JP2005060554A - Release agent composition for silicone adhesive and release sheet using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone release agent having an easy releasability without using a fluorine-based release agent or a fluorine-based solvent, and a release sheet coated with the same. <P>SOLUTION: The release agent composition for a silicone adhesive comprises the following (A)-(D): (A) 100 pts.wt. fluoroalkyl-modified polydimethyl siloxane having at least two alkenyl groups and at least one fluoroalkyl group in one molecule, 0.02-0.20 mol/100g alkenyl group content, 0.05-0.50 mol/100g fluoroalkyl group content and 50-100,000 mPa×s viscosity at 25°C; (B) a polyorganohydrogensiloxane having at least three hydrogen atoms bonding to silicon atoms in one molecule, wherein the mol number of the hydrogen atoms bonding to the silicon atoms is equivalent to 0.5-5 times mol of the alkenyl group in the component (A) by pts.wt.; (C) a catalytic amount of a platinum group compound; and (D) 0.01-10 pts.wt. reaction controller. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an addition-curable silicone composition in which a base polymer containing a siloxane unit having a fluoroalkyl group is blended as a component for releasing a silicone pressure-sensitive adhesive. Furthermore, the base polymer to be used is for a silicone pressure-sensitive adhesive characterized by light release and a release force with excellent temporal stability by blending a high vinyl value and a low vinyl value. It relates to a release agent.

  It has been known for a long time to obtain a material that exhibits peelability to pressure-sensitive adhesives and other adhesive materials by forming a peelable cured film on the surface of various substrates such as paper, plastic film, and synthetic fiber cloth. Yes. Silicone compositions are frequently used as a material for forming such a peelable cured film. For example, in Patent Documents 1 and 2, a silicone composition comprising an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and a platinum compound. Things have been proposed.

  Also, pressure-sensitive adhesive tapes and pressure-sensitive adhesive labels that use silicone pressure-sensitive adhesives are acrylic pressure-sensitive adhesives and rubber-based pressure-sensitive adhesives because the silicone pressure-sensitive adhesive layer has excellent heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. , Urethane adhesives, epoxy adhesives, etc. can be used in harsh environments where they are altered or deteriorated. Further, since it adheres to the surface of the silicone material, it has a feature that it can be adhered to an article treated with silicone for the purpose of water repellency, mold release, silicone release paper, and silicone rubber.

  In order to produce a pressure-sensitive adhesive tape using a silicone pressure-sensitive adhesive, a silicone pressure-sensitive adhesive is applied to a base material such as a plastic film, and a cross-linking reaction is performed to improve the pressure-sensitive adhesive properties, and then cured. For such adhesive tape applications, heat-resistant adhesive tapes, heat-resistant masking tapes, chemical-resistant masking tapes, electrical insulating tapes, and silicone release papers manufactured by applying a silicone adhesive to a heat-resistant substrate are used. There are splicing tapes for coupling.

  However, in order to protect the adhesive surface of adhesive tape coated with a silicone adhesive, it is strong against release films and release papers coated with a silicone release agent that is commonly used to protect adhesive processed products. Since it would stick, a release film coated with a fluorine-based release agent, release paper, a fluororesin sheet, and the like were bonded together (see, for example, Patent Document 3).

  Conventionally, as a typical release agent used for a silicone adhesive, there is one based on a fluorine-based polymer. This is excellent in characteristics, but has a problem in terms of cost and environment in that the curing property and the solvent to be used must use a fluorinated solvent. Silicone pressure-sensitive adhesives have become a major obstacle for generalization as industrial materials. Other non-silicone release agents may be used, but they are unsatisfactory in terms of cost and characteristics.

  Moreover, in order to apply a fluorine-based polymer-based release agent to a substrate, a fluorine-containing organic solvent is usually used. This is because the fluorine-based polymer cannot be dissolved with the non-fluorine-containing organic solvent. If the fluorine-containing organic solvent leaks into the environment, such as in the atmosphere, it may affect the ozone layer destruction. Due to the high volatility, it is difficult to recover the solvent from the coating apparatus.

  In order to solve these problems, it has been proposed that peeling is possible with a combination of a silicone pressure-sensitive adhesive containing a phenyl group and an addition reaction type silicone release agent (see, for example, Patent Document 4). There were problems such as increased power.

Japanese Patent Publication No.49-26798 JP-A-62-86061 JP-A 64-74268 Japanese Patent Laid-Open No. 10-147758

  An object of this invention is to provide the silicone release agent which can be lightly peeled without using a fluorine-type release agent and a fluorine-type solvent, and the peeling sheet which coated this.

  As a result of intensive studies, the present inventors have at least two alkenyl groups and at least one fluoroalkyl group in one molecule, and the alkenyl group content is 0.02 to 0.20 mol / 100 g. And an addition-curable silicone composition based on a fluoroalkyl-modified polydimethylsiloxane having a fluoroalkyl group content of 0.05 to 0.50 mol / 100 g and a viscosity at 25 ° C. of 50 to 100,000 mPa · s. It was found that the cured product had a high residual adhesion rate and could be lightly peeled without using a fluorine-based release agent, and the present invention was made.

That is, the present invention
(A) It has at least two alkenyl groups and at least one fluoroalkyl group in one molecule, and the alkenyl group content is 0.02 to 0.20 mol / 100 g, and the fluoroalkyl group content is 0. Fluoroalkyl-modified polydimethylsiloxane having a viscosity at 25 ° C. of 0.5 to 0.50 mol / 100 g and a viscosity of 50 to 100,000 mPa · s 100 parts by weight (B) Hydrogen atom bonded to silicon atom in one molecule (hereinafter referred to as SiH A polyorganohydrodienesiloxane having at least three, and the number of moles of hydrogen atoms bonded to silicon atoms is equivalent to 0.5 to 5 moles of the alkenyl group in component (A),
(C) a catalytic amount of a platinum group compound,
(D) 0.01-10 parts by weight of a reaction control agent,
(E) The cured product of the release agent composition for a silicone pressure-sensitive adhesive containing an arbitrary amount of an organic solvent has a high residual adhesion rate and can be easily peeled off with light release and stable over time without using a fluorine-based release agent. As a result, the present invention has been made.

  Accordingly, the present invention provides a silicone release agent comprising the above components (A) to (E) and a release sheet formed by coating and curing the silicone release agent.

  The composition of the present invention is applied to paper, laminated paper, plastic film, and the like and cured by heating to form a cured film having an appropriate peeling force for various silicone pressure-sensitive adhesives. The formed cured film exhibits good adhesion to various substrates without reducing the adhesive strength of the adhesive. In addition, shelf life and pot life are good, workability is excellent, and a hydrocarbon-based solvent can be used. The composition of the present invention can be more preferably used than a conventional composition for a silicone pressure-sensitive adhesive by blending a fluoroalkyl-modified polydimethylsiloxane having a specific structure.

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

  Examples of the structure of the fluoroalkyl-modified polydimethylsiloxane as the component (A) include those represented by the following general formula (1).

（式中、Ｒ^１はアルケニル基又はアルケニル基を除く一価の炭化水素基、Ｒ^２は１価のフロロアルキル基を表す。また、ｑ、ｒ、ｓは正数、ｔ、ｕは０又は正数である。）

(In the formula, R ¹ represents an alkenyl group or a monovalent hydrocarbon group excluding an alkenyl group, R ² represents a monovalent fluoroalkyl group, and q, r, and s are positive numbers, and t and u are 0 or (It is a positive number.)

In the above formula (1), R ¹ may be an alkenyl group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, or a pentenyl group, but is preferably a vinyl group industrially. The monovalent hydrocarbon group excluding the alkenyl group is not particularly limited. Specific examples of the monovalent hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cyclopentyl group, and a cyclohexyl group. And monovalent hydrocarbon groups having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms such as aryl groups such as cycloalkyl groups, phenyl groups and naphthyl groups.

The fluoroalkyl group of R ^{2 is} an alkyl group having up to 8 carbon atoms in which part or all of the hydrogen is substituted with fluorine. For example, 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, and the like. Industrially, a CF ₃ CH ₂ CH ₂ group is preferable.

q, r, s, t, and u are selected so that the viscosity of the fluoroalkyl-modified polydimethylsiloxane at 25 ° C. is 50 to 100,000 mPa · s, preferably 100 to 50,000 mPa · s. If this value is less than 50 mPa · s, repellency is likely to occur when coating, and if it exceeds 100,000 mPa · s, the coating property of the composition is lowered, making it unsuitable for actual use.

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

  The alkenyl group content contained in the fluoroalkyl-modified polydimethylsiloxane as the component (A) is preferably 0.02 to 0.20 mol / 100 g, and more preferably 0.03 to 0.15 mol / 100 g. When the alkenyl content contained in the fluoroalkyl-modified polydimethylsiloxane is about 0.02 mol / 100 g or less, it is not preferable because the degree of crosslinking may be insufficient and a curing failure may occur, and the alkenyl content is about 0. In the case of 20 mol / 100 g or more, the peelability of the cured product may be impaired, which is not preferable.

  The fluoroalkyl content contained in the fluoroalkyl-modified polydimethylsiloxane as the component (A) is preferably 0.05 to 0.50 mol / 100 g, and more preferably 0.05 to 0.30 mol / 100 g. When the fluoroalkyl content contained in the fluoroalkyl-modified polydimethylsiloxane is 0.05 mol / 100 g or less, it is not preferable because the peeling property with the silicone adhesive is lowered, and the fluoroalkyl content is 0.50 mol / 100 g or more. In this case, the solubility in hydrocarbon solvents is lowered, which is disadvantageous in terms of cost.

  As the component (A), the above-described fluoroalkyl-modified polydimethylsiloxane can be used alone or in combination of two or more.

  The fluoroalkyl-modified polydimethylsiloxane as component (A) contains 0.1 to 2.0 mol%, more preferably 0.2 to 1.0 mol%, of a siloxane unit having an alkenyl group in one molecule. Fluoroalkyl-modified polydimethylsiloxane (A-2) containing the modified polydimethylsiloxane (A-1) and siloxane units having an alkenyl group in an amount of 4.0 to 15.0 mol%, more preferably 5.0 to 12.0 mol%. ) In a weight ratio of about 20:80 to 80:20, more preferably 40:60 to 60:40.

  The alkenyl group content and fluoroalkyl group content contained in the component (A) may be a single fluoroalkyl-modified polydimethylsiloxane or a siloxane unit having an alkenyl group in one molecule as described above. Fluoroalkyl-modified polydimethylsiloxane (A-1) containing 0.1 to 2.0 mol% and fluoroalkyl-modified polydimethylsiloxane (A-) containing 4.0 to 15.0 mol% of siloxane units having an alkenyl group Even when 2) is used in combination of two kinds consisting of 20:80 to 80:20 by weight ratio, the alkenyl group content contained is 0.01 to 0.20 mol / 100 g on average, The group content must be 0.05 to 0.50 mol / 100 g on average.

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

The (B) component organohydrogenpolysiloxane acts as a crosslinking agent for curing the composition by hydrosilylation reaction with the (A) component fluoroalkyl-modified polydimethylsiloxane. The following 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 is a methyl group, and x and y are 0.7 ≦ x ≦ 2.1, 0.001 ≦ y ≦ 1.0, And 0.8 ≦ x + y ≦ 2.6, preferably 0.8 ≦ x ≦ 2, 0.01 ≦ y ≦ 1, and 1 ≦ x + y ≦ 2.4. Have at least three SiH bonds.

Here, R ³ is a monovalent saturated hydrocarbon group, preferably an alkyl group. Further, at least 80% or more is preferably a methyl group.

Examples of the organohydrogenpolysiloxane include 1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane and methylhydrogensiloxane copolymer Dimethylpolysiloxane having both ends dimethylhydrogensiloxy group blocked, dimethylsiloxane / methylhydrogensiloxane copolymer having both ends dimethylhydrogensiloxy group, methylhydrogensiloxane / diphenylsiloxane copolymer having both ends trimethylsiloxy group blocked, both end trimethylsiloxy-blocked methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane _copolymer, and _(CH 3) 2 _{HSiO 1/2} units copolymers comprising iO _{4/2 units,} and copolymers consisting of _(CH 3) 2 _{HSiO 1/2} units and _{SiO 4/2} units and _{(C 6} H _{5) SiO 3/2} units .

  The molecular structure of this organohydrogenpolysiloxane may be any of linear, cyclic, branched and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is 4 to 1000. In particular, about 4 to 300 can be used.

  Further, the viscosity of this organohydrogenpolysiloxane at 25 ° C. may be in the range of several mPa · s to tens of thousands mPa · s, preferably 1000 mPa · s or less, more preferably 1 to 400 mPa · s. It is preferable.

  The following organopolysiloxanes can be mentioned as specific examples of the organohydropolysiloxane.

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

  The amount of the organohydrodiene polysiloxane blended as the component (B) is such that the number of moles of SiH contained corresponds to 0.5 to 5 times the total number of moles of alkenyl groups contained in the component (A), preferably May be 0.7 to 2 times the amount. When the SiH mole number contained in the blending amount of the component (B) is less than 0.5 times the total mole number of alkenyl groups contained in the component (A), the curability of the silicone composition for release paper of the present invention is insufficient. On the other hand, even if it is blended 5 times or more, a significant increase in the effect is not seen, but it causes a change in peelability with time. The blending part by weight of a general organohydrodiene polysiloxane is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyorganosiloxane of component (A).

  The platinum group compound as the component (C) used in the composition of the present invention is used for promoting a so-called addition reaction between the component (A) and the component (B) to form a cured film. Examples of the addition reaction catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, rhodium, rhodium-olefin complex, and the like. The addition reaction catalyst may be blended in an amount of 5 to 1000 ppm (weight ratio) with respect to the total weight of the polyorganosiloxane as the component (A) and the organohydropolyene polysiloxane as the component (B). Although it is preferable for forming a sufficient cured film, it can be appropriately increased or decreased depending on the reactivity of the components or the desired curing rate.

  As the component (D) of the composition of the present invention, those known as the reaction control agent can be used. For example, acetylenic alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol, 3 -Acetylene compounds such as methyl-3--1-penten-1-yne and 3,5-dimethyl-1-hexyne-3-yne, and these acetylene compounds and alkoxysilane or siloxane or hydrogensilane or siloxane Examples include reactants, vinylsiloxanes such as tetramethylvinylsiloxane cyclics, organic nitrogen compounds such as benzotriazole, and other organic phosphorus compounds, oxime compounds, and organic chromium compounds.

  Component (D) may be blended in an amount that provides good treatment bath stability, and is generally 0.01 to 10 parts by weight, preferably 0.05 to 5 parts per 100 parts by weight of component (A). Used by weight.

  In the composition of the present invention, as an optional component, the organic solvent (E) is used for the purpose of improving the storage stability of the treatment bath, improving the coating property on various substrates, and adjusting the coating amount and the treatment bath viscosity. Can do. As this (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, hexane, can be used, for example. It may not be used depending on the components of other selected compositions and coating methods.

  The composition of the present invention can be easily produced by uniformly mixing the components (A), (B), (C) and, if necessary, (E). In this mixing, it is advantageous that the components (A), (B), and (D) are uniformly dissolved in the component (E) and then the component (C) is mixed. Moreover, in order to ensure sufficient pot life, the component (C) should be added and mixed immediately before producing release paper or the like.

  If necessary, the composition of the present invention may further contain an inorganic filler such as silica or a pigment.

  When producing a release paper or the like using the composition of the present invention, the composition of the present invention is directly or diluted with an appropriate organic solvent, and then a bar coater, roll coater, reverse coater, gravure coater, air knife coater. Furthermore, the thin film is coated on a substrate such as paper by a known coating method such as a high-precision offset coater or a multi-stage roll coater.

The amount of the composition of the present invention applied to the substrate varies depending on the type of material of the substrate to be coated, but the solid content is preferably in the range of 0.1 to 2.0 g / m ² . The substrate coated with the composition of the present invention as described above is heated at 80 to 180 ° C. for about 5 to about 60 seconds to form a cured film on the surface of the composition. A release sheet having the above can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, a part shows a weight part in the following example. The evaluation methods used in the following examples are as follows.

A. The evaluation results of the silicone composition and cured film properties are shown in Table 1. The evaluation of each item and the display of the results were in accordance with the following method.

1) Curability The catalyst-added silicone composition was applied to polyethylene laminated paper (basis weight 100 g / m ² ) in a solid content of 0.2 g / m ² , and heat-treated for 30 seconds with a 100 ° C. hot air circulating dryer. A cured film was formed to prepare a sample for measuring curability. The surface of the cured film of the sample was rubbed with a finger, and the presence or absence of cloudiness and dropping off of the surface was observed and evaluated according to the following criteria.
(Double-circle): There is no cloudiness and omission at 100 degreeC x 15 second heating.
○: No cloudiness or dropping off when heated at 100 ° C. for 30 seconds.
Δ: Slightly cloudy or falling off occurs.
X: Cloudy and falling off occur.

2) Peeling force The catalyst-added silicone composition was applied to polyethylene laminated paper (basis weight 100 g / m ² ) in a solid form of 0.2 g / m ² and heat-treated for 30 seconds with a 140 ° C. hot air circulating dryer. A cured film was formed. Apply silicone adhesive [KR-3700 (manufactured by Shin-Etsu Chemical Co., Ltd.)] to the surface of the cured film using an applicator so that the thickness after curing is 30 μm on a polyester film substrate having a thickness of 25 μm and a width of 25 mm. Then, it applied and heat-treated at 130 ° C. for 1 minute. Next, the sample for peeling property evaluation was pasted on this treated surface, pressed once with a 2 kg roller, aged at 25 ° C. for 20 hours, and then peeled at an angle of 180 ° using a tensile tester at a rate of 0.3 m. The laminated paper was pulled at a rate of / min and the force (N) required for peeling was measured. Moreover, after aging at 50 ° C. for 7 days after bonding, the force (N) required for pulling and peeling the bonded paper at a peeling speed of 0.3 m / min at an angle of 180 ° using a tensile tester. It was measured.

3) Residual adhesion rate The pressure-sensitive adhesive sheet after measuring the peel force was attached to a stainless steel plate, and pressure-bonded by reciprocating a rubber-coated roller having a weight of 2 kg. After standing at room temperature for about 3 hours, the force (N / 25 mm) required to peel the adhesive sheet from the stainless steel plate at a speed of 300 mm / min and an angle of 180 ° was measured using a tensile tester. The pressure-sensitive adhesive sheet was bonded to a polytetrafluoroethylene sheet and allowed to stand at room temperature for about 3 hours.

Example 1
As component (A), 100 parts of a fluoroalkyl-modified polydimethylsiloxane represented by the following formula and symbol 1 in Table 1, and as component (B), both ends of the molecular chain are blocked with trimethylsilyl groups and represented by MeHSiO _2/2. 23 parts of methylhydropolysiloxane having a viscosity of 25 mPa · s, 2 parts of 3-methyl-1-butyn-3-ol, and toluene and heptane as component (D) The mixture was diluted to 900 parts by weight in a 1: 1 mixture. Immediately before coating on the substrate, a complex salt of platinum and vinylsiloxane as component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The results of treating this composition under the conditions described above are shown in Table 2.

Example 2
As the component (A), 50 parts of a fluoroalkyl-modified polydimethylsiloxane represented by the following formula and symbol 2-1 in Table 1, 50 parts of a fluoroalkyl-modified polydimethylsiloxane represented by symbol 2-2 of the following formula and Table 1, As component (B), 4 parts of methylhydropolysiloxane having both ends of the molecular chain blocked with a trimethylsilyl group and containing 95 mol% of a unit represented by MeHSiO _2/2 and having a viscosity of 25 mPa · s, (D 2) 3-methyl-1-butyn-3-ol as a component was diluted to 900 parts by mixing toluene and heptane at a weight ratio of 1: 1 as component (E). Immediately before coating on the substrate, a complex salt of platinum and vinylsiloxane as component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The results of treating this composition under the conditions described above are shown in Table 2.

Example 3
As component (A), 100 parts of fluoroalkyl-modified polydimethylsiloxane represented by the following formula and symbol 3 in Table 1, and as component (B), both ends of the molecular chain are blocked with a trimethylsilyl group and represented by MeHSiO _2/2. 23 parts of methylhydropolysiloxane having a viscosity of 25 mPa · s, 2 parts of 3-methyl-1-butyn-3-ol, and toluene and heptane as component (D) It was mixed 1: 1 by weight. Immediately before coating on the substrate, a complex salt of platinum and vinylsiloxane as component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The results of treating this composition under the conditions described above are shown in Table 2.

Example 4
As the component (A), 25 parts of a fluoroalkyl-modified polydimethylsiloxane represented by the following formula and symbol 4-1 in Table 1; 75 parts of a fluoroalkyl-modified polydimethylsiloxane represented by symbol 4-2 of the following formula and table 1; As component (B), 7 parts of methylhydropolysiloxane having both ends of the molecular chain blocked with a trimethylsilyl group and containing 95 mol% of a unit represented by MeHSiO _2/2 and having a viscosity of 25 mPa · s, ( As component (D), 2 parts of 3-methyl-1-butyn-3-ol was diluted as component (E) to 900 parts of a mixture of toluene and heptane at a weight ratio of 1: 1. Immediately before coating on the substrate, a complex salt of platinum and vinylsiloxane as component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The results of treating this composition under the conditions described above are shown in Table 2.

Comparative Example 1
A 1% toluene solution of a long-chain alkyl pendant type polymer, Pyroyl 1010 (product name, Yushi Kogyo Co., Ltd.) was applied to the substrate so as to be 0.1 g / m ² and dried at 120 ° C. for 30 seconds. The results of treating this substrate in the same manner as in the above example are shown in Table 2.

Comparative Example 2
As component (A), 100 parts of phenyl-modified polydimethylsiloxane represented by the following formula and symbol 5 in Table 1, and as component (B), both ends of the molecular chain are blocked with trimethylsilyl groups, and represented by MeHSiO _2/2. 4 parts of methylhydropolysiloxane having a viscosity of 25 mPa · s and 2 parts of 3-methyl-1-butyn-3-ol as component (D) As components, toluene and heptane mixed at a weight ratio of 1: 1 were diluted to 900 parts. Immediately before coating on the substrate, a complex salt of platinum and vinylsiloxane as component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The results of treating this composition under the conditions described above are shown in Table 2.

Comparative Example 3
As component (A), 100 parts of a fluoroalkyl-modified polydimethylsiloxane represented by the following formula and symbol 6 in Table 1, and as component (B), both ends of the molecular chain are blocked with trimethylsilyl groups and represented by MeHSiO _2/2. 2 parts of methylhydropolysiloxane containing 95 mol% unit and having a viscosity of 25 mPa · s, 2 parts of 3-methyl-1-butyn-3-ol as component (D), and toluene and heptane by weight The mixture was diluted to 900 parts by mixing at a ratio of 1: 1. Immediately before coating on the substrate, a complex salt of platinum and vinylsiloxane as component (C) was added in an amount of 100 ppm in terms of platinum to prepare a composition. The results of treating this composition under the conditions described above are shown in Table 2.

Comparative Example 4
A 10% FR thinner (fluorine-based solvent) solution of a fluorine-based mold release agent, X-70-201 (Shin-Etsu Chemical Co., Ltd. product name), was applied to the substrate so as to be 0.2 g / m ^2, and 150 ° C. For 60 seconds. The results for this substrate are shown in Table 2.

General formula of fluoroalkyl-modified polydimethylsiloxane used in the examples

Structure of fluoroalkyl-modified polydimethylsiloxane used in Examples

Formulation and properties of silicone compositions

Claims (6)

(A) It has at least two alkenyl groups and at least one fluoroalkyl group in one molecule, and the alkenyl group content is 0.02 to 0.20 mol / 100 g, and the fluoroalkyl group content is 0. Fluoroalkyl-modified polydimethylsiloxane having a viscosity at 25 ° C. of 0.05 to 0.50 mol / 100 g and a viscosity of 50 to 100,000 mPa · s 100 parts by weight (B) At least 3 hydrogen atoms bonded to silicon atoms in one molecule Polyorganohydrodiene siloxane having a number of moles of hydrogen atoms bonded to silicon atoms corresponding to 0.5 to 5 times moles of alkenyl groups in component (A),
(C) a catalytic amount of a platinum group compound,
(D) 0.01-10 parts by weight of a reaction control agent,
(E) A release agent composition for a silicone pressure-sensitive adhesive containing an arbitrary amount of an organic solvent. The fluoroalkyl-modified polydimethylsiloxane (A-1), which is the component (A), contains 0.1 to 2.0 mol% of a siloxane unit having an alkenyl group in one molecule, and an alkenyl group. The silicone according to claim 1, wherein the fluoroalkyl-modified polydimethylsiloxane (A-2) containing 4.0 to 15.0 mol% of siloxane units having a weight ratio of 20:80 to 80:20. Release agent composition for pressure-sensitive adhesives. The (A) component fluoroalkyl-modified polydimethylsiloxane is represented by the following general formula (1):

(In the formula, R ¹ represents an alkenyl group or a monovalent hydrocarbon group excluding an alkenyl group, R ² represents a monovalent fluoroalkyl group, and q, r, and s are positive numbers, and t and u are 0 or The mold release agent composition for silicone pressure-sensitive adhesives according to claim 1 or 2, which is a compound represented by the formula: Component (B) is an organohydrodienesiloxane represented by the following general formula (2)
R ³ _x H _y SiO _{(4-xy) / 2} (2)
(In the formula, R ³ is a monovalent hydrocarbon group excluding an alkenyl group, at least 80% is a methyl group, and x and y are 0.7 ≦ x ≦ 2.1, 0.001 ≦ y ≦ 1. 0.0 and 0.8 ≦ x + y ≦ 2.6, preferably 0.8 ≦ x ≦ 2, 0.01 ≦ y ≦ 1, and 1 ≦ x + y ≦ 2.4. The mold release agent composition for silicone adhesives of Claim 1 which has at least 3 hydrogen atoms couple | bonded with the silicon atom in 1 molecule. The release agent composition for a silicone pressure-sensitive adhesive according to claims 1 to 3, wherein the fluoroalkyl group of the fluoroalkyl-modified polydimethylsiloxane as component (A) is a 3,3,3-trifluoropropyl group. A release sheet obtained by treating the release agent composition for a silicone pressure-sensitive adhesive according to claim 1 on a substrate such as paper or a plastic film.