CN1590489A - Mold release agent composition for polyorganosiloxane adhesive and mold release plate using the composition - Google Patents

Abstract

An object of the present invention is to provide a silicone release agent that can be easily released without using a fluorine-based release agent or a fluorine-based solvent, and a release sheet coated with the release agent. The release agent composition for polysiloxane adhesives of the present invention contains (A) at least 2 alkenyl groups and at least 1 fluoroalkyl group in 1 molecule, and the content of the alkenyl group is 0.02- 0.20mol/100g, the content of fluoroalkyl group is 0.05～0.50mol/100g, the viscosity at 25 ℃ is 100 weights of fluoroalkyl modified polydimethylsiloxane of 50～100,000MPa·s; (B) Polyorganohydrogensiloxane having at least 3 hydrogen atoms bonded to silicon atoms in one molecule, the content of which is such that the number of moles of hydrogen atoms bonded to silicon atoms corresponds to 0.5 of the alkenyl group in component (A) ～5 times molar parts by weight; (C) catalyst amount of platinum group compound; (D) 0.01～10 parts by weight of reaction control agent.

Description

Release agent composition for polysiloxane adhesive and release sheet using same

technical field

The present invention relates to an addition-curable polysiloxane composition in which a base polymer containing siloxane units having fluorinated alkyl. The present invention also relates to a release agent for polysiloxane adhesives, characterized in that the base polymer used is blended with polymers having a high ethylene value and a low ethylene value, so that the peeling force is light and stable over time.

Background technique

A method of producing a material exhibiting releasability to adhesive substances such as pressure-sensitive adhesives by forming a releasable cured film on the surface of various substrates such as paper, plastic film, and synthetic fiber cloth has been known. As a material for forming such a peelable cured film, polysiloxane compositions are often used. For example, in Patent Documents 1 and 2, polyorganosiloxanes and polyorganohydrogensiloxanes containing alkenyl groups and polyorganohydrogensiloxanes are proposed. Polysiloxane composition composed of platinum compounds.

In addition, adhesive tapes and adhesive labels using polysiloxane adhesives have the following characteristics because of the heat resistance, cold resistance, weather resistance, electrical insulation, and chemical resistance of the polysiloxane adhesive layer. Excellent performance, can be used in severe environments where acrylic adhesives, rubber adhesives, urethane adhesives, epoxy adhesives, etc. deteriorate or deteriorate. In addition, since it adheres to the surface of polysiloxane-based materials, it is also suitable for articles treated with polysiloxane for waterproofing, mold release, etc., as well as polysiloxane-based release paper and polysiloxane rubber. bonding.

When producing adhesive tapes and the like using polysiloxane adhesives, the polysiloxane adhesives are applied to substrates such as plastic films, and then undergo a crosslinking reaction to improve adhesive properties and then cured. The use of this adhesive tape can be listed as follows: heat-resistant adhesive tapes made by coating polysiloxane adhesives on heat-resistant substrates, heat-resistant masking tapes, chemical-resistant Masking tape, electrical insulating tape, adhesive tape of polyorganosiloxane release paper, etc.

However, in order to protect the adhesive surface of an adhesive tape coated with a silicone adhesive, since a release film or release paper coated with a silicone-based release agent commonly used to protect bonded processed products has a strong Therefore, the release film or release paper coated with a fluorine-based release agent and a fluororesin sheet are bonded together (for example, refer to Patent Document 3).

Typical release agents conventionally used for silicone adhesives include fluoropolymer-based release agents. It has excellent curability (curability), but it must use a fluorine-based solvent, so there are problems in terms of cost and environment. This has become a major obstacle to the widespread use of polysiloxane adhesives as industrial raw materials. In addition, other non-polysiloxane-based release agents may also be used, but they are not satisfactory in terms of cost and performance.

In addition, in order to coat a fluorine-based polymer-based release agent on a substrate, a fluorine-containing organic solvent is generally used. This is due to the inability to dissolve fluoropolymers with non-fluorine-containing organic solvents. When fluorine-containing organic solvents leak into the atmosphere and other environments, they will affect the destruction of the ozone layer. Due to the high volatility, it is difficult to recover the solvent from the coating equipment.

In order to solve these problems, it is proposed that a phenyl group-containing polysiloxane adhesive and an addition reaction type polysiloxane release agent be combined so that it can be peeled off (for example, refer to Patent Document 4), but there are Problems such as increased peeling force over time.

[Patent Document 1] Special Publication No. 49-26798

[Patent Document 2] JP-A No. 62-86061

[Patent Document 3] JP-A-64-74268

[Patent Document 4] Japanese Unexamined Patent Publication No. 10-147758

Contents of the invention

An object of the present invention is to provide a silicone release agent that can be easily released without using a fluorine-based release agent or a fluorine-based solvent, and a release sheet coated with the release agent.

The present inventors conducted careful research and found that, with at least 2 alkenyl groups and at least 1 fluoroalkyl group in one molecule, and the content of alkenyl group is 0.02-0.20mol/100g, the fluoroalkyl group Curing of addition-curable polysiloxane compositions based on fluoroalkyl-modified polydimethylsiloxane with a content of 0.05 to 0.50 mol/100g and a viscosity of 50 to 100,000 mPa·s at 25°C Even without a fluorine-based release agent, the residual adhesion rate can be high, and it can be easily peeled off, thus completing the present invention.

That is, the present inventors have found that a cured product of a release agent composition for polysiloxane adhesives containing the following components can have a high residual adhesion rate, can be easily peeled off, and has a durable When stable peeling property, thus complete the present invention:

(A) There are at least 2 alkenyl groups and at least 1 fluoroalkyl group in one molecule, and the content of alkenyl groups is 0.02-0.20 mol/100g, and the content of fluoroalkyl groups is 0.05-0.50 mol/100g 100 parts by weight of fluoroalkyl-modified polydimethylsiloxane with a viscosity of 50 to 100,000 mPa·s at 25°C;

(B) Polyorganohydrogensiloxane having at least 3 hydrogen atoms (hereinafter represented by SiH) bonded to silicon atoms in one molecule, the content of which is such that the number of moles of hydrogen atoms bonded to silicon atoms is equivalent to ( A) parts by weight of 0.5 to 5 times the mole of the alkenyl group in the component;

(C) platinum group compound of catalytic amount;

(D) 0.01 to 10 parts by weight of a reaction control agent;

(E) Any amount of organic solvent.

Therefore, the present invention provides a silicone release agent containing the above-mentioned components (A) to (E), and a release sheet obtained by applying and curing the release agent.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in more detail below. The fluoroalkyl-modified polydimethylsiloxane as component (A) used in the present invention has at least two alkenyl groups in one molecule and at least one fluoroalkyl group in one molecule , the content of alkenyl group is 0.02-0.20mol/100g, the content of fluoroalkyl group is 0.05-0.50mol/100g, and the viscosity at 25°C is 50-100,000mPa·s.

As the structure of the fluoroalkyl-modified polydimethylsiloxane of the (A) component, for example, a structure represented by the following general formula (1):

【Chemical 2】

(wherein, R ¹ represents alkenyl or a monovalent hydrocarbon group other than alkenyl, R ² represents a monovalent fluoroalkyl group. In addition, q, r, s are positive numbers, t, u are 0 or positive number).

In the above formula (1), examples of ^R1 include alkenyl groups having 2 to 8 carbon atoms such as vinyl, allyl, butenyl, and pentenyl, among which vinyl is preferred industrially. Monovalent hydrocarbon groups other than alkenyl groups are not particularly limited. Specific examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, and butyl, and cycloalkyl groups such as cyclopentyl and cyclohexyl. Monovalent hydrocarbon groups having 1 to 12, especially 1 to 8, carbon atoms such as aryl groups such as phenyl and naphthyl.

As the fluoroalkyl group of R ² , in an alkyl group having 8 or less carbon atoms, some or all of the hydrogen atoms are substituted by fluorine, such as CF ₃ group, CF ₃ CH ₂ CH ₂ group , C ₄ F ₉ CH ₂ CH ₂ group, C ₈ F ₁₇ CH ₂ CH ₂ group, etc. Industrially, a CF ₃ CH ₂ CH ₂ group is preferred.

q, r, s, t, u can be appropriately selected so that the viscosity of the fluoroalkyl-modified polydimethylsiloxane at 25°C is 50-100,000 mPa·s, preferably 100-50,000 mPa·s, When the value is less than 50 mPa·s, defects such as repelling are likely to occur during coating, and when it is greater than 100,000 mPa·s, the coatability of the composition decreases and cannot be practically used.

Specific examples of (A) component fluoroalkyl-modified polydimethylsiloxane include compounds represented by the following formula:

【Chemical 3】

【Chemical 4】

In the fluoroalkyl-modified polydimethylsiloxane as the component (A), the content of the alkenyl group is preferably 0.02 to 0.20 mol/100 g, more preferably 0.03 to 0.15 mol/100 g. In the fluoroalkyl-modified polydimethylsiloxane, when the alkenyl group content is about 0.02 mol/100 g or less, the degree of crosslinking may be insufficient and curing may be poor, which is not preferable. When the content of the alkenyl group is about 0.20 mol/100 g or more, the peeling property of the cured product may be impaired, which is not preferable.

In the fluoroalkyl-modified polydimethylsiloxane of the component (A), the content of the fluoroalkyl group is preferably 0.05 to 0.50 mol/100 g, more preferably 0.05 to 0.30 mol/100 g. In the fluoroalkyl-modified polydimethylsiloxane, when the content of the fluoroalkyl group is 0.05mol/100g or less, the peeling characteristics with the polysiloxane adhesive will be reduced, which is not ideal. When the content of the alkyl group is 0.50 mol/100 g or more, the solubility in hydrocarbon solvents decreases, which is also disadvantageous in terms of cost, which is not preferable.

Among the components (A), the above-mentioned fluoroalkyl-modified polydimethylsiloxanes may be used alone or in combination of two or more.

(A) Component fluoroalkyl-modified polydimethylsiloxane More preferably fluoroalkyl-modified polydimethylsiloxane (A-1) and fluoroalkyl-modified polydimethylsiloxane Alkane (A-2) is a mixture of about 20:80 to 80:20, preferably 40:60 to 60:40 by weight. The fluoroalkyl-modified polydimethylsiloxane (A-1) contains 0.1-2.0 mol% of siloxane units with alkenyl groups in one molecule, more preferably 0.2-1.0 mol%; The fluoroalkyl-modified polydimethylsiloxane (A-2) contains 4.0 to 15.0 mol % of siloxane units having an alkenyl group, more preferably 5.0 to 12.0 mol %.

(A) The alkenyl group content and the fluoroalkyl group content in the component, when using one kind of fluoroalkyl-modified polydimethylsiloxane alone, or as mentioned above, one molecule contains Fluoroalkyl-modified polydimethylsiloxane (A-1) containing 0.1 to 2.0 mol% of alkenyl siloxane units and fluorinated polydimethylsiloxane containing 4.0 to 15.0 mol% of alkenyl siloxane units When two types of alkyl-modified polydimethylsiloxane (A-2) are used in combination at a weight ratio of about 20:80 to 80:20, the average alkenyl content is 0.01 to 0.20 mol/100g, and the fluorine The average content of the substituted alkyl group is 0.05-0.50 mol/100g, which is necessary.

The polyorganohydrogensiloxane having at least 3 SiH in one molecule as the component (B) of the present invention is not particularly limited, and any molecular structure may be linear, branched or cyclic. .

(B) component polyorganohydrogensiloxane functions as a crosslinking agent, which cures the composition by hydrosilylation reaction with (A) component fluoroalkyl-modified polydimethylsiloxane, and is the following Compounds having at least 3 SiH bonds in one molecule represented by the average composition formula (2):

R ³ _x H _y SiO _(4-xy)/2 (2) (wherein, R ³ is a monovalent saturated hydrocarbon group, at least 80% or more of which is methyl, and x and y satisfy 0.7≤x≤2.1, 0.001≤y≤1.0, and 0.8≤x+y≤2.6, preferably a positive number of 0.8≤x≤2, 0.01≤y≤1, 1≤x+y≤2.4).

Here ^R3 is a monovalent saturated hydrocarbon group, preferably an alkyl group. In addition, it is preferable that at least 80% or more are methyl groups.

Examples of the above-mentioned polyorganohydrogensiloxane include 1,3,5,7-tetramethylcyclotetrasiloxane, polymethylhydrogensiloxane whose both terminals are terminated with trimethylsiloxy groups, Copolymer of dimethylsiloxane and methylhydrogensiloxane endcapped with trimethylsiloxy groups, polydimethylsiloxane endcapped with dimethylhydrogensiloxy groups at both ends, polydimethylsiloxane at both ends Polydimethylsiloxane-methylhydrogensiloxane copolymer terminated with dimethylhydrogensiloxy, methylhydrogensiloxane-biphenyl terminated with trimethylsiloxy at both ends Siloxane copolymer, methylhydrogensiloxane·diphenylsiloxane·dimethylsiloxane copolymer terminated with trimethylsiloxy groups at both ends, (CH ₃ ) ₂ HSiO _1/2 Copolymers composed of units and SiO _4/2 units, copolymers composed of (CH ₃ ) ₂ HSiO _1/2 units, SiO _41/2 units, and (C ₆ H ₅ ) SiO _3/2 units, etc.

The molecular structure of the polyorganohydrogensiloxane can be any of linear, cyclic, branched, and three-dimensional network structures, and the number of silicon atoms (or degree of polymerization) in one molecule can be 4-4. 1000, especially polyorganohydrogensiloxane around 4-300.

In addition, the viscosity of the polyorganohydrogensiloxane at 25°C may range from several mPa·s to tens of thousands of mPa·s, but is preferably 1000 mPa·s or less, more preferably 1 to 400 mPa·s.

As specific examples of polyorganohydrogensiloxanes, the following polyorganosiloxanes can be cited:

【Chemical 5】

In the formula, Me is a methyl group, Y and Z are groups represented by the following structural formula, and a to p are positive integers in the range shown below. a, g are 3~500, i, l are 1~500, b, c, d, h, j, k, m, n, o, p are 0~500, e are 3~8, f are 0~ 8, and 3≤e+f≤8.

【Chemical 6】

The blending amount of the polyorganohydrogensiloxane of the above-mentioned component (B) is such that the number of moles of SiH contained therein corresponds to 0.5 to 5 times the total number of moles of alkenyl groups contained in the component (A), preferably 0.7 to 5 times. 2 times the amount. When the number of moles of SiH contained in component (B) is less than 0.5 times the total number of moles of alkenyl groups contained in component (A), the curability of the polysiloxane composition for release paper of the present invention is insufficient , On the other hand, even if it is blended 5 times or more, the effect is not significantly increased, but it becomes the cause of the change in peelability over time. The compounding weight part of polyorganohydrogensiloxane is generally 0.1-20 weight part with respect to 100 weight part of polyorganosiloxane of (A) component, Preferably it is 0.5-10 weight part.

The platinum group compound which is (C)component used for the composition of this invention is for promoting the so-called addition reaction of (A) component and (B)component, and to form a cured film. Examples of the catalyst for the addition reaction include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol complex, rhodium, rhodium-olefin complex, and the like. The catalyst for the addition reaction is mixed in a metal amount of 5 to 1000 ppm (weight ratio) with respect to the total weight of the polyorganosiloxane as the component (A) and the polyorganohydrogensiloxane as the component (B). It is preferable to form a sufficient cured film, but it can be appropriately increased or decreased according to the reactivity of the above-mentioned components or the desired curing speed.

As (D)component of this invention composition, what is known as the said reaction control agent can be used. For example, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, Alkyne alcohols such as phenylbutynol, acetylenic compounds such as 3-methyl-3-1-penten-1-yne, 3,5-dimethyl-1-hexyne-3-yne, etc. Compounds and reactants of alkoxysilane or siloxane or hydrosilane or siloxane, vinyl siloxanes such as tetramethylvinylsiloxane rings, organic nitrogen compounds such as benzotriazole and other organic Phosphorus compounds, oxime compounds, organic chromium compounds, etc.

(D) The compounding quantity of a component should just be the quantity which can obtain favorable process bath stability, Generally, 0.01-10 weight part is used with respect to 100 weight part of (A) components, Preferably it is 0.05-5 weight part.

In the composition of the present invention, the organic solvent (E) component as an optional component can be used for improving the storage stability of the treatment bath, the coatability to various substrates, and the adjustment of the coating amount and the viscosity of the treatment bath. As such (E) component, the organic solvent which can melt|dissolve the composition of this invention uniformly, such as toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, and hexane, can be used, for example. Depending on other selected composition components and coating methods, it may not be used.

The composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components (A), (B), (C) and, if necessary, (E). When mixing, it is advantageous to mix (C) component after uniformly dissolving (A), (B), and (D) components in (E) component. In addition, in order to secure a sufficient effective life, (C) component should be added and mixed before manufacturing release paper etc.

In the composition of the present invention, an inorganic filler such as silica or a pigment may be further compounded as necessary.

When using the composition of the present invention to manufacture release paper, etc., the composition of the present invention can be directly or diluted with an appropriate organic solvent, and then the composition can be coated with a bar coater, roll coater, or reverse coater (リバスココ).タ1), gravure roll coater (ゲラビアアタタ), air knife coater (エアナイイフコタタ), and high-precision offset coater (Ofsetto Coater) used in film coating , Multi-stage roll coater and other known coating methods, and coated on substrates such as paper.

The coating amount of the composition of the present invention on the substrate also varies depending on the material of the substrate to be coated, but the amount as a solid content is preferably in the range of 0.1 to 2.0 g/m ² . The substrate coated with the above-mentioned composition of the present invention is heated at 80-180° C. for about 5 to 60 seconds, thereby forming a cured film on the surface of the composition, thereby obtaining a product having desired peeling force and residual adhesive force. Peel off the sheet.

Example

Examples and comparative examples are given below to specifically illustrate the present invention, but the present invention is not limited by the following examples. Also, "parts" in the following examples mean "parts by weight". In addition, the evaluation methods used in the following examples are as follows.

A. Evaluation of Polysiloxane Composition and Cured Film Properties

The evaluation results are shown in Table 1. The evaluation of each item and the presentation of the results were performed in the following manner.

1) Curability

Coat the polysiloxane composition added with the catalyst on polyethylene laminated paper (meter weight 100g/m ² ), make the solid content reach 0.2g/m ² , heat treatment with 100°C hot air circulation dryer for 30 Seconds, a cured film is formed, and a curability measurement sample is made. Wipe the surface of the cured film of the sample with your fingers, observe whether the surface is blurred or peeled off, and evaluate according to the following standards.

◎: Heated at 100°C for 15 seconds, no blurring or peeling off at all

○: Heated at 100°C for 30 seconds, no blurring or peeling off at all

△: Slightly blurred and falling off

×: Blurring and peeling occurred

2) Peel force

Coat the polysiloxane composition added with the catalyst on polyethylene laminated paper (meter weight 100g/m ² ), make the solid content reach 0.2g/m ² , heat treatment with 140°C hot air circulation dryer for 30 Seconds, a cured film is formed. Apply polysiloxane adhesive [KR-3700 (manufactured by Shin-Etsu Chemical Co., Ltd.)] on the surface of the cured film using a feeder (Apuri Keta) to make a polyester film with a thickness of 25 μm and a width of 25 mm The thickness after curing on the substrate reaches 30 μm, and heat treatment at 130° C. for 1 minute after coating. Then, paste the above-mentioned peeling characteristic evaluation sample on the treated surface, press and bond once with a 2kg roller back and forth, and age (Ejing) at 25°C for 20 hours, use a tensile tester at an angle of 180°, 0.3 The bonded paper was stretched at a peeling speed of m/min, and the force (N) required for peeling was measured. In addition, after aging at 50°C for 7 days after pasting, the pasted paper was stretched with a tensile tester at an angle of 180° and a peeling speed of 0.3 m/min, and the force (N) required for peeling was measured.

3) Residual adhesion rate

The adhesive sheet after the peel force measurement was pasted on the stainless steel plate, and a rubber-coated roller weighing 2 kg was used to reciprocate once to perform pressure bonding. After standing at room temperature for about 3 hours, use a tensile tester to peel off the adhesive sheet from the stainless steel plate at a speed of 300mm/min at an angle of 180°, and measure the required force (N/25mm). The adhesive sheet was pasted on a polytetrafluoroethylene sheet, and the ratio of the adhesive force after standing at room temperature for about 3 hours to the above force was taken as the residual adhesive ratio.

Example 1

With 100 parts of fluoroalkyl-modified polydimethylsiloxane represented by the following formula as component (A) and label 1 in Table 1, as component (B), use trimethylsilane at both ends of the molecular chain 23 parts of group-terminated polymethylhydrogensiloxane containing 95 mol % of units represented by MeHSiO _2/2 and having a viscosity of 25 mPa·s, and 3-methyl-1-butyne-3 as component (D) - 2 parts of alcohol, diluted with 900 parts of a mixture of toluene and heptane (1:1 by weight). Before coating on the substrate, a complex salt of platinum and vinylsiloxane as the component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The composition was treated under the aforementioned conditions, and the results are shown in Table 2.

Example 2

50 parts of the fluoroalkyl-modified polydimethylsiloxane represented by the following formula and the label 2-1 in Table 1 as the component (A), the fluoroalkane represented by the following formula and the label 2-2 in Table 1 50 parts of radical-modified polydimethylsiloxane, as (B) component, both ends of the molecular chain are terminated with trimethylsilyl groups, containing 95 mol% of units represented by MeHSiO _2/2 , and having a viscosity of 25 mPa 4 parts of polymethylhydrogensiloxane of s; 2 parts of 3-methyl-1-butyn-3-alcohol as (D) component, with toluene and heptane (by weight) as (E) component 1:1) of the mixture was diluted to 900 parts. Before coating on the substrate, a complex salt of platinum and vinylsiloxane as the component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The composition was treated under the aforementioned conditions, and the results are shown in Table 2.

Example 3

With 100 parts of fluoroalkyl-modified polydimethylsiloxane represented by the following formula and number 3 in Table 1 as component (A), as component (B), use trimethylsilane at both ends of the molecular chain 23 parts of group-terminated polymethylhydrogensiloxane containing 95 mol % of units represented by MeHSiO _2/2 and having a viscosity of 25 mPa·s, 3-methyl-1-butyne-3 as component (D) - 2 parts of alcohol, diluted with 900 parts of a mixture of toluene and heptane (1:1 by weight). Before coating on the substrate, a complex salt of platinum and vinylsiloxane as the component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. Table 2 shows the results of treating the composition under the aforementioned conditions.

Example 4

25 parts of the fluoroalkyl modified polydimethylsiloxane represented by the following formula and the label 4-1 in Table 1 as the (A) component, the fluoroalkane represented by the following formula and the label 4-2 in Table 1 75 parts of radical-modified polydimethylsiloxane, which is (B) component, whose molecular chain ends are terminated with trimethylsilyl groups, contains 95 mol% of units represented by MeHSiO _2/2 , and has a viscosity of 25 mPa 7 parts of polymethylhydrogensiloxane of s, 2 parts of 3-methyl-1-butyn-3-alcohol as (D) component, with toluene and heptane (by weight) as (E) component 1:1) of the mixture was diluted to 900 parts. Before coating on the substrate, a complex salt of platinum and vinylsiloxane as the component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The composition was treated under the aforementioned conditions, and the results are shown in Table 2.

Comparative example 1

A 1% toluene solution of a long-chain alkyl side chain (Pendant) type polymer, Pilroil 1010 (manufactured by Kabashisha Oil Industry Co., Ltd., trade name) was coated on the substrate to a concentration of 0.1 g/m ² , Dry at 120°C for 30 seconds. Table 2 shows the results of treating this substrate in the same manner as in the above-mentioned examples.

Comparative example 2

With 100 parts of phenyl-modified polydimethylsiloxane represented by the following formula and the label 5 in Table 1 as the (A) component, as the (B) component, the two ends of the molecular chain are sealed with trimethylsilyl groups. 4 parts of terminal polymethylhydrogensiloxane containing 95 mol % of units represented by MeHSiO _2/2 and having a viscosity of 25 mPa·s, 3-methyl-1-butyn-3-ol as component (D) 2 parts were diluted with 900 parts of a mixture of toluene and heptane (1:1 by weight) as the component (E). Before coating on the substrate, a complex salt of platinum and vinylsiloxane as the component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The composition was treated under the aforementioned conditions, and the results are shown in Table 2.

Comparative example 3

100 parts of the fluoroalkyl-modified polydimethylsiloxane represented by the following formula as the (A) component and the number 6 in Table 1, and as the (B) component, use trimethylsilane at both ends of the molecular chain 2 parts of group-terminated polymethylhydrogensiloxane containing 95 mol % of units represented by MeHSiO _2/2 and having a viscosity of 25 mPa·s, 3-methyl-1-butyne-3 as component (D) - 2 parts of alcohol, diluted with 900 parts of a mixture of toluene and heptane (1:1 by weight). Before coating on the substrate, a complex salt of platinum and vinylsiloxane as the component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The composition was treated under the aforementioned conditions, and the results are shown in Table 2.

Comparative example 4

A 10% FR シンナ-(fluorine solvent) solution of X-70-201 (manufactured by Shin-Etsu Chemical Co., Ltd., product name) was coated on the substrate to reach 0.2 g/m ² . Dry at 150°C for 60 seconds. The results for this substrate are shown in Table 2.

The general formula of the fluoroalkyl modified polydimethylsiloxane used in the embodiment:

【Chemical 7】

The structure of the fluoroalkyl-modified polydimethylsiloxane used in the examples.

Table 1 Structural formula of fluoroalkyl modified dimethylsiloxane Siloxane Molecular Weight Content (mol/100g) Example No. label Q R S T V CH ₂ ＝CH group CF ₃ C ₂ H ₄ group Example 1 1 2 twenty two 9 174 0 16,358 0.13 0.06 Example 2 2-1 2 8 135 755 0 77,804 0.01 0.17 2-2 2 88 135 675 0 78,764 0.11 0.17 Example 3 3 2 6 15 34 0 5,558 0.11 0.27 Example 4 4-1 2 8 135 755 0 77,804 0.01 0.17 4-2 2 43 180 675 0 81,914 0.05 0.22 Comparative example 2 5 2 6 0 34 18 5,666 0.11 0 Comparative example 3 6 2 8 180 710 0 81,494 0.01 0.22

Blending and Properties of Silicone Compositions

Table 2 Coating curability Peel force(N/25mm) Residual adhesion rate (%) 25℃/1 day 50℃/7 days Example 1 ◎ ◎ 3.3 4.5 88 Example 2 ◎ ◎ 0.42 0.69 89 Example 3 ◎ ◎ 0.60 1.53 97 Example 4 ◎ ◎ 0.65 1.20 98 Comparative example 1 x x 9.0 no peeling 71 Comparative example 2 ◎ ○ 10.8 no peeling 88 Comparative example 3 ◎ ◎ 0.18 12.3 97 Comparative example 4 x △ 0.07 0.10 99

Invention effect

The composition of the present invention is coated on paper, laminated paper, plastic film, etc., and cured by heating, and quickly cures to form a cured film having moderate peeling force against various polysiloxane adhesives. The formed cured film exhibits good adhesion to various substrates without reducing the adhesive force of the adhesive. In addition, the storage life and effective life are good, and the workability is also good, and a hydrocarbon solvent can be used. The composition of the present invention can be used better than conventional silicone adhesive compositions by mixing a fluoroalkyl-modified polydimethylsiloxane having a specific structure.

Claims (6)

1. polyorganosiloxane adhesive mold release compositions, wherein contain:

(A) in 1 molecule at least 2 alkenyls and at least 1 fluoro-alkyl are arranged, and the content of alkenyl is 0.02～0.20mol/100g, the content of fluoro-alkyl is 0.05～0.50mol/100g, viscosity in the time of 25 ℃ is 50～100, fluoro-alkyl modified dimethyl polysiloxane 100 weight parts of 000mPas;

(B) in 1 molecule at least 3 poly-organohydrogensiloxanes that are combined in the hydrogen atom on the Siliciumatom are arranged, its content is to make the hydrogen atom mole number that wherein is combined on the Siliciumatom be equivalent to the weight part of 0.5～5 times of mole of alkenyl in (A) composition;

(C) the platinum group type compound of catalytic amount;

(D) reaction control agent 0.01～10 weight part;

(E) organic solvent of any amount.

2. the described polyorganosiloxane adhesive mold release compositions of claim 1, wherein the fluoro-alkyl modified dimethyl polysiloxane as (A) composition is the mixture that fluoro-alkyl modified dimethyl polysiloxane (A-1) and fluoro-alkyl modified dimethyl polysiloxane (A-2) constituted with weight ratio in 20: 80～80: 20, described fluoro-alkyl modified dimethyl polysiloxane (A-1) contains 0.1～2.0 mole of % of siloxane unit with alkenyl in 1 molecule, fluoro-alkyl modified dimethyl polysiloxane (A-2) contains 4.0～15.0 moles of % of siloxane unit with alkenyl.

3. claim 1 or 2 described polyorganosiloxane adhesive mold release compositions wherein, are the compounds of following general formula (1) expression as the fluoro-alkyl modified dimethyl polysiloxane of (A) composition:

(in the formula, R ¹Expression alkenyl or the monovalence alkyl except that alkenyl, R ²Expression univalent fluoro-alkyl, in addition, q, r, s are positive number, t, u be 0 or positive number).

4. the described polyorganosiloxane adhesive mold release compositions of claim 1, wherein, (B) organohydrogensiloxanes of composition is that at least 3 compounds that are combined in the hydrogen atom on the Siliciumatom are arranged in 1 molecule of following general formula (2) expression:

R ³ _xH _ySiO _(4-x-y)/2??????????????????????????????????(2)

(in the formula, R ³For the monovalence alkyl except that alkenyl, more than at least 80% or 80% is methyl, and x, y preferably satisfy the positive number of 0.8≤x≤2,0.01≤y≤1,1≤x+y≤2.4 for satisfying 0.7≤x≤2.1,0.001≤y≤1.0 and 0.8≤x+y≤2.6).

5. the described polyorganosiloxane adhesive mold release compositions of claim 1～3, wherein, (A) fluoro-alkyl of composition fluoro-alkyl modified dimethyl polysiloxane is 3,3, the 3-trifluoro propyl.

6. stripping film, it is with mold release compositions base materials such as paper, plastic film to be handled and the stripping film that obtains with the described polyorganosiloxane adhesive of claim 1～5.