KR20160028378A - Silicone composition for release paper or release film, release paper and release film - Google Patents

Abstract

The present invention provides: a silicone composition for a release paper or a release film of a addition reaction curing type which adds a release agent film suppressing the transition of a release agent, not having a bad influence on residual adhesive strength and peel strength, and having exposure resistance; and a release paper and a release film where a cured film in the composition is formed. A specific amount of one or more compounds selected from silane and the disiloxane having alkene and alkadiene having an unsaturated bond at a terminal end and an alkenyl group having an unsaturated bond at a terminal end is mixed into the silicone composition of a addition reaction curing type of the present invention.

Description

TECHNICAL FIELD [0001] The present invention relates to a silicone composition, a release paper and a release film for a release paper or a release film,

The present invention relates to a silicone composition suitable for the preparation of release paper and release film excellent in the effect of suppressing the phenomenon of heavy wear due to exposure to the atmosphere (hereinafter referred to as "resistance to weathering"), To a silicone composition capable of maintaining a good peeling property even when the coated surface of the silicone release paper and the release film undergoes atmospheric exposure, and a release paper and a release film on which the cured coating of the composition is formed.

The release film or the release liner is coated with a silicone release agent on the surface of a substrate such as a plastic film or paper, and is formed into a cured film by a cross-linking reaction, and is widely used as a release agent film for adhesive or adhesive substances.

As such a curable organopolysiloxane composition, an addition cure type separating composition which comprises a vinyl group-containing organopolysiloxane and an organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom as a main component and is cured by a hydrosilylation reaction is well known And is widely used as a composition for peeling because it has an advantage of being able to change the peeling property in various ways and has a high curing speed. However, the addition reaction curing type peeling composition has pointed out that, when the coating obtained by curing is exposed to the outside air, the peeling force becomes unusually heavy or can not be peeled off in some cases. Therefore, if the silicone coating film is exposed to the atmosphere in the process of producing labels or adhesive tapes using a release or release film in which the release agent film is formed using the addition reaction curable release composition, And the peeling failure is caused, leading to a serious deterioration of the quality.

In order to solve this problem, a method of blending an alcohol-modified organopolysiloxane or a polyether-modified organopolysiloxane with an addition reaction curable peeling composition (JP-A-55-3460 (Patent Document 1) (Japanese Patent Application Laid-Open No. 1-217068: Patent Document 2) has been reported as a part of a hydrogenpolysiloxane having a hydrosilyl group at only one silicon atom at one end. However, these methods have an effect of suppressing the phenomenon of heavy damage due to exposure to the atmosphere, but it is not sufficient. The residual adhesive force of the adhesive layer is lowered.

Japanese Patent No. 2934118 (Patent Document 3) discloses a method of specifying the structure of a crosslinking agent, and the deterioration of the residual adhesive force is improved, but the peeling force is heavy, and other peeling properties are greatly affected.

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

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an additional reaction curing type release paper or a release film film for imparting releasability to a release film, which is capable of suppressing the releasability of the release agent, And a release film and a release film on which a cured coating of the composition is formed.

As a result of intensive investigations to achieve the above object, the present inventors have found that an addition reaction curable silicone composition can be produced by adding an alkene and an alkadiene having an unsaturated bond at the terminal, a silane having an alkenyl group having an unsaturated bond at the terminal, A silicone composition for a release paper or a release film which imparts a releasing agent film having resistance to weathering without adversely affecting residual adhesive force and peeling force by suppressing the releasability of the release agent by blending a specified amount of at least one selected compound And the release film and the release film on which the cured film of the composition is formed are excellent in the resistance to weathering and peeling, and even if the release film and the cured film formed on the release film are exposed to the air for a long time, And the present invention has been accomplished.

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

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

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

A group represented by, X ⁴ are each independently formula: (3-1), X ⁵ has the formula (3-2) to each independently, X ⁶ is a chemical formula (3-3) to each independently

Group and, R ^1, R ² are as defined above represented by, a1, a2, a11, a21 , a31, a41, a51, a61 are each independently from 0 to 3 constant, a3 is a positive number, a4 to a6, a2 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 are 0 or a positive number, and they have a viscosity at 25 deg. C of the organopolysiloxane of not less than 0.05 Pa · s and not more than 30 mass% The viscosity is selected to be in a range of 70 Pa · s or less)

(B) an alkene having 8 to 30 carbon atoms and having an unsaturated bond at the end represented by the following formula (4), an alkadiene having 10 to 32 carbon atoms and having an unsaturated bond at both terminals, represented by the following formula (5) Silane having 1 to 4 alkenyl groups having 8 to 30 carbon atoms and unsaturated bonds at the terminals represented by the following formula (6), and alkenyl groups having 8 to 30 carbon atoms having an unsaturated bond at the terminal represented by the following formula (7) 5 to 20 parts by mass of at least one compound selected from disiloxanes having 6 to 6 carbon atoms,

(Wherein R ³ is independently a divalent hydrocarbon group having 6 to 28 carbon atoms, R ⁴ is independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 10 carbon atoms, b 1 is an integer of 1 to 4, b 2 Is independently an integer of 1 to 3)

(C) an organohydrogenpolysiloxane represented by the following average composition formula (8) and having a hydrogen atom bonded to at least two silicon atoms in one molecule: the number of moles of hydrogen atoms bonded to silicon atoms in the component (C) And the component (B) is 1 to 20 times the total number of moles of the alkenyl group and the unsaturated group,

(In the formula, R ² is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, c 1 is a positive number of 0.1 to 2, c 2 is a positive number of 0.01 to 2, c 1 + c2 is a positive number of 3 or less, and has at least two SiH groups in one molecule, and the viscosity at 25 DEG C is selected to fall within a range of 0.005 to 10 Pa · s)

(D) a catalytic amount of a platinum group metal catalyst,

(E) Organic solvent: 0 to 100,000 parts by mass

Wherein the silicone rubber is a silicone rubber.

[2] The silicone composition for a release or release film according to [1], wherein the component (C) is an organohydrogenpolysiloxane represented by the following formula (9) and / or the following formula (10).

(Wherein, in the formula, Me is a methyl group, R ² is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ⁵ is each independently a hydrogen atom or an aliphatic unsaturated bond And R ⁶ and R ⁷ each independently represent an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group other than Me which contains no aliphatic unsaturated bond, hydrocarbon group, Y ³ is the formula are each independently (11-1), Y ⁴ are each independently formula to (11-2), Y ⁵ is the following formula (11-3) are each independently

A group represented by, general formula Y ⁶ are each independently to (12-1), Y ⁷ of the formula (12-2) to each independently, Y ⁸ has the formula (12-3) to each independently

A group represented by, R ^5, R ^6, R ⁷ are as described above, c11, c12, c31, c41, c51, c61, c71, c81 are each independently from 0 to 3 integers, c23 is an integer of 2 or greater, c23 + c24 + c25 + c26 + c27 + c28 + c29 wherein c13 to c19, c24 to c29, c32 to c38, c42 to c48, c52 to c58, c62 to c66, c72 to c76, 3 or more and has hydrogen atoms bonded to two or more silicon atoms in one molecule and is selected so that the viscosity at 25 ° C falls within a range of 0.005 to 10 Pa · s)

[3] The positive resist composition according to any _{one of} [1] to [3], wherein the component (C) has at least ^two R ² ₂ HSiO _1/2 units (wherein R ² is an unsubstituted or halogen atom- or cyano-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond) A silicone composition for a release or release film according to [1] or [2], wherein the organopolysiloxane is an organohydrogenpolysiloxane or a mixture containing a part of the organohydrogenpolysiloxane.

[4] The positive resist composition according to [1], wherein the component (C) is a mixture of an organohydrogenpolysiloxane containing no aromatic substituent (C1) and an organohydrogenpolysiloxane containing an aromatic substituent (C2) The silicone composition for a release or release film according to any one of [1] to [3], wherein the mass ratio (C1) / (C2) is 1/9 to 9/1.

[5] The foil according to any one of [1] to [4], further comprising 0.1 to 30 parts by mass of an organopolysiloxane represented by the following formula (13) as a component (F) based on 100 parts by mass of the component (A) ≪ / RTI >

(Wherein, in the formula, Me is a methyl group, R ⁸ is independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group, and R ⁹ is independently an unsubstituted or halogen atom which does not contain a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, And R ¹⁰ is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group other than Me, which does not contain a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, f1, f2 is an integer of 1 to 3, and f3 to f5 are integers selected so that the viscosity of the organopolysiloxane at 25 DEG C is in a range of 1 Pa · s to 30 Pa0% toluene diluted viscosity of 100 Pa · s or less)

[6] have at least two alkenyl groups as component _{^{(G), R 2 (3-g1)}} R 1 g1 SiO 1/2 siloxane units (M ^R1R2 unit), 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 or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and g 1 is an integer of 1 to 3) ^Wherein the molar ratio of M ^{R1R 2} units / T ^R 2 is 2/8 to 8/2, the viscosity at 25 ° C is in a range of 0.001 to 1 Pa · s, the molecular end is an M ^{R1R 2} unit, Or a release paper or a release film according to any one of [1] to [5], further comprising 10 to 100 parts by mass of an organopolysiloxane having an M ^R1R2 unit and a part of which is a silanol group or an alkoxy group based on 100 parts by mass of the component (A) ≪ / RTI >

[7] An organosilane represented by the following formula (14) having at least an epoxy group and an alkoxysilyl group in one molecule and / or a partially hydrolyzed (co) condensation siloxane represented by the following average composition formula (15) 1] to [6], further comprising 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A).

(A monovalent organic group containing a formula of, R ¹¹ is an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms, may contain an ether bond, some of which may be a hydrolyzed hydroxyl group, R ¹³ is H1 and h2 are integers and satisfy 1? H1, 1? H2, 2? H1 + h2? 4, h3 to h5 are positive numbers, 0 <h3 (Positive) condensation siloxane having a viscosity of from 0.001 to 1 Pa · s at 25 ° C, and 0 <h4, 0≤h5 and 1 <h3 + h4 + h5≤3, Selected)

[8] A process for producing a silicone resin composition, comprising the steps of: mixing a siloxane unit (M unit) represented by the following formula (16) and a siloxane unit (Q unit) represented by the following formula (17) A silicone composition for a release or release film according to any one of [1] to [7], further comprising 1 to 100 parts by mass of MQ resin in an amount of 1 to 100 parts by mass based on 100 parts by mass of the component (A)

(Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and i 1 is an integer of 0 to 3)

[9] The release liner or the release film for a film according to any one of [1] to [8], further comprising 0.1 to 5 parts by mass of a nonionic surfactant as a component (J) based on 100 parts by mass of the component (A) .

[10] A release paper or a release film on which a cured film of a silicone composition for a release paper or a release film described in any one of [1] to [9] is formed.

The release agent and release film of the present invention are excellent in resistance to weathering and peeling. The release liner and the release film coated and cured by the silicone composition for release liner or release film of the present invention can substantially maintain the releasability before exposure even if the silicone coated surface is exposed to the air for a long time.

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

[Silicone composition for release paper or release film]

The silicone composition for a release paper or a release film of the present invention is an addition reaction curable silicone composition comprising the following components (A) to (D) and optionally (E) to (J) .

(A) Component

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

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

A group represented by, X ⁴ are each independently formula: (3-1), X ⁵ has the formula (3-2) to each independently, X ⁶ is a chemical formula (3-3) to each independently

Group and, R ^1, R ² are as defined above represented by, a1, a2, a11, a21 , a31, a41, a51, a61 are each independently from 0 to 3 constant, a3 is a positive number, a4 to a6, a2 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 are 0 or a positive number, and they have a viscosity at 25 deg. C of the organopolysiloxane of not less than 0.05 Pa · s and not more than 30 mass% The viscosity is selected to be in a range of 70 Pa · s or less)

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

R ² is an unsubstituted or substituted monovalent hydrocarbon group free of the same or different aliphatic unsaturated bonds and is an alkyl group such as a methyl group, ethyl group, propyl group or butyl group, a cycloalkyl group such as a cyclohexyl group, A halogen atom such as fluorine, chlorine or bromine, a chloromethyl group substituted with a cyano group, a trifluoropropyl group, a cyano group Preferably an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and the like. R ² is preferably a methyl group or a phenyl group in an amount of not less than 80 mol%, and more preferably not less than 40 mol%, particularly preferably not less than 50 mol%, of the R ² is a methyl group and not more than 40 mol% of the R ² is a phenyl group.

The number of alkenyl groups in one molecule of the organopolysiloxane of the component (A) is two or more, and if it is less than two, there is a high possibility that uncrosslinked molecules remain after curing, and the curability is lowered. The alkenyl group content per 100 g of the organopolysiloxane 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, the curing property may be lowered. If the content is more than 0.5 mol, the solubility time may be shortened and the handling may become difficult.

It is preferable that the number of alkenyl groups in one molecule in the formula (1) is selected to be in the range of 2 to 300, especially 3 to 280. [ In this case, the number of alkenyl groups is [a1 + a2 + a4 + a5 x {a11 + a13 + a14 x a41 + a43 + a15 x a51 + a53 + a61 + a63) a31 + a33 + (a24 + a34) x (a41 + a43) + (a25 + a35) x 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.

In the formula (1), 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, Lt; / RTI &gt;

The viscosity of the organopolysiloxane of component (A) at 25 占 폚 is in the range of not less than 0.05 Pa · s and not more than 70 Pa · s as 30 mass% toluene diluted viscosity, preferably not less than 0.1 Pa · s and not more than 30 mass% 60 Pa · s or less. If the viscosity is less than 0.05 Pa · s, the releasability is not sufficient. If the viscosity is more than 70 Pa · s at 30 mass% toluene dilution viscosity, the workability is lowered. Here, the viscosity can be measured by a rotational viscometer (hereinafter the same).

The polymerization degree in the above formula (1) is preferably selected to be in the range of 50 to 20,000, particularly 55 to 19,000. In this case, the degree of polymerization is represented by [2 + a3 + a4 + a5 x {2 + a12 + a13 + a14 x (2 + a42 + a43) + a15 x (3 + a52 + a53 + a62 + + a22 + a23 + a32 + a33 + (a24 + a34) x2 + a42 + a43 + a25 + a35x3 + a52 + a53 + a62 + a63)}.

The main skeleton structure of the organopolysiloxane of the component (A) is a linear structure as shown in the case where a5 and a6 in the formula (1) are 0, or a linear structure in which a5 and / or a6 in the formula (1) Lt; / RTI &gt; structure as shown in Fig.

Specific examples of the component (A) include those shown below.

Component (B)

The component (B) of the present invention is blended as one of the components for improving the resistance to weatherability, and includes an alkene having 8 to 30 carbon atoms and an unsaturated bond at the terminal represented by the following formula (4) , Alkane dienes having unsaturated bonds at both ends thereof, alkane dienes having 1 to 4, particularly 1 to 3, alkenyl groups having 8 to 30 carbon atoms having unsaturated bonds at the terminals and represented by the following formula (6) , And disiloxane having 2 to 6, especially 2 to 4, alkenyl groups having 8 to 30 carbon atoms and having an unsaturated bond at the end represented by the following formula (7) are used.

(Wherein R ³ is independently a divalent hydrocarbon group having 6 to 28 carbon atoms, R ⁴ is independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 10 carbon atoms, b 1 is an integer of 1 to 4, b 2 Is independently an integer of 1 to 3)

In the formulas (4) to (7), R ³ is a divalent hydrocarbon group having 6 to 28, preferably 6 to 24 carbon atoms, and is preferably a hexamethylene group, a heptamethylene group, an octamethylene group, A cyclohexylene group, an octamethylene group, an octamethylene group, an octamethylene group, an undecamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, A cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, a cyclododecylene group, a cyclododecylene group, a cyclopentadiene group, a cyclopentadiene group, A cycloalkylene group such as a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, a cyclohexadecylene group, &Lt; / RTI & Phenylene group, and the like are an alkylene group such as methylene-phenylene-methylene group.

R ⁴ is a monovalent hydrocarbon group of 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or a hydrocarbonoxy group of 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and the monovalent hydrocarbon group contains an aliphatic unsaturated bond And examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and octyl group, cycloalkyl groups such as cyclohexyl group , An aryl group such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group, and the hydrocarbonoxy group includes, for example, a methoxy group, Propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, methoxyethyl group, Ethoxyethyl group, ethoxybutyl group, ethoxyhexyl group, A butyl group, a propyl group, a butyl group, and a butyl group.

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

Specific examples of the alkene represented by the formula (4) include 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, Octadecene, 1-eicosene, 1-doocosen, 1-tetracosene, 1-hexacosene, 1-octacosene and 1-triacontene.

Specific examples of the alkadiene represented by the formula (5) include 1,7-octadiene, 1,9-decadiene, 1,11-dodecadien, 1,13-tetradecadiene, , 1,17-octadecadiene, 1,19-eicosadiene, 1,21-docosadiene, 1,2,3-tetracosadiene, 1,25-hexacosadiene, 1,2,7-octacosadiene, 1 , 29-triacontadiene, and the like.

As the silane represented by the formula (6), specifically,

And the like.

As the disiloxane represented by the formula (7), specifically,

And the like.

The structure of the alkenyl compound of the component (B) having a low or no Si content is such that the volatility is suppressed by using a compound having a relatively high molecular weight and most of the alkenyl compound is capable of forming a chemical bond in the cured coating (B) component in the cured coating formed by the crosslinking of the component (A) as the main component is influenced to exhibit a tendency to separate the vicinity of the surface and the inside of the coating film I guess. It is considered that an effect of improving the resistance to weathering is exhibited by forming a portion having a high hydrocarbon concentration. In addition, the combination of these alkenyl compounds is suitable as a method of preventing heavy peeling, deteriorated residual adhesive force, and the development of transit property while hardly affecting the peeling property.

The blending amount of the component (B) is 5 to 20 parts by mass, preferably 7 to 18 parts by mass based on 100 parts by mass of the component (A). If the amount is less than 5 parts by mass, the effect of improving the resistance to weathering of the cured coating of the composition is insufficient, and if it exceeds 20 parts by mass, the curing property is deteriorated.

(C) Component

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

(In the formula, R ² is as defined above, c 1 is a positive number of 0.1 to 2, c 2 is a positive number of 0.01 to 2, c 1 + c 2 is a positive number of 3 or less, Lt; 0 &gt; C to be in the range of 0.005 to 10 Pa · s)

Such as the equation (8) of, R ² may have 1 which does not contain an aliphatic unsaturated bond of R ² and similar to those of the above formula (1) may be mentioned a hydrocarbon group, Of these, methyl, ethyl, propyl, butyl A cycloalkyl group such as an alkyl group and a cyclohexyl group, and an aryl group such as a phenyl group.

Further, c1 is a positive number of 0.1 to 2, preferably 0.2 to 2, c2 is a positive number of 0.01 to 2, preferably 0.04 to 1.5, more preferably 0.1 to 1, c1 + c2 is 3 or less, Is a positive number of 0.5 to 3, more preferably 1 to 3, and has at least two SiH groups in one molecule and has a viscosity at 25 DEG C in the range of 0.005 to 10 Pa · s, preferably 0.01 to 10 Pa · s . Outside this range of viscosity, the curability deteriorates.

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

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

The molecular structure of component (C) may be linear, branched or cyclic, and may be a combination thereof, or a mixture of two or more thereof may be used.

(8) Specifically, methyl hydrogen of the polymer comprising the Me ₃ SiO _1/2, and Me (H) SiO _2/2 siloxane units, a straight-chain siloxane which is a compound represented by; Me ₂ (H) Methyl hydrogen siloxane SiO _{1/2 a, Me (H) SiO 2/} 2 , and Me ₂ polymer containing SiO _2/2 siloxane units, a straight-chain; Phenyl hydrogen siloxane polymer is linear, including the _{Me 3 SiO 1/2, Me} (H) SiO 2/2 and MePhSiO _{2/2; Me 2 (H) SiO 1/2,} Me (H) SiO 2/2 and Ph ₂ SiO _{2/2-methylphenyl} of a linear polymer containing siloxane units hydrogen siloxane; Methyl hydrogen siloxane in the siloxane Me ₃ SiO _{1/2 a, Me (H) SiO 2/} 2 and MeSiO polymer containing the _3/2 siloxane units branched; Me ₂ (H) SiO phenyl hydrogen siloxane of _{1/2, Me (H) SiO 2/} 2, Ph 2 SiO 2/2 and a polymer comprising a PhSiO _3/2 siloxane units branched; Cyclic methylhydrogen siloxane, which is a polymer containing only Me (H) SiO2 _{/ 2} siloxane units; Methyl hydrogen siloxane in the annular Me ₂ SiO _2/2 and Me (H) SiO _2/2 polymers containing siloxane units; MePhSiO the like _2/2 and Me (H) SiO _2/2-phenyl hydrogen of the cyclic polymers containing siloxane units of the siloxane.

(C), more preferably an organohydrogenpolysiloxane having a linear or branched structure represented by the following formula (9) and / or an organohydrogenpolysiloxane having a cyclic structure represented by the following formula (10) Or an organohydrogenpolysiloxane having a straight chain structure and a cyclic structure simultaneously in one molecule.

(Wherein R ² is as defined above, R ⁵ is independently an unsubstituted or halogen or cyano-substituted monovalent hydrocarbon group containing no hydrogen atom or aliphatic unsaturated bond, R ⁶ and R ⁷ are Each independently represents an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group other than Me which contains no aliphatic unsaturated bond, Y ³ each independently represents a group represented by the following general formula (11-1) and Y ⁴ independently represents (11-2) and Y &lt; ⁵ &gt; each independently represent a group represented by the following formula (11-3)

A group represented by, general formula Y ⁶ are each independently to (12-1), Y ⁷ of the formula (12-2) to each independently, Y ⁸ has the formula (12-3) to each independently

A group represented by, R ^5, R ^6, R ⁷ are as described above, c11, c12, c31, c41, c51, c61, c71, c81 are each independently from 0 to 3 integers, c23 is an integer of 2 or greater, c23 + c24 + c25 + c26 + c27 + c28 + c29 wherein c13 to c19, c24 to c29, c32 to c38, c42 to c48, c52 to c58, c62 to c66, c72 to c76, 3 or more, and has at least 2 SiH groups in the molecule, particularly at least 3 SiH groups, and the viscosity at 25 캜 is selected to fall within the range of 0.005 to 10 Pa · s)

The formula (9), (10), R ² may have 1 which does not contain an aliphatic unsaturated bond of R ² and similar to those of the above formula (1) may be mentioned a hydrocarbon group, among them methyl group, ethyl group, propyl group, An alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group.

R ⁵ each independently represents an unsubstituted or substituted monovalent hydrocarbon group which contains no hydrogen atom or aliphatic unsaturated bond and is a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group An aryl group such as a phenyl group or a tolyl group, or a substituted or unsubstituted aryl group such as a chloromethyl group substituted by a halogen atom such as fluorine, chlorine or bromine, a chloromethyl group substituted by a cyano group, a trifluoropropyl group Unsubstituted or substituted monovalent hydrocarbon groups which do not contain an aliphatic unsaturated bond having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a cyano group, and the like. Of these, hydrogen atoms , Alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group.

Each of R ⁶ and R ⁷ is independently an unsubstituted or substituted monovalent hydrocarbon group other than Me containing no aliphatic unsaturated bond, and is preferably an alkyl group such as an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group An aryl group such as a phenyl group or a tolyl group, or a substituted or unsubstituted aryl group such as a chloromethyl group substituted by a halogen atom such as fluorine, chlorine or bromine, a chloromethyl group substituted by a cyano group, a trifluoropropyl group , A cyanoethyl group and the like, preferably an unsubstituted or substituted monovalent hydrocarbon group containing 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, which contains no aliphatic unsaturated bond.

Among them, an alkyl group is preferable as R ⁶ , and an effect of changing the performance of a cured coating is obtained by using a substituent having a changed carbon number. However, when the number of carbon atoms becomes too large, the curability tends to decrease. Therefore, the number of carbon atoms is preferably 4 or less, and the ethyl group and the propyl group are industrially preferable. The ethyl group having 2 carbon atoms is a preferred choice for withdrawing the releasability. R ⁷ is preferably an alkyl group such as an ethyl group, a propyl group or a butyl group, or a cycloalkyl group such as a cyclohexyl group.

The substituents contained in one molecule of the component (C) may be different from each other, but it is economically advantageous that the methyl group is preferably at least 50 mol%, more preferably at least 80 mol%, of the total substituents. In the case of the release film, there are many applications requiring higher transparency of the cured film and adhesion to the substrate. In this case, by replacing the substituent of the component (C) with a bulky substituent having a larger number of carbon atoms than the methyl group or an aromatic substituent, An effect of promoting wetting or interaction with the surface of the film substrate is obtained. When the component (C) having no aromatic substituent is used as the component (C1) and the component (C) having the aromatic substituent is used as the component (C2), the mass ratio of (C1) / , Especially 2/8 to 9/1 organohydrogenpolysiloxane, is preferable, and it is easy to balance with the other characteristics such as the peeling force of the cured coating.

Here, (C1) components as the formula (9) and / or in the general formula (10), the one other than the aromatic group for R ² which does not contain an aliphatic unsaturated bond, a hydrocarbon group, R ⁵ a hydrogen atom or an aliphatic unsaturated A structure in which monovalent hydrocarbon groups other than the aromatic group not containing a bond and R ⁶ and R ⁷ are monovalent hydrocarbon groups other than aromatic groups not containing an aliphatic unsaturated bond are preferable.

As the component (C2), a structure in which at least one of R ² and R ⁵ to R ⁷ in the above formula (9) and / or the above formula (10) is a monovalent hydrocarbon group having an aromatic group is preferable.

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

(C) an organohydrogenpolysiloxane is R ^{₂ 2} HSiO ^_1/2 units organohydrogenpolysiloxane or or the organohydrogenpolysiloxane having two or more in a molecule a (R ² is the same also as defined above) of components It is preferable that it is a mixture containing some.

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

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

The SiH groups in the organohydrogenpolysiloxanes represented by the above formulas (9) and (10) are not less than 2, especially not less than 3, and when less than 2, the production time is long and the production efficiency is lowered.

It is preferable that the number of SiH groups in one molecule in the formula (9) is selected to be in the range of 2 to 1,000, particularly 3 to 1,000, particularly 3 to 500. In this case, the number of SiH groups in one molecule is [c11 + c12 + c13 + c14 + c15 x {c31 + c32 + c33 + c34 x c52 + c53 + (c44 + c54) x (c61 + c62 + c63) + (c45 + c55) x c71 + c72 + c73 + c81 + c82 + c83}.

The number of SiH groups in one molecule in the formula (10) is preferably in the range of 2 to 100, particularly 3 to 100, particularly 4 to 50. In this case, the number of SiH groups in one molecule can be represented by [c23 + c24 + c25 x {c31 + c32 + c33 + c34 x (c61 + c62 + c63)} + c26 x {c41 + c42 + c43 + c51 + (c44 + c54) x (c61 + c62 + c63) + (c45 + c55) x (c71 + c72 + c73 + c81 + c82 + c83)}.

In the formula (9), the degree of polymerization is preferably selected to be in the range of 3 to 1,000, more preferably 3 to 500. [ In this case, the degree of polymerization [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] from the calculations are.

The polymerization degree in the formula (10) is preferably selected to be in the range of 3 to 100, particularly 4 to 50. [ In this case, the degree of polymerization [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] from the calculations are.

Specific examples of the organohydrogenpolysiloxane represented by the above formulas (9) and (10) include those shown below.

Examples of the organohydrogenpolysiloxane having a straight chain structure and a cyclic structure simultaneously in one molecule include organohydrogenpolysiloxanes represented by the formula (9) and organohydrogenpolysiloxanes represented by the formula (10) Hydrogenpolysiloxane is crosslinked between one of the molecular chain terminal SiH groups of the formula (9) and one of the SiH groups of the formula (10), and Si atoms are bonded to each other by a divalent organic group (-CH ₂ -CH ₂ - Or an organohydrogenpolysiloxane having two structures of a linear structure and a cyclic structure bonded through an oxygen atom (-O-) or the like.

Since the cross-linked state of the cured film is different in each of the linear structure, the branched structure and the cyclic structure, the peeling property can be controlled by separately using them. The cyclic structure is effective for making the hardened coating harder and lowering the rate dependency of the peeling force. The linear structure is effective in lightening the peeling force of the cured coating. The branched structure is effective for improving the curability of the composition in that it can introduce a large number of terminal SiH functional groups favorable for the curing reaction.

The formula (9) minutes, which is represented by the ground organo hydrogen minutes of special structure of the polysiloxane examples of ground organohydrogenpolysiloxane, sex R ² 1 functional ₂ HSiO _1/2 siloxane units (R ² are as defined above (hereinafter referred to as the same), since M also indicated as ^H units) and / or R _{² 3} SiO _^1/2 siloxane units (also described as after the M units) and trifunctional R ² SiO _3/2 siloxane units (as described hereinafter T units hereinafter described as siloxane (hereinafter HMQ siloxane containing siloxane (hereinafter described as HMT siloxane), hereinafter indicated as M ^H units or M units and tetrafunctional castle SiO _4/2 siloxane units (hereinafter Q unit) including a box) ).

Any siloxane group represented by R ² is industrially a Me group or a Ph group.

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

Similarly for HMQ siloxane, the molar ratio of (M ^H units + M units) / Q units is 2/8 to 8/2, especially 3/7 to 7/3, and the molar ratio of M units / M ^H units is 0/10 to 9 / 1, in particular, 0/10 to 8/2, and it is preferable that the molecular end is bound to the M ^H unit or the M unit. However, the silanol group and the alkoxy group may form a terminal with some silanol group or alkoxy group.

Specific examples of these HMT siloxanes and HMQ siloxanes are shown below.

These HMT siloxanes and HMQ siloxanes exhibit the effect of improving the resistance to weathering, and even if they are used singly, the effects can be expected to some extent. However, when they are used in combination with the component (B), the resistance to weathering can be further improved. It is presumed that the organohydrogenpolysiloxane having a branched structure tends to collect on the surface of the cured coating due to its structural characteristics and forms a surface which is not easily exposed.

Further, in the case of HMQ siloxane, it is preferable to increase the molar ratio of the unit (M ^H units + M units) / Q unit or to lower the degree of polymerization in order to suppress the occurrence of heavy streaking. Conventionally, HMQ siloxane is known to be used as a medium-flow control agent. However, when the molar ratio of (M ^H units + M units) / Q units is set to be high or the polymerization degree is reduced, It is also possible to expect the similar effect by the bi-functional castle (R ²⁾ ₂ in which the siloxane-containing HMDQ (indicated as D units after the box) SiO _2/2 siloxane units. HMT siloxane can also be improved by the same method as needed.

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

The blending amount of the organohydrogenpolysiloxane as the component (C) is such that the number of moles of the hydrogen atoms (SiH groups) bonded to the silicon atoms in the component (C) exceeds the number of moles of the components (A) and (B) Is an amount corresponding to 1 to 20 times, preferably 1.1 to 15 times the total number of moles of the alkenyl group (unsaturated group). When the number of moles of SiH groups in the component (C) is less than 1 times the total number of moles of the alkenyl group (unsaturated group), the curability becomes insufficient. On the other hand, even when the amount exceeds 20 times, , Rather, it causes a change with time and becomes economically disadvantageous. The blending amount of the organohydrogenpolysiloxane may be in the range of 0.1 to 30 parts by mass based on 100 parts by mass of the organopolysiloxane of component (A).

(D) Component

The platinum group metal catalyst (catalyst for addition reaction) which is the component (D) of the present invention promotes the crosslinking reaction between the components (A) and (B) (or any component thereof and an alkenyl group- And is used to form a cured coating. Examples of such catalysts for addition reaction include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, platinum vinyl group-containing siloxane coordination compound, rhodium, rhodium-olefin complex and the like.

The amount of the catalyst for addition reaction is a catalytic amount and can be suitably increased or decreased according to the reactivity or desired curing rate of the component. However, the amount of the platinum or the amount of rhodium is preferably 5 to 100 parts by weight, 1,000 ppm (by mass) is preferable for forming a sufficient cured coating.

(E) Component

The organic solvent (E) of the present invention is blended as needed for the purpose of improving the stability of the treatment bath and improving the coating properties on various substrates, coating amount and viscosity. Particularly, as a silicone composition for a release film, it is advantageous to provide a thin film coating and a favorable effect of improving the smoothness of the surface of the cured coating film. As the organic solvent, for example, those capable of uniformly dissolving compositions such as toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, hexane, and 2-butanone can be used.

The component (E) is an optional component and can be used as a silicone composition for a solvent-free release film or a release film, without incorporating it if the risk or safety of the organic solvent is undesirable.

The organic solvent of component (E) may be used singly or in combination of two or more kinds.

The amount of the component (E) to be used is preferably 10 to 100,000 parts by mass, more preferably 10 to 10,000 parts by mass, per 100 parts by mass of the component (A). If the blending amount is too large, it may be difficult to control the amount of coating. If the blending amount is too small, the effect of blending the solvent and the improvement of the coatability and the usable time may not be exhibited.

The silicone composition of the present invention can be easily prepared by uniformly mixing the above components (A), (B), (C), and (D) and, if necessary, component (E). However, The component (C) or the component (D) is preferably added and mixed immediately before coating. In the case of using the organic solvent as the component (E), it is preferable to mix the components (B) and (C) or the components (B) and (D) after uniformly dissolving the component (A) It is advantageous.

In the silicone composition of the present invention, the following components (F) to (J) may also be used as optional ingredients as long as they do not reduce the effects of the present invention.

(F) Component

(F) is an organopolysiloxane represented by the following 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 an unsubstituted or halogen or cyano group-substituted monovalent group containing no hydroxyl group, alkoxy group, alkoxyalkyl group and aliphatic unsaturated bond And R ¹⁰ is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group other than Me, which does not contain a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, f 1 and f 2 each represent an integer of 1 to 3 And f3 to f5 are integers selected so that the viscosity of the organopolysiloxane at 25 DEG C is in a range of 1 Pa · s or more and 30 mass% toluene dilution viscosity of 100 Pa · s or less)

In the formula (13), R ⁸ are independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group, an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n- butoxy group, sec- butoxy group, tert -Butoxy group, and the like. Examples of the alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a methoxybutyl group, and an ethoxybutyl group. 6 &lt; / RTI &gt;

R ⁹ is independently an unsubstituted or substituted monovalent hydrocarbon group free of a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cyclohexyl group , A halogen atom such as fluorine, chlorine or bromine, a chloromethyl group substituted with a cyano group, a trialkylsilyl group such as a chloromethyl group substituted with a cyano group, a tri An unsubstituted or substituted monovalent hydrocarbon group of 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a fluoropropyl group and a cyanoethyl group, and the like, and examples thereof include a hydroxyl group, an alkoxy group and an aliphatic unsaturated bond Is preferably an unsubstituted monovalent hydrocarbon group which does not contain an alkyl group such as methyl group, ethyl group, propyl group or butyl group, a cycloalkyl group such as cyclohexyl group An aryl group such as a methyl group, an ethyl group, a propyl group,

R ¹⁰ is an unsubstituted or substituted monovalent hydrocarbon group other than Me which does not contain a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, and specifically includes an alkyl group such as an ethyl group, a propyl group or a butyl group, An aryl group such as a phenyl group or a tolyl group, or a substituted or unsubstituted aryl group such as a chloromethyl group substituted with a cyano group, a halogen atom such as fluorine, chlorine or bromine, An unsubstituted or substituted monovalent hydrocarbon group of 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a trifluoropropyl group and a cyanoethyl group, and the like, and examples thereof include a hydroxyl group, an alkoxy group and an aliphatic unsaturated An unsubstituted monovalent hydrocarbon group not containing a bond is preferable, and an alkyl group such as an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, An aryl group such as a phenyl group or a tolyl group is more preferable.

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

The viscosity of the organopolysiloxane as component (F) at 25 캜 is in the range of 1 Pa · s or more and 30 mass% of toluene diluted viscosity of 100 Pa · s or less, particularly in the range of 10 Pa · s to 30 mass% of toluene diluted viscosity of 50 Pa · s . If the viscosity is too low, slipping of the cured coating may be insufficient. If the viscosity is too high, industrial handling may become difficult.

The siloxane having no functional group on the side chain as a straight chain polymer is effective for imparting slidability to the cured coating, and an effect of lightening the peeling force without lowering the residual adhesive force can also be expected. In the peeling film, an effect of preventing slippage is also exhibited by the effect of sliding.

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

When the component (F) is blended, the blending amount is preferably 0.1 to 30 parts by mass, and more preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the component (A). If the amount is less than 0.1 part by mass, the effect of imparting a slip property may not be obtained. If the amount is more than 30 parts by mass, the residual adhesive force may be lowered.

(G) Component

As the component (G), a component for improving the substrate adhesion property can be blended. (G) component is an organopolysiloxane having at least two alkenyl groups, and the monofunctional R ² _(3-g ¹ ₎ R ¹ _g ¹ SiO _1/2 siloxane unit (wherein R ¹ and R ² are the same as above (the same below), g1 is an integer from 1 to 3, hereafter indicated as M ^R1R2 unit), and the trifunctional R _² SiO _^3/2 siloxane unit (hereinafter described as T ^R2 units) as an essential unit, It is preferable that the organopolysiloxane has a molar ratio of M ^{R1R 2} units / T ^{R 2} units of 2/8 to 8/2 and has a viscosity at 25 ° C in the range of 0.001 to 1 Pa · s. Although it is preferable that the M &lt; 1 &gt; ^R &lt; ² &gt; unit binds to the molecular terminal, it may be formed with some silanol group or alkoxy group to form a terminal.

In the formula, R ¹ may be mentioned alkenyl groups of the same as R ¹ of Formula (1), Among these, vinyl group is preferred industrially. In addition, R ² may have 1 which does not contain an aliphatic unsaturated bond of R ² and similar to those of the above formula (1) may be mentioned a hydrocarbon group, a methyl group, among them, it is phenyl group is preferred industrially. g1 is an integer of 1 to 3, preferably 1 or 2.

(G) is an organopolysiloxane in which the molar ratio of the M ^R1R2 units / T ^R2 units is 2/8 to 8/2, preferably 3/7 to 7/3. When the molar ratio is less than 2/8, the effect of improving the adhesion may be small. When the molar ratio is more than 8/2, industrial production becomes difficult.

Further, as (G) of effect bifunctional Castle R ² _{(2- g2)} from that do not damage the components of the R ¹ SiO _2/2 siloxane units, _g2 (in the formula, and g2 is 0, 1 or 2, D ^R1R2 unit described hereinafter), tetrafunctional castle SiO _4/2 siloxane units, (but also including the Q unit), in particular stripping if needed a stronger adhesion according to the film, which does not contain them M ^R1R2 units / T ^R2 molar ratio of the unit Is from 2/8 to 8/2 is preferred. When D ^R1R2 unit or Q unit is included, it is necessary to use a small amount for both of M ^R1R2 unit and T ^R2 unit.

The component (G) is different from the component (A) in that the T ^R2 unit is ^larger than the D ^R1R2 unit.

The amount of the alkenyl group of the organopolysiloxane as the component (G) is preferably 0.01 to 2.5 mol, more preferably 0.03 to 2.0 mol, and still more preferably 0.05 to 1.5 mol, per alkenyl group content per 100 g of the organopolysiloxane . If the content is too small, the effect of improving the adhesion may be small. If the content is too large, the usable time may be shortened.

The organopolysiloxane of component (G) preferably has a viscosity at 25 ° C of from 0.001 to 1 Pa · s, particularly preferably from 0.005 to 0.5 Pa · s, more preferably from 0.01 to 0.1 Pa · s, Is preferably in the range of 0.01 to 0.05 Pa · s, and it is preferable that the polymerization degree is in the range of this viscosity. If the viscosity is less than 0.001 Pa · s, the effect of improving the adhesion may be small. If the viscosity is more than 1 Pa · s, the solubility or dispersibility in the composition may be lowered.

In addition, the component (G) can be expected to have an effect of further increasing the effect of improving the resistance to weathering by using the component (C) in combination with the branched organohydrogenpolysiloxane. It is presumed that the branching structure can be drawn more strongly by binding with the branched organohydrogenpolysiloxane by an addition reaction.

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

When the component (G) is blended, the blending amount is preferably 10 to 100 parts by mass, more preferably 15 to 100 parts by mass, per 100 parts by mass of the component (A). When the amount is less than 10 parts by mass, the effect of improving the adhesion of the base material may be small. When the amount is more than 100 parts by mass, the intermediate bead may become large.

When the component (G) is blended, the molar ratio (SiH group / alkenyl group) of the SiH groups in the component (C) to the number of moles of the alkenyl groups in the component (G) (C) is preferably added in order to prevent deterioration of the curability.

(H) Component

(H) an organosilane represented by the following formula (14) having at least an epoxy group and an alkoxysilyl group in one molecule and / or an organosilane represented by the formula (14) represented by the following average composition formula (15) Partially hydrolyzable (co) condensation siloxanes of organosilanes can be used.

(A monovalent organic group containing a formula of, R ¹¹ is an epoxy group, R ¹² may be also be, and some hydrolyzed hydroxyl group, including the alkyl group, an ether bond with a carbon number of 1 to 6, R ¹³ is H1 and h2 are integers and satisfy 1? H1, 1? H2, 2? H1 + h2? 4, h3 to h5 are positive numbers, 0 <h3, Selected from a positive number satisfying 0 <h4, 0? H5 and 1 <h3 + h4 + h5? 3 and having a viscosity of the partially hydrolyzed (co) condensation siloxane at 25 DEG C in the range of 0.001 to 1 Pa · s )

The partial hydrolyzed (co) condensation siloxane represented by the formula (15) of the component (H) is different from the component (A) and the component (F) in that it has an epoxy group.

Examples of monovalent organic groups containing an epoxy group of R &lt; ¹¹ &gt; in the formulas (14) and (15) include 3- glycidoxyalkyl groups such as 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl (2-hydroxyethyl) propyl group, and the like.

Examples of the alkyl group having 1 to 6 carbon atoms for R ¹² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, Examples of the bond include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a butoxyethyl group, a methoxypropyl group, an ethoxypropyl group, And alkoxyalkyl groups having 1 to 6 carbon atoms such as methoxyethyl, ethoxybutyl and the like. Examples of the alkoxyalkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, A methyl group, a propoxymethyl group, a butoxymethyl group, a methoxyethyl group and an ethoxyethyl group are preferable. Examples of the OR ¹² group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxy methoxy group, a methoxyethoxy group, an ethoxy methoxy group, and an ethoxyethoxy group.

R ¹³ is an unsubstituted or substituted monovalent hydrocarbon group, specifically, an alkyl group such as methyl group, ethyl group, propyl group or butyl group, a cycloalkyl group such as cyclohexyl group, an alkenyl group such as vinyl group, allyl group or propenyl group An aryl group such as a phenyl group or a tolyl group, or a substituted or unsubstituted aryl group such as a chloromethyl group substituted by a halogen atom such as fluorine, chlorine or bromine, a chloromethyl group substituted by a cyano group, a trifluoropropyl group Unsubstituted or substituted monovalent hydrocarbon groups which do not contain an aliphatic unsaturated bond having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, such as a cyano group, and the like, and an aliphatic unsaturated bond-containing , And more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and a phenyl group.

H1 and h2 are integers and satisfy 1? H1, 1? H2, 2? H1 + h2? 4, h3 to h5 are positive numbers, 0 <h3, 0 <h4, 0? H5, 1 <h3 + h4 + h5? 3, and is a positive number satisfying the viscosity described later.

The viscosity of the partially hydrolyzed (co) condensation siloxane represented by the above formula (15) at 25 캜 is preferably 0.001 to 1 Pa · s, more preferably 0.001 to 0.1 Pa · s, particularly preferably 0.001 to 0.05 Pa · s . If the viscosity is too low, the effect of improving the adhesion may be small. If the viscosity is too high, the solubility or dispersibility of the composition may be deteriorated.

The partially hydrolyzed (co) condensed siloxane represented by the formula (15) can be obtained by adding water to the silane represented by the formula (14) and adding a catalyst such as hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, maleic acid, phosphoric acid, , And removing the produced alcohol by distillation. The silane represented by the formula (14) and other alkoxysilanes may be mixed and reacted to form a partially hydrolyzed cocondensed silane.

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

(H) is preferably from 0.1 to 10 parts by mass, more preferably from 1 to 8 parts by mass based on 100 parts by mass of the component (A). If the amount is less than 0.1 part by mass, the adhesion improving effect may not be obtained. If the amount is more than 10 parts by mass, the residual adhesive strength may be lowered.

In the present invention, a catalytic amount of an acid, an alkali, and a metal compound may be added in order to further draw out the effect of improving the adhesion of the component (H). Examples of the acid include formic acid, acetic acid, lactic acid, oxalic acid, malonic acid, malonic acid, benzoic acid, hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, phosphoric acid, ammonium chloride and ammonium sulfate. Examples of the alkali include ammonia, sodium acetate, Sodium hydroxide, and ammonium hydroxide. Examples of the metal compound include aluminum chloride, trisacetylacetonato aluminum, octyl iron, trisacetylacetonato iron and trisacetylacetonato zircon.

These are also used for activating the functional groups of the component (G), and the addition amount thereof is preferably controlled within a range not affecting the curability, the use time and the storage stability of the composition, and is preferably 0.0001 To 0.01 parts by mass.

(I) Component

In addition, (I) to a component formula 16 siloxane units (M ^R1R2 units) and the following formula (17) siloxane units molar ratio (Q unit) (M ^R1R2 unit / Q unit) represented by the represented by the 2 / 8 to 8/2 can be used.

(Wherein R ¹ and R ² are as defined above and i 1 is an integer of 0 to 3)

In the formula, R ¹ may be mentioned alkenyl groups of the same as R ¹ in the formula (1), Among these, preferred is alkenyl such as vinyl group, allyl group, propenyl group. In addition, R ² may have 1 which does not contain an aliphatic unsaturated bond of R ² and similar to those of the above formula (1) may be mentioned a hydrocarbon group, among them methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group , A phenyl group, and a cyclohexyl group are preferable. i1 is an integer of 0 to 3, preferably 0, 1 or 2;

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

Further, within a range not to impair the effects of the present invention the bifunctional Castle R ² _(2-i2) R ¹ _i2 SiO _2/2 siloxane units (in the formula, and i2 is 0, 1 or 2, D ^R1R2 unit), 3 also including functional castle R _² SiO _^3/2 siloxane unit (T unit ^R2), or R ¹ SiO _3/2 siloxane units (T units ^R1). Further, the ratio of the D ^R1R2 unit to the T ^R2 unit is made smaller than either the M ^R1R2 unit or the Q unit, and the effect is also different since the ratio is different from that of the (G) component.

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

This component is generally used as a release force control agent, but an effect of improving the resistance to weathering can be obtained even if a small amount of the composition does not exhibit the control effect. In the siloxane unit represented by the formula (16), the MQ resin composed only of il = 0 has an advantage of obtaining an effect of stably improving the resistance to spark irrespective of the method of use such as coating conditions. On the other hand, the MQ resin having a non-zero alkenyl group of il has a tendency to be difficult to use because of a large variation in the resistance to weathering. However, by using the component (C) in combination with the branched organohydrogenpolysiloxane, The improvement effect can be stably drawn out more greatly. It is presumed that the branching structure can be drawn more strongly by binding with the branched organohydrogenpolysiloxane by an addition reaction.

The amount of the alkenyl group of the MQ resin of the component (I) is preferably 0 to 2.4 moles, more preferably 0 to 2.0 moles, and still more preferably 0 to 1.5 moles, per alkenyl group content per 100 g of the organopolysiloxane. When the content is too small, the effect of heavy bleeding may deteriorate with time, while when it is too large, the time of use may be shortened.

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

When the component (I) is blended, the blending amount is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the component (A). If the amount is less than 1 part by mass, the effect of improving the resistance to weathering may be reduced. If the amount is more than 100 parts by mass, the resulting intermediate layer may become too heavy.

When the component (I) to be compounded has an alkenyl group, the molar ratio (SiH group / alkenyl group) of the SiH group in the component (C) to the number of moles of the alkenyl group in the component (I) (C) is added in order to prevent the lowering of the curability.

(J) Component

 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 ether such as polyoxyethylene lauryl ether and polyoxyethylene polyoxypropylene alkyl ether such as polyoxyethylene polyoxypropylene stearyl ether.

The component (J) is also expected to have an effect of improving the compatibility with a hydrophobic component such as a conductive agent component of a conductive polymer composition to be described later, which can be blended. Further, by improving the leveling by the (J) nonionic surfactant, transparency and smoothness of the cured coating can also be expected to be improved.

The addition of the component (J) is expected to improve the resistance to weathering due to the antistatic effect. For this purpose, the addition amount is preferably 0.1 to 5 parts by mass, particularly 0.2 to 4 parts by mass, relative to 100 parts by mass of the component (A) . If the addition amount is too large, the curability of the composition may be lowered.

Other components

To the silicone composition of the present invention, 0.01 to 1 part by mass of a bath life-extending agent such as 3-methyl-1-butyne-3-ol, ethynylcyclohexanol or ethynylcyclohexane relative to 100 parts by mass of the component (A) Can be compounded.

The silicone composition of the present invention may contain other organic resin. The organic resin is a component blended for the purpose of stability of the treatment bath, improvement of coatability to various substrates, improvement of film formability, adjustment of peeling property, adjustment of coating amount and viscosity and, for example, polyvinyl alcohol, poly ) Acrylate, polyester, cellulose, and their derivatives can be used and can be contained in an amount of 2 to 400 parts by mass based on 100 parts by mass of the component (A), but if they affect the peeling property and the antistatic property .

Specific examples of the derivatives include those obtained by etherifying a part of the hydroxyl group of cellulose with an alkyl group, and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and an ethyl group is preferable.

The silicone composition of the present invention may be blended with a conductive polymer composition for the purpose of preventing electrification or imparting conductivity and / or for improving atmospheric exposure. The conductive polymer composition comprises (a) a π-conjugated conductive polymer, (b) a polyanion doped in the (a) π-conjugated conductive polymer, (c) a solvent containing a solubilizing agent, Is preferably dispersed in water. When the conductive polymer composition is blended, the blending amount is preferably 5 to 50 parts by mass based on 100 parts by mass of the component (A).

[Release paper or release film]

The release paper or release film according to the second aspect of the present invention comprises a base material including paper or a plastic film and a release agent layer formed on at least one side of the base material.

The release agent layer constituting the release paper or release film of the present invention is a layer formed by the cured coating of the silicone composition.

The thickness of the release film is preferably 2 to 500 mu m, more preferably 10 to 100 mu m. The thickness of the release paper is preferably 10 to 1,000 mu m, more preferably 50 to 300 mu m. These thicknesses can be measured by a known thickness gauge such as a dial gauge, an ultrasonic thickness gauge, or the like.

In the release paper and the release film, the thickness of the release agent layer is preferably 0.1 to 5.0 占 퐉, more preferably 0.1 to 2.0 占 퐉. Here, the &quot; thickness of the release agent layer &quot; can be measured by a fluorescence X measuring apparatus.

Examples of the resin material constituting the plastic film include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacrylic, polycarbonate, A polyether sulfone, a polyether ether ketone, a polyphenylene sulfide, a polyarylate, a polyimide, a polycarbonate, a cellulose triacetate, and a cellulose triacetate. Cellulose acetate propionate and the like. Among these resin materials, polyethylene terephthalate is preferable in view of transparency, flexibility, antifouling property and strength.

As the paper, a high-quality paper, a kraft paper, a coated paper, or the like can be used.

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

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

Examples of the drying method include a method of removing volatile components and solvent components by heating. Specific examples thereof include a hot air dryer and an IR dryer. Alternatively, it may be allowed to stand at room temperature. The temperature at the time of drying is preferably 50 to 200 占 폚, more preferably 70 to 180 占 폚. The time for drying is preferably 1 to 120 seconds, more preferably 5 to 90 seconds.

The release paper or the release film according to the second aspect of the present invention has a release agent layer containing a cured coating of the silicone composition, and therefore has both excellent resistance to weathering and peelability. Therefore, the release paper or the release film of the present invention is preferably used 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 type viscometer (manufactured by Toki San). In the following examples, "part" means "mass part" and "%" means "mass%".

[Example 1]

As the component (A), and 30% and a viscosity at 25 ℃ of a toluene solution 20Pa · s, in which both ends of the molecular chain _{(CH 3) 2 (CH 2} = CH) SiO dimethyl vinyl silyl group represented by _1/2 this blockade is, the main skeleton, excluding the terminal _{(CH 3) (CH 2 =} CH) SiO 2 / methyl vinyl siloxane units, 0.7 mol% represented by ₂ and (CH _{3) 2} siloxane unit represented by SiO _2/2 99.3 100 parts of an organopolysiloxane (A-1) (vinyl group content = 0.01 mol / 100 g) composed of 1 mol% ) Were placed in a flask, and dissolved by stirring at 20 to 40 占 폚.

1-octadecene as the component (B), the resulting solution (B-1) to (unsaturated group content = 0.4 mole / 100g) as 15 parts, (C) component is both ends of a molecule chain _{(CH 3) 3 SiO 1/} 2 and blockade trimethylsilyl group represented by, (CH _{3) 2} HSiO _{/ 2} containing 95 mol% of methyl hydrogen siloxane units represented by, and the viscosity at 25 ℃ 0.03Pa · s straight-chain organohydrogenpolysiloxane (The number of moles of hydrogen atoms directly connected to the silicon atom is 1.3 times the total number of moles of unsaturated groups contained in the component (A) and the component (B)), 1 part of 3-methyl-1-butyn-3-ol as a bath life-extending agent, and the mixture was stirred at 20 to 40 ° C for 1 hour.

Just before coating the obtained solution, a platinum-vinylsiloxane complex as a catalyst of the component (D) was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst to prepare a coating composition.

[Example 2]

(A) has a viscosity at 25 ℃ a 30% toluene solution as a component is 10Pa · s, the ends of the molecular chain _{(CH 3) 2 (CH 2} = CH) SiO dimethyl vinyl and blocked silyl group represented by _{1/2 , (CH 3) (CH 2} = CH) 2.8 mole% methyl vinyl siloxane unit represented by SiO _2/2 and _{(CH 3) 2 SiO 2/} 2 a dimethylsiloxane units and 96.9% by mole represented by (CH ₃ ) 100 parts of an organopolysiloxane (A-2) (vinyl group content = 0.04 mol / 100 g) containing 0.1 mol% of methylsiloxane units represented by SiO _{3 /} And 1,102 parts of 2-butanone (E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.

5 parts of 1,7-octadiene (B-2) (unsaturated group content = 1.8 mol / 100 g) as a component (B), 5 parts of a linear organohydrogenpolysiloxane of Example 1 C-1) (SiH content = 1.5 mol / 100g) the part 8, and (CH _{3) 2} HSiO _{/ 2} include a methyl hydrogen siloxane to 100 mol% of units represented by, and a viscosity at 25 ℃ 0.005Pa · 3 parts of a cyclic organohydrogenpolysiloxane (C-2) (SiH content = 1.7 mol / 100 g) having a total number of moles of hydrogen atoms directly connected to silicon atoms in component (C) 1 part of 3-methyl-1-butyn-3-ol as a bath life-extending agent was mixed and stirred at 20 to 40 ° C for 1 hour.

Just before coating the obtained solution, a platinum-vinylsiloxane complex as a catalyst of the component (D) was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst to prepare a coating composition.

[Example 3]

100 parts of the organopolysiloxane (A-1) (vinyl group content = 0.01 mol / 100 g) of Example 1 as the component (A), 1,121 parts of toluene (E-1) E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.

As the component (B), the following formula

, 10 parts of silane (B-3) (unsaturated group content = 0.47 mol / 100 g) represented by the following formula (1), and the straight chain organohydrogenpolysiloxane (C-1) / 100g) the part 4, and a molecular chain, both ends (CH _{3) 2} HSiO dimethyl being blocked group hydrogen silyl represented by _{1/2, (CH 3)} HSiO the methyl hydrogen siloxane unit represented by the _2/2 A straight chain organopolysiloxane (C-3) containing 25 mol% of dimethylsiloxane units represented by (CH ₃ ) ₂ SiO _2/2 and having a viscosity of 0.04 Pa · s at 25 ° C (SiH content = 1.2 mol / 100 g) was added in an amount of 4 parts (the total molar number of hydrogen atoms directly connected to the silicon atom of the component (C) was 1.3 times the total number of moles of unsaturated groups contained in the component (A) 1 part of 3-methyl-1-butyn-3-ol as a bath life-extending agent, and the mixture was stirred at 20 to 40 ° C for 1 hour.

Just before coating the obtained solution, a platinum-vinylsiloxane complex as a catalyst of the component (D) was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst to prepare a coating composition.

[Example 4]

(A) is 30% and a viscosity at 25 ℃ of a toluene solution 15Pa · s, both ends of the molecular chain as the component _{(CH 3) 2 (CH 2} = CH) SiO dimethyl vinyl silyl group containment represented by _1/2 and, the main skeleton other than the terminal _{(CH 3) (CH 2 =} CH) SiO 2/2 -methyl vinyl siloxane units and 1.5 mol% of (CH ₃₎ dimethyl siloxane unit represented by SiO _{2/2 2} represented by 98.5 mol 100 parts of an organopolysiloxane (A-3) (vinyl group content = 0.02 mol / 100 g) consisting of 1% 1,121 parts were put in a flask and dissolved by stirring at 20 to 40 ° C.

As the component (B), the following formula

10 parts of the disiloxane (B-4) (unsaturated group content = 0.56 mol / 100 g) represented by the following formula (1) and the linear organohydrogenpolysiloxane (C-1) 4 parts of a mol / 100g), and (CH _{3) 2} HSiO 50% mol of dimethyl hydrogen silyl group represented by _1/2, (CH ₃₎ contains siloxane units of 50 mole% represented by SiO _3/2 , 4 parts of a branched organohydrogenpolysiloxane (C-4) (SiH content = 0.75 mol / 100 g) having a viscosity of 0.01 Pa · s at 25 ° C 1 part of 3-methyl-1-butyn-3-ol as a bath life-extending agent is blended, and the total molar number of the component (B) is 1.4 times as much as the total number of moles of the unsaturated group contained in the component (A) And the mixture was stirred at 20 to 40 DEG C for 1 hour.

Just before coating the obtained solution, a platinum-vinylsiloxane complex as a catalyst of the component (D) was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst to prepare a coating composition.

[Example 5]

(A) is 30% and a viscosity at 25 ℃ of a toluene solution 15Pa · s, both ends of the molecular chain as the component _{(CH 3) 2 (CH 2} = CH) SiO dimethyl vinyl silyl group containment represented by _1/2 and, the main skeleton other than the terminal _{(CH 3) (CH 2 =} CH) SiO methylvinylsiloxane unit 4 mol% represented by the _2/2 and (CH ₃₎ dimethylsiloxane units 91 mole represented by ₂ SiO _2/2 100 parts of an organopolysiloxane (A-4) (vinyl group content = 0.04 mol / 100 g) composed of 5 mol% of diphenylsiloxane units represented by the formula (C ₆ H ₅ ) ₂ SiO _{2 /} 1,121 parts of toluene (E-1) and 1,121 parts of 2-butanone (E-2) were taken in a flask and dissolved by stirring at 20 to 40 ° C.

10 parts of the disiloxane (B-4) (unsaturated group content = 0.56 mol / 100 g) of Example 4 as the component (B), 10 parts of the linear organohydrogenpolysiloxane of Example 1 C-1) (SiH content = 1.5 mol / 100g) the part 4, and (CH ₃₎ represented by the ₂ HSiO _1/2 45% mol of dimethyl hydrogen silyl group represented _{by, (CH 3) 2 SiO 2} /2 of dimethylsiloxane units 10 mole%, SiO _4/2 siloxane containing 45 mol% of units, and a viscosity at 25 ℃ 0.01Pa · s represented by one where the ground organohydrogenpolysiloxane (C-5) (SiH content = 0.75 mol / 100 g) was added in an amount of 4 parts (equivalent to 1.4 times the total number of moles of hydrogen atoms directly connected to the silicon atom of component (C) with respect to the total number of moles of unsaturated groups contained in component (A) And 1 part of 3-methyl-1-butyn-3-ol as a bath life-extending agent were mixed and stirred at 20 to 40 ° C for 1 hour.

Just before coating the obtained solution, a platinum-vinylsiloxane complex as a catalyst of the component (D) was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst to prepare a coating composition.

[Example 6]

100 parts of the organopolysiloxane (A-1) (vinyl group content = 0.01 mol / 100 g) of Example 1 as the component (A), 1,168 parts of toluene (E-1) E-2) were placed in a flask and dissolved by stirring at 20 to 40 ° C.

As the component (B), the following formula

15 parts of 1-hexadecene (B-5) (unsaturated group content = 0.45 mol / 100 g) represented by the following formula (1) and the straight chain organohydrogenpolysiloxane (C-1) in which both ends = 1.5 mol / 100g) to 6 parts, and the molecular chain, _{(CH 3) 2 HSiO 1/} 2 the dimethyl and blocked groups hydrogen silyl, main skeleton other than the terminal thereof represented by (CH ₃₎ HSiO _2/2 methyl hydrogen and siloxane units of 60 mole% represented by _{(CH 3) 3 SiO 1/} 2 and siloxane units of 20 mole%, represented by _{(C 6 H 5) 2 SiO} 2/2 diphenylsiloxane units 20 represented by (C-6) (SiH content = 0.68 mol / 100 g) having a viscosity at 25 ° C of 0.5 Pa · s (the component (C) The total molar number of hydrogen atoms directly connected is 1.3 times as much as the total number of moles of unsaturated groups contained in the component (A) and the component (B)), 3-methyl-1-butyn- 1 part, And the mixture was stirred at 40 ° C for 1 hour.

Just before coating the obtained solution, a platinum-vinylsiloxane complex as a catalyst of the component (D) was added in an amount corresponding to 0.02 part (20 mg) of platinum as a catalyst to prepare a coating composition.

[Example 7]

In the same manner as in Example 1 except that the 30% toluene solution as the component (F) had a viscosity of 40 Pa · s at 25 ° C, both ends of the molecular chain were blocked with dimethylhydroxylsilyl groups, and the main skeleton excluding the terminals was dimethylsiloxane unit 100 (C-1) of the organopolysiloxane (C-1) of Example 1 was further blended with 1 part of the organopolysiloxane (F) (hydroxyl group content = 0.0002 mol / is the (SiH content = 1.5 mol / 100g) 5 parts, and the molecular chain, both ends (CH _{3) 2} HSiO groups are blocked dimethyl hydrogen silyl group represented by the _1/2, (CH _{3) 2} SiO _2/2 shown as 5 parts ((C)) of a straight chain organohydrogenpolysiloxane (C-7) (SiH content = 0.1 mol / 100 g) having a dimethylsiloxane unit in an amount of 90 mol% and a viscosity at 25 ° C of 0.02 Pa · s, (A), the component (B) and the component (F), the total number of moles of the hydrogen atoms directly connected to the silicon atom of the component (E-1) and 1,197 parts of 2-butanone (E-2) in the same manner as in Example 1, except that the amount of the component (E) was increased to 1,197 parts of toluene (E-1) and 1,197 parts of 2-

[Example 8]

In the same manner as in Example 4, except that the component (G) had a viscosity at 25 ° C of 0.03 Pa · s, the molecular chain end was blocked with a dimethylvinylsilyl group and the main skeleton excluding the terminal was (CH ₃ ) ₂ CH ₂ = CHSiO _{1 / 2} units perform 50 mol% and a CH ₃ SiO _{3/2 units,} organopolysiloxane (G) consisting of 50 mol% (vinyl group content = 0.6 mole / 100g) 20 parts of added compounding, and the component (C), for example, 11 parts of the linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) and the branched organohydrogenpolysiloxane (C-4) (SiH content = 0.75 mol / 100 g) was added to 11 parts (the total number of moles of hydrogen atoms directly connected to the silicon atom of the component (C) was 1.3 times the total number of moles of the unsaturated groups contained in the component (A), the component (B) And the component (E) was increased to 1,444 parts of toluene (E-1) and 1,444 parts of 2-butanone (E-2).

[Example 9]

In Example 4, the component (H)

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

And 3 parts of a siloxane oligomer (H) having an epoxy group having an average degree of polymerization of 3 and a viscosity of 0.1 Pa · s at 25 ° C were further added and the component (E) was mixed with 1,149 parts of toluene (E-1) A composition was prepared in the same manner as in Example 4 except that the amount of the compound (E-2) was increased to 1,149 parts.

[Example 10]

Implemented as a (I) component in Example _{5 CH 2 = CH (CH 3} ) 2 SiO 1/2 units of 5 _{mol%, (CH 3) 3 SiO} 1/2 units 45 mol%, SiO _4/2 units 50 mol% (C-1) of the organopolysiloxane (C-1) having an average degree of polymerization of 100 (the vinyl group content: 0.07 mol / 100 g) , 8 parts of a silane coupling agent (SiH content = 1.5 mol / 100 g) and 6 parts of a branched organohydrogenpolysiloxane (C-5) (SiH content = 0.75 mol / 100 g) The molar amount of the hydrogen atoms directly connected to the atom is increased to 1.5 times the total number of moles of the unsaturated group contained in the component (A), the component (B) and the component (I)) and the component (E) (E-1) and 1,368 parts of 2-butanone (E-2).

[Example 11]

Example A (I) component in the _{1 (CH 3) 3 SiO 1} /2 units 55 mol%, SiO _{4 /} organopolysiloxane of the _second unit the average degree of polymerisation of 70 comprising 45 mole% (I-2) 2 additional parts And the component (E) was increased to 1,159 parts of toluene (E-1) and 1,159 parts of 2-butanone (E-2).

[Example 12]

1 part of a nonionic surfactant (J) represented by polyoxyethylene dodecyl ether (number of bonds of oxyethylene: 5 to 15) was further added as component (J) in Example 1, and component (E) -1) and 1,149 parts of 2-butanone (E-2).

[Example 13]

Component (A) as a siloxane unit represented by the viscosity of 0.5Pa · s, the ends of the molecular chain are blocked dimethyl vinyl silyl group, and dimethyl siloxane units in 25 ℃ to 97 mol%, CH ₃ SiO _3/2 100 parts of a branched organopolysiloxane (A-5) (vinyl group content = 0.02 mol / 100 g) containing 1 mol% of a disiloxane (B-4) (C-1) (SiH content = 1.5 mol / 100 g) as the component (C) (the amount of the silicon atom (C) is the number of moles of hydrogen atoms directly connected to the component (a), (B) component and the (G) corresponds to 1.3 times the total molar amount of the unsaturated group, which component is contained), of example 8 as a component (G) (CH _{3 ) 2 CH 2 = CHSiO 1/} 2 units 50 mol%, CH ₃ SiO _3/2 units of organopolysiloxane (G) containing 50 mole% poly (vinyl group content = 20 parts of a 0.6 mol / 100g), bath life extension 3-methyl-1-butyn-3-ol (E) were mixed with stirring at 20 to 40 ° C for 1 hour without mixing.

A composition was prepared by adding a platinum-vinyl siloxane complex as a catalyst of component (D) in an amount corresponding to 0.02 parts (20 mg) of platinum.

[Comparative Example 1]

The component (B) was omitted in Example 1, and 1 part of the linear organohydrogenpolysiloxane (C-1) (SiH content = 1.5 mol / 100 g) of Example 1 as the component (C) (E) was dissolved in 959 parts of toluene (E-1), and the amount of the hydrogen atoms directly connected was maintained at 1.3 times as much as the total number of moles of the unsaturated groups contained in the components (A) And 959 parts of 2-butanone (E-2).

<Evaluation>

[Curability]

The obtained composition (exfoliating agent) was applied to a PE laminate paper having a thickness of 100 占 퐉 by a # 14 bar coater and heated in a hot air dryer at 120 占 폚 for 1 minute to form a exfoliating agent layer. The composition of Example 12 was coated using an IR tester and dried at 120 캜 for 30 seconds to form a release agent layer. The transfer amount was adjusted so that the coating amount became 0.8 g / m ² as a solid content. The peeling agent layer was rubbed with the fingers 10 times, and the presence or absence of blurring and peeling was visually observed and evaluated according to the following criteria.

A: I did not see cloudiness and dropouts.

B: Blurred or missing.

[Adhesion]

The obtained composition (exfoliating agent) was applied to a PET film having a thickness of 38 탆 by a # 5 bar coater and heated in a hot air dryer at 120 캜 for one minute to form a release agent layer. The composition of Example 12 was coated using an IR tester and dried at 120 캜 for 30 seconds to form a release agent layer. The transfer amount was adjusted so that the coating amount was 0.2 g / m ² as a solid content. The release agent layer was stored at 25 DEG C and 50% RH for one week or at 60 DEG C and 90% RH for one week. The peeling agent layer was rubbed with the fingers 10 times, and the presence or absence of blurring and peeling was visually observed and evaluated according to the following criteria.

A: No cloudiness or dropout was observed even after one week at 60 占 폚 and 90% RH.

B: Blurred and dropped off at 60 ° C and 90% RH after one week, but no blurring or dropout was observed at 25 ° C and 50% RH for one week.

C: Blurred or missing at 25 ° C, 50% RH for one week.

[Peel strength]

A polyester adhesive tape (NITTO 31B, trade name, manufactured by Nitto Denko Corporation) having a width of 50 mm was loaded on the surface of the release agent layer in the same manner as in the evaluation of the curability, and then a load of 1,976 Pa was loaded on the adhesive tape Followed by heat treatment at 70 캜 for 20 hours to bond a polyester adhesive tape to the release agent layer. Then, a polyester adhesive tape was peeled from the release agent layer at an angle of 180 DEG (peeling rate: 0.3 m / min) using a tensile tester, and the peel force was measured.

[Residual Adhesion Rate]

A polyester adhesive tape was bonded to the release agent layer in the same manner as in the measurement of the peeling force. Thereafter, the polyester adhesive tape was peeled from the release agent layer, and the polyester adhesive tape was attached to the stainless steel plate. Subsequently, the polyester adhesive tape was peeled from the stainless steel plate using a tensile tester, and the peel force X was measured.

Further, a polyester adhesive tape was bonded to a tetrafluoroethylene plate in the same manner as the release agent layer, and the peel force Y measured was measured.

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

The higher the residual adhesion rate, the better the peeling property of the peeling agent layer and the lowering of the adhesive strength of the polyester adhesive tape by bonding to the peeling agent layer is suppressed.

[My Exposure Castle]

The release agent layer was formed in the same manner as in the evaluation of the curability, and left standing at 25 ° C and 50% RH for 8 hours and one day at room temperature with the release agent layer in the room. The releasing agent layer was treated in the same manner as the peeling force described above to measure the peeling force after atmospheric exposure.

Claims (10)

(A) 100 parts by mass of an organopolysiloxane represented by the following formula (1) and having at least two alkenyl groups in one molecule,

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

A group represented by, X ⁴ are each independently formula: (3-1), X ⁵ has the formula (3-2) to each independently, X ⁶ is a chemical formula (3-3) to each independently

Group and, R ^1, R ² are as defined above represented by, a1, a2, a11, a21 , a31, a41, a51, a61 are each independently from 0 to 3 constant, a3 is a positive number, a4 to a6, a2 to a15, a22 to a25, a32 to a35, a42, a43, a52, a53, a62 and a63 are 0 or a positive number, and they have a viscosity at 25 deg. C of the organopolysiloxane of not less than 0.05 Pa · s and not more than 30 mass% The viscosity is selected to be in a range of 70 Pa · s or less)
(B) an alkene having 8 to 30 carbon atoms and having an unsaturated bond at the end represented by the following formula (4), an alkadiene having 10 to 32 carbon atoms and having an unsaturated bond at both terminals, represented by the following formula (5) Silane having 1 to 4 alkenyl groups having 8 to 30 carbon atoms and unsaturated bonds at the terminals represented by the following formula (6), and alkenyl groups having 8 to 30 carbon atoms having an unsaturated bond at the terminal represented by the following formula (7) 5 to 20 parts by mass of at least one compound selected from disiloxanes having 6 to 6 carbon atoms,

(Wherein R ³ is independently a divalent hydrocarbon group having 6 to 28 carbon atoms, R ⁴ is independently a monovalent hydrocarbon group or hydrocarbon oxy group having 1 to 10 carbon atoms, b 1 is an integer of 1 to 4, b 2 Is independently an integer of 1 to 3)
(C) an organohydrogenpolysiloxane represented by the following average composition formula (8) and having a hydrogen atom bonded to at least two silicon atoms in one molecule: the number of moles of hydrogen atoms bonded to silicon atoms in the component (C) And the component (B) is 1 to 20 times the total number of moles of the alkenyl group and the unsaturated group,

(In the formula, R ² is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, c 1 is a positive number of 0.1 to 2, c 2 is a positive number of 0.01 to 2, c 1 + c2 is a positive number of 3 or less and has at least two SiH groups in one molecule and the viscosity at 25 DEG C is selected to fall within the range of 0.005 to 10 Pa · s)
(D) a catalytic amount of a platinum group metal catalyst,
(E) Organic solvent: 0 to 100,000 parts by mass
Wherein the silicone rubber is a silicone rubber. The silicone composition for a release or release film according to claim 1, wherein component (C) is an organohydrogenpolysiloxane represented by the following chemical formula (9) and / or chemical formula (10)

(Wherein, in the formula, Me is a methyl group, R ² is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ⁵ is each independently a hydrogen atom or an aliphatic unsaturated bond And R ⁶ and R ⁷ each independently represent an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group other than Me which contains no aliphatic unsaturated bond, hydrocarbon group, Y ³ is the formula are each independently (11-1), Y ⁴ are each independently formula to (11-2), Y ⁵ is the following formula (11-3) are each independently

A group represented by, general formula Y ⁶ are each independently to (12-1), Y ⁷ of the formula (12-2) to each independently, Y ⁸ has the formula (12-3) to each independently

A group represented by, R ^5, R ^6, R ⁷ are as described above, c11, c12, c31, c41, c51, c61, c71, c81 are each independently from 0 to 3 integers, c23 is an integer of 2 or greater, c23 + c24 + c25 + c26 + c27 + c28 + c29 wherein c13 to c19, c24 to c29, c32 to c38, c42 to c48, c52 to c58, c62 to c66, c72 to c76, 3 or more, hydrogen atoms bonded to two or more silicon atoms in one molecule, and a viscosity at 25 캜 is selected to fall within a range of 0.005 to 10 Pa · s) According to claim 1 or claim 2, (C) component is R ² ₂ HSiO _1/2 units (R ² is an unsubstituted or a halogen atom or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds), the Wherein the organohydrogenpolysiloxane is an organohydrogenpolysiloxane having at least two or more organohydrogenpolysiloxanes in one molecule, or a mixture containing a part of the organohydrogenpolysiloxane. The composition according to claim 1 or 2, wherein the component (C) is a mixture of an organohydrogenpolysiloxane containing no (C1) aromatic substituent and an organohydrogenpolysiloxane containing (C2) ) And the mass ratio (C1) / (C2) of the component (C2) is 1/9 to 9/1. A release or release film according to any one of claims 1 to 3, further comprising 0.1 to 30 parts by mass of an organopolysiloxane represented by the following formula (13) as a component (F) based on 100 parts by mass of the component (A) Silicone composition.

(Wherein, in the formula, Me is a methyl group, R ⁸ is independently a hydroxyl group, an alkoxy group or an alkoxyalkyl group, and R ⁹ is independently an unsubstituted or halogen atom which does not contain a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, And R ¹⁰ is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group other than Me, which does not contain a hydroxyl group, an alkoxy group, an alkoxyalkyl group and an aliphatic unsaturated bond, f1, f2 is an integer of 1 to 3, and f3 to f5 are integers selected so that the viscosity of the organopolysiloxane at 25 DEG C is in a range of 1 Pa · s to 30 Pa0% toluene diluted viscosity of 100 Pa · s or less) Article according to any one of the preceding claims, having at least two alkenyl groups as component (G), R ² _{(3-g1) g1} R ¹ SiO _1/2 siloxane units (M unit ^R1R2), R ² SiO _{3 /} of ₂ siloxane units (T ^R2 units) (the formula, R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen atoms that do not contain an aliphatic unsaturated bond or cyano group-substituted monovalent hydrocarbon group, g1 Has a molar ratio of M ^{R1R 2} units / T ^R 2 of from 2/8 to 8/2 and a viscosity at 25 ° C of from 0.001 to 1 Pa · s, Further comprising 10 to 100 parts by mass of 100 parts by mass of the component (A), wherein the molecular end is an M ^R1R2 unit or an M ^R1R2 unit and an organopolysiloxane partially containing a silanol group or an alkoxy group. The positive resist composition according to claim 1 or 2, wherein the organosilane represented by the following formula (14) having at least an epoxy group and an alkoxysilyl group in one molecule and / or an organosilane represented by the following average composition formula (15) Wherein the silicone composition further contains 0.1 to 10 parts by mass of a hydrolyzed (co) condensation siloxane based on 100 parts by mass of the component (A).

(A monovalent organic group containing a formula of, R ¹¹ is an epoxy group, R ¹² is an alkyl group having 1 to 6 carbon atoms, may contain an ether bond, some of which may be a hydrolyzed hydroxyl group, R ¹³ is H1 and h2 are integers and satisfy 1? H1, 1? H2, 2? H1 + h2? 4, h3 to h5 are positive numbers, 0 <h3 (Positive) condensation siloxane having a viscosity of from 0.001 to 1 Pa · s at 25 ° C, and 0 <h4, 0≤h5 and 1 <h3 + h4 + h5≤3, Selected) The positive resist composition according to claim 1 or 2, wherein the siloxane unit (M unit) represented by the following formula (16) and the siloxane unit (Q unit) represented by the following formula (17) Q unit) of 2/8 to 8/2 in an amount of 1 to 100 parts by mass based on 100 parts by mass of the component (A).

(Wherein R ¹ is independently an alkenyl group, R ² is independently an unsubstituted or halogen or cyano group-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and i 1 is an integer of 0 to 3) The silicone composition for a release or release film according to claim 1 or 2, further comprising 0.1 to 5 parts by mass of a nonionic surfactant as a component (J) based on 100 parts by mass of the component (A). A release or release film on which a cured film of a silicone composition for a release paper or a release film according to any one of claims 1 to 3 is formed.