂ HSiO _1/2 units in one molecule (R ² is an unsubstituted or A halogen atom or a cyano-substituted monovalent hydrocarbon group) of an organohydrogenpolysiloxane, or a mixture containing a part of the organohydrogenpolysiloxane. For example, the polysilicone composition of claim 1 or 2, wherein (C) component is (C1) an organohydrogen polysiloxane containing no aromatic substituents and (C2) an organohydrogen polysiloxane containing aromatic substituents A mixture of alkanes, and the mass ratio (C1) / (C2) of these (C1) and (C2) components is 1/9 to 9/1. The polysiloxane composition according to claim 1 or 2, which further contains, as a component (F), an organopolysiloxane represented by the following general formula (13) with respect to 100 parts by mass of the (A) component, 0.1 to 30. Mass parts, (In the formula, Me is methyl, R ^{8 is} independently hydroxy, alkoxy, or alkoxyalkyl, and R ^{9 is} independently hydroxy, alkoxy, alkoxyalkyl, and free of aliphatic unsaturated bonds. A substituted or halogen atom or a cyano-substituted monovalent hydrocarbon group. R ^{10 is} independently an unsubstituted or halogen atom or a cyano group other than hydroxyl, alkoxy, alkoxyalkyl, and Me containing no aliphatic unsaturated bond. Monovalent hydrocarbon group, f1 and f2 are integers of 1 ~ 3, f3 ~ f5 is the range where the viscosity of the organopolysiloxane at 25 ° C falls above 1Pa‧s, and the dilution viscosity of 30% by mass of toluene is below 100Pa‧s To choose). For example, the polysiloxane composition of claim 1 or 2 further contains 10 to 100 parts by mass of an organopolysiloxane as the (G) component with respect to 100 parts by mass of the (A) component, and the organopolysiloxane is at least It has two alkenyl groups, with R ² _(3-g1) R ¹ _g1 SiO _1/2 siloxane units (M ^R1R2 units) and R ² SiO _3/2 siloxane units (T ^R2 units) (where, R ^{1 is} independently an alkenyl group, R ^{2 is} independently an unsubstituted or halogen atom or a cyano-substituted monovalent hydrocarbon group without an aliphatic unsaturated bond, g1 is an integer of 1 to 3) as an essential unit, M ^R1R2 unit / T The molar ratio of ^R2 units meets 2/8 ~ 8/2, the viscosity at 25 ° C has a range of 0.001 ~ 1Pa · s, and the molecular ends are M ^R1R2 units, or M ^R1R2 units and a part is silanol group or Alkoxy. For example, the polysiloxane composition according to claim 1 or 2 further contains the following general with respect to 100 parts by mass of the component (A) and further contains at least an epoxy group and an alkoxysilane group in one molecule as the component (H). The organosilane represented by formula (14) and / or the partially hydrolyzed (co) condensed siloxane represented by the following average composition formula (15), 0.1 to 10 parts by mass, R ¹¹ _h1 (OR ¹² ) _h2 Si (R ¹³ ) _(4-h1-h2) (14) R ¹¹ _h3 (OR ¹² ) _h4 (R ¹³ ) _h5 SiO _{(4-h3-h4-h5) / 2} (15) (where R ¹¹ is epoxy-containing Is a monovalent organic group, R ¹² is an alkyl group having 1 to 6 carbon atoms, and may contain an ether bond, and a part thereof may be hydrolyzed to a hydroxyl group; R ¹³ is an unsubstituted or halogen atom or a cyano substituted monovalent hydrocarbon group; h1 and h2 are integers and satisfy 1 ≦ h1, 1 ≦ h2, 2 ≦ h1 + h2 ≦ 4, h3 ~ h5 are positive numbers and satisfy 0 <h3, 0 <h4, 0 ≦ h5, 1 <h3 + h4 + h5 ≦ 3, selected from the positive value of the viscosity of the partially hydrolyzed (co) condensed siloxane at 25 ° C in the range of 0.001 ~ 1Pa · s). The polysiloxane composition according to claim 1 or 2, further containing a siloxane unit (M unit) represented by the following general formula (16) as the (I) component with respect to 100 parts by mass of the (A) component. The siloxane unit (Q unit) represented by the following formula (17) is 1 to 100 parts by mass of MQ resin with a molar ratio (M unit / Q unit) of 2/8 to 8/2, and R ² _{( 3-i1)} R ¹ _i1 SiO _1/2 (16) SiO _4/2 (17) (wherein R ^{1 is} independently an alkenyl group, and R ^{2 is} independently an unsubstituted or halogen atom having no aliphatic unsaturated bond or A cyano substituted monovalent hydrocarbon group, i1 is an integer of 0 to 3). For example, the polysiloxane composition according to claim 1 or 2 further contains 0.1 to 5 parts by mass of a nonionic surfactant as the (J) component with respect to 100 parts by mass of the component (A). A release paper having a cured film of a polysiloxane composition as described in any one of claims 1 to 9. A release film comprising a hardened film of a polysiloxane composition according to any one of claims 1 to 9.