JP2007186804A - Solventless curable silicone releasing agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an addition reaction-type solventless silicone composition having excellent thin film coatability and curability, exhibiting excellent releasing performance and giving a releasable cured silicone film generating little cissing of an emulsion-type adhesive. <P>SOLUTION: The curable silicone releasing agent composition contains the following components (A) to (E), has a viscosity of 50-1,000 mPa s at 25°C and is free from organic solvent. (A) A diorganopolysiloxane having an alkenyl group bonded to a silicon atom at a molecular chain terminal; (B) a diorganopolysiloxane having hydrogen atom bonded to a silicon atom at the molecular chain terminal; (C) an organohydrogenpolysiloxane having at least 3 hydrogen atoms bonded to silicon atom in one molecule; (D) a resin copolymer composed of the units of general formula R<SB>3</SB>SiO<SB>1/2</SB>(M unit) and SiO<SB>4/2</SB>(Q unit); and (E) a platinum-group metal catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is excellent in thin film coatability, curability and releasability, and in the process of producing an adhesive processed paper using an emulsion-type adhesive, a peelable silicone cured film free from coating defects due to repelling of the adhesive. The present invention relates to an addition reaction type solventless type silicone release agent composition to be applied and a release paper on which a cured film of the composition is formed.

  Conventionally, for the purpose of preventing adhesion or adhesion between a base material such as paper or plastic film and an adhesive substance, it is possible to form a cured film of the silicone composition on the surface of the base material to impart releasability. Has been done.

  In this case, as a method of forming a silicone film on the surface of the substrate, a method of forming a peelable film by addition reaction of an organopolysiloxane containing an alkenyl group and an organohydrogenpolysiloxane using a platinum compound as a catalyst. (See, for example, Japanese Patent Application Laid-Open No. 47-32072) is widely used.

  In recent years, silicone release agents have been switched from a solvent type to a solventless type in terms of safety and hygiene. Further, high-speed coating is required from the viewpoint of productivity, and a solventless type having a lower viscosity is required from the viewpoint of leveling properties and prevention of mist generation.

  The ratio of the emulsion type is also large from the viewpoint of safety and hygiene for the pressure-sensitive adhesive used for the production of pressure-sensitive adhesive paper. Also, high-speed coating is required from the viewpoint of productivity, and for the same reason, a lower viscosity emulsion-type pressure-sensitive adhesive is required.

  However, in the case of applying a low viscosity emulsion type adhesive to the silicone coated paper during the production of the so-called transfer method adhesive paper where the adhesive is applied to the silicone coated surface side of the silicone coated paper and the surface substrate is bonded. As a result, glue repelling occurs and pinholes are likely to occur, and application defects of the adhesive often become a problem.

  In addition to improving adhesives and coating equipment, improvement of silicone release agents is also required, but until now, an addition reaction type solvent-free silicone release agent composition with excellent release performance and coating performance. The thing was not obtained.

Japanese Patent Laid-Open No. 47-32072 Japanese Patent Publication No. 52-47485 JP 02-145649 A

  The present invention has been made in view of the above circumstances. It has excellent thin film coatability and curability, has excellent peeling performance, and provides an exfoliated silicone cured film with less repellency of the emulsion-type pressure-sensitive adhesive. An object is to provide a solvent-type silicone composition.

  In order to achieve the above object, the present inventor conducted intensive studies on an organohydrogenpolysiloxane that undergoes a hydrosilylation reaction with an alkenyl group-containing organopolysiloxane that is a main component, and as a result of MQ type resinous copolymer. Diorganopolysiloxane having alkenyl group bonded to silicon atom, MQ silicone resin not containing aliphatic unsaturated bond, and diorganopolysiloxane having hydrogen atom bonded to silicon atom at both ends of molecular chain and one molecule Emulsion-type pressure-sensitive adhesive without lowering curability, adhesion to the substrate, slipperiness, and peeling performance by using together an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms Has found that the effect of preventing repellency can be obtained, and has reached the present invention

That is, the present invention
(A) The following general formula (1)

（ここで、Ｒ^１はアルケニル基、Ｒは脂肪族不飽和結合を含有しない同種又は異種の一価炭化水素基であり、４５≦ｎ≦３５０）で示され、２５℃における粘度が５０〜１，５００ｍＰａ・ｓである分子鎖末端にケイ素原子に結合したアルケニル基を有するジオルガノポリシロキサンを１００質量、
（Ｂ）下記一般式（２）

(Wherein R ¹ is an alkenyl group, R is the same or different monovalent hydrocarbon group not containing an aliphatic unsaturated bond, 45 ≦ n ≦ 350), and the viscosity at 25 ° C. is 50-1 100 mass of a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at the end of a molecular chain of .500 mPa · s,
(B) The following general formula (2)

（ここで、Ｈは水素原子、Ｒは脂肪族不飽和結合を含有しない同種又は異種の一価炭化水素基であり、２≦ｍ≦２０）で示され、２５℃における粘度が２〜３０ｍＰａ・ｓである分子鎖末端にケイ素原子に結合した水素原子を有し、（Ａ）成分のアルケニル基量に対する水素原子の量がモル比で０．３〜０．８の範囲であるジオルガノポリシロキサンを０．５〜１５．０質量部、
（Ｃ）１分子中にけい素原子に結合した水素原子を少なくとも３個有し、（Ａ）成分のアルケニル基量に対する水素原子の量がモル比で０．４〜３．０の範囲であるオルガノハイドロジェンポリシロキサンを０．３〜１０．０質量部、
（Ｄ）一般式Ｒ_３ＳｉＯ_１／２（Ｍ単位）、及びＳｉＯ_４／２（Ｑ単位）から成る（ここで、Ｒは脂肪族不飽和結合を含有しない同種又は異種の一価炭化水素基であり、Ｍ単位とＱ単位との比率が０．６／１ 〜 １．２／１の範囲である）トルエンに可溶な樹脂状共重合体を０．１〜２０．０質量部、
（Ｅ）白金族金属系触媒を、（Ａ）成分１００重量部に対して白金族金属量として１〜１，０００ｐｐｍ、とを必須成分とすることを特徴とし、２５℃における粘度が５０〜１，０００ｍＰａ・ｓの範囲内である実質的に有機溶剤を含有しない無溶剤型硬化性シリコ−ン剥離剤組成物及びこの組成物の硬化皮膜が形成されてなる剥離紙を提供する。

(Wherein H is a hydrogen atom, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, 2 ≦ m ≦ 20), and the viscosity at 25 ° C. is 2 to 30 mPa · diorganopolysiloxane having a hydrogen atom bonded to a silicon atom at the molecular chain terminal, and having a molar ratio of the hydrogen atom to the amount of the alkenyl group of component (A) in the range of 0.3 to 0.8 0.5 to 15.0 parts by mass,
(C) The molecule has at least three hydrogen atoms bonded to silicon atoms, and the amount of hydrogen atoms with respect to the amount of alkenyl groups in component (A) is in the range of 0.4 to 3.0 in terms of molar ratio. 0.3 to 10.0 parts by mass of organohydrogenpolysiloxane,
(D) consisting of general formula R ₃ SiO _1/2 (M unit) and SiO _4/2 (Q unit) (wherein R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond) The ratio of M units to Q units is in the range of 0.6 / 1 to 1.2 / 1) 0.1-20.0 parts by weight of a resinous copolymer soluble in toluene,
(E) The platinum group metal catalyst is characterized by having 1 to 1,000 ppm as an amount of platinum group metal with respect to 100 parts by weight of component (A), and has a viscosity at 25 ° C. of 50 to 1 The present invention provides a solvent-free curable silicone release agent composition substantially free of an organic solvent within a range of 1,000 mPa · s and a release paper on which a cured film of this composition is formed.

  The solventless silicone composition of the present invention is excellent in thin film coatability and curable adhesiveness, and both the SiH groups of the (B) and (C) components react with the alkenyl group of the (A) component. However, since the (B) component having the SiH group only at the highly reactive terminal and the (A) component first react to extend the chain length, and the remaining alkenyl group reacts with the SiH group of the (C) component, curing In addition to being able to reduce the hardness of the film and preventing emulsion-type adhesives from repelling, the (D) component MQ resin is dispersed in a small amount in the silicone cured film, so the peelability and slipperiness are not reduced. In addition, it is possible to further prevent emulsion-type pressure-sensitive adhesive repellency, and can cope with high-speed coating using a low-viscosity-type emulsion-type pressure-sensitive adhesive at the time of producing pressure-sensitive adhesive paper.

  The solventless silicone composition of the present invention is excellent in thin film coatability and curable adhesiveness, and can further prevent repellency of the emulsion-type pressure-sensitive adhesive without reducing the peelability and slipperiness. At the time of paper manufacture, it can cope with high-speed coating using a low-viscosity emulsion-type adhesive.

Hereinafter, the present invention will be described in more detail. The organopolysiloxane of the component (A) in the present invention suppresses the curability and hardness of the film after curing, and suppresses the repellency of the emulsion-type pressure-sensitive adhesive. It is shown by the following general formula (1) having an alkenyl group R ¹ bonded to

ここで、Ｒ^１のアルケニル基としてはビニル基、アリル基、プロペニル基、ヘキセニル基、オクテニル基、デセニル基等が例示される。

Here, examples of the alkenyl group for R ¹ include a vinyl group, an allyl group, a propenyl group, a hexenyl group, an octenyl group, and a decenyl group.

  R is the same or different monovalent hydrocarbon group containing 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond, specifically a methyl group or an ethyl group. , An alkyl group such as a propyl group, and an aryl group such as a phenyl group and a tolyl group, but 80 mol% or more is preferably a methyl group from the viewpoint of improving curability and peelability.

  Furthermore, when the viscosity at 25 ° C. is lower than 50 mPa · s, there is a disadvantage that the penetration into the substrate increases. When the viscosity is higher than 1,500 mPa · s, the coating property is lowered and the problem of mist generation in high-speed coating is removed. Therefore, the viscosity at 25 ° C. is 50 to 1,500 mPa · s, preferably 70 to 1,300 mPa · s. For this purpose, the degree of polymerization n is in the range of 45 to 350, preferably 50 to 300.

  The diorganopolysiloxane of component (B) in the present invention is represented by the following general formula (2) having one hydrogen atom bonded to a silicon atom at both ends of the molecular chain. This SiH group and the alkenyl group in the component (A) undergo an addition reaction to produce an effect of chain extension.

ここで、Ｒで示される基としては、上記と同様の炭素原子数１〜１２、好ましくは炭素原子数１〜６の脂肪族不飽和結合を含有しない同種又は異種の一価の炭化水素基であり、具体的にはメチル基，エチル基，プロピル基等のアルキル基、フェニル基，トリル基等のアリール基などが挙げられるが、硬化性、剥離性向上の点から８０モル％以上がメチル基であることが好ましい。

Here, the group represented by R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, as described above. Specific examples include alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group and tolyl group. More than 80 mol% is methyl group from the viewpoint of improving curability and peelability. It is preferable that

  On the other hand, if m is smaller than 2, the boiling point is lowered, and there is a disadvantage that it volatilizes during heat curing. When m is larger than 20, the adhesion with the substrate is lowered, so that the degree of polymerization m is in the range of 2 to 20, preferably 4 to 18. Accordingly, the viscosity at 25 ° C. is 2 to 30 mPa · s, preferably 3 to 25 mPa · s.

  The amount of component (B) is 0.3 to 10.0 parts by weight, preferably 0.4 to 9.5 parts by weight, based on 100 parts by weight of component (A). It is adjusted by the amount of SiH group and is in the range of 0.3 to 0.8, preferably 0.35 to 0.75 in terms of molar ratio. When the molar ratio is less than 0.3, the targeted effect of preventing glue repellency cannot be obtained, and when the molar ratio is greater than 0.8, the adhesion with the substrate is lowered.

The organohydrogenpolysiloxane of component (C) in the present invention has at least 3 hydrogen atoms bonded to silicon atoms in one minute, and this SiH group and the vinyl group in component (A) are added. A cured film is formed by reaction, and the following general formula R _b H _C SiO _{(4-b-C) / 2}
(Where R is the same monovalent hydrocarbon group as described above, and b and c are each b + c ≦ 3.
It is a positive number that satisfies ).

This type of polysiloxane includes RHSiO _2/2 units, HSiO _3/2 units, R ₂ SiO _2/2 units, R ₂ HSiO _1/2 units, RSiO _3/2 units, and R ₃ SiO _1/2 units. The polymer or the copolymer is exemplified, but this may be either linear or cyclic, and the viscosity at 25 ° C. should be 5 to 500 mPa · s.

The (C) component organohydrogenpolysiloxane has (RHSiO _2/2 ) units and / or (RHSiO _2/2 ) units and a molecular chain side each having one hydrogen atom on each of the silicon atoms of the molecular chain side difference. no hydrogen atoms to silicon atoms of the difference consists and _{(R 2 SiO 2/2) units,} and (R _{2 SiO 2/2)} to include a number of units low-temperature curability of the base material for improved are those Since the adhesiveness is remarkably reduced, the ratio of (R ₂ SiO _2/2 ) units in one molecule is preferably 50% or less.

  Here, as R, the same or different monovalent hydrocarbon group containing 1 to 12 carbon atoms as described above, preferably 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond, may be a methyl group. And an alkyl group such as an ethyl group and a propyl group, and an aryl group such as a phenyl group and a tolyl group, and a methyl group is preferable from the viewpoint of improving the addition reaction rate.

  Specific examples of the component (C) include a chain as shown in the following general formula (3) and a ring as shown in (4).

（ここで、Ｈは水素原子、Ｒは上記したと同様の一価炭化水素基、ｐは ３≦ｐ≦２００の整数、ｑは０≦ｑ≦１００の整数で、３≦ｐ＋ｑ≦２００、ｘは０または１である。）

(Here, H is a hydrogen atom, R is a monovalent hydrocarbon group as described above, p is an integer of 3 ≦ p ≦ 200, q is an integer of 0 ≦ q ≦ 100, 3 ≦ p + q ≦ 200, x Is 0 or 1.)

（ここで、Ｈは水素原子、Ｒは上記したと同様の一価炭化水素基、ｒは３≦ｒ≦２０の整数、ｓは０≦ｓ≦１０の整数で、３≦ｒ＋ｓ≦２０である。）

(Where H is a hydrogen atom, R is a monovalent hydrocarbon group as described above, r is an integer of 3 ≦ r ≦ 20, s is an integer of 0 ≦ s ≦ 10, and 3 ≦ r + s ≦ 20. .)

  The amount of component (C) is 0.3 to 10.0 parts by weight, preferably 0.5 to 9.5 parts by weight per 100 parts by weight of component (A). It is adjusted by the amount of SiH groups and is in the range of 0.4 to 3.0, preferably 0.5 to 2.7 in terms of molar ratio. This is because if the molar ratio is less than 0.4, the curability decreases, and if it exceeds 3.0, the peeling performance decreases.

  The SiH groups of the (B) and (C) components both react with the alkenyl group of the (A) component, but the (B) component and the (A) component having an SiH group only at the highly reactive terminal are first. It reacts to extend the chain length, and the remaining alkenyl group reacts with the SiH group of the component (C), which is effective in preventing repellency when the hardness of the cured film is lowered.

The component (D) is a toluene-soluble resinous copolymer composed of R ₃ SiO _1/2 (M unit) and SiO _4/2 (Q unit). The wettability of the mold pressure-sensitive adhesive is improved and has an effect of preventing repellency.

  Here, R is the same or different monovalent hydrocarbon group or hydroxyl group that does not contain an aliphatic unsaturated bond, and examples of the organic group represented by R include alkyl groups such as methyl, ethyl, and propyl groups, phenyl An aryl group such as a group and a tolyl group is exemplified, but from the viewpoint of compatibility, 80 mol% or more is preferably a methyl group. When R contains an aliphatic unsaturated bond, the addition of a small amount is less effective for preventing repellency, and if it is added in a large amount, it is effective for preventing repellency, but the peelability and slipperiness are extremely lowered, which is not preferable.

  The ratio of (M unit) to (Q unit) is in the range of 0.6 / 1 to 1.2 / 1, preferably 0.62 / 1 to 1.15 / 1, and is smaller than 0.6. Manufacturing becomes difficult, and if it exceeds 1.2, the effect of preventing repellency is reduced, and the range of 0.65 / 1 to 1.1 / 1 is more preferable.

  Furthermore, the compounding quantity of (D) component is 0.1-20.0 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.2-15.0 mass parts. If it is less than 0.1, the emulsion-type pressure-sensitive adhesive is not effective for preventing repellency, and if it exceeds 20.0, it is effective for preventing repellency, but the peelability and slipperiness are extremely lowered.

  The component (E) platinum group metal catalyst is a catalyst for promoting the addition reaction between the component (A) and the components (B) and (C), and any known addition reaction catalyst can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, and rhodium-based catalysts, and among these, platinum-based catalysts are particularly preferable. Examples of such platinum-based catalysts include chloroplatinic acid, chloroplatinic acid alcohol solutions and aldehyde solutions, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like.

  Although the addition amount of these platinum group metal catalysts is a catalyst amount, from the economical viewpoint while obtaining a good cured film, the platinum group metal amount is 1 to 1,000 ppm with respect to 100 parts by weight of component (A), Preferably it is 5 to 500 ppm.

  The composition of the present invention can be obtained by blending predetermined amounts of the above components (A) to (E), but in addition to the above components, other optional components such as a platinum group metal catalyst. To suppress the activity, various activity inhibitors such as various organic nitrogen compounds, organophosphorus compounds, acetylene compounds, oxime compounds, and organic chloro compounds are used at the end to control the peeling force and the frictional resistance of the cured film. Diorganopolysiloxanes having hydroxyl groups bonded to silicon atoms, alkenyl groups bonded to silicon atoms, diorganopolysiloxanes not containing hydroxyl groups and hydrogen atoms, and polymer dimers having alkenyl groups bonded to silicon atoms. Organopolysiloxane and the like can be added as necessary. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  In preparing the silicone composition of the present invention, the components (A) and (D) are uniformly mixed, and then toluene in the component (D) is distilled off under reduced pressure and heating according to a conventional method. The component (E) is preferably added after the component and optional component are uniformly mixed in advance, and each component may be used alone or in combination of two or more. However, the viscosity at 25 ° C. of the entire composition is in the range of 50 to 1,000 mPa · s, preferably 80 to 800 mPa · s. If it exceeds 1,000 mPa · s, it is from between the coating rolls at the time of coating. Due to the generated mist, high-speed coating cannot be performed and productivity is lowered, which makes it difficult to use practically.

  The silicone composition thus prepared is applied to a substrate such as paper or plastic film, and then cured by heating in a conventional manner. As a substrate on which the composition of the present invention is applied and a cured film is formed, a paper substrate such as glassine paper, kraft paper, clay coat paper, laminated paper such as polyethylene laminated fine paper, polyethylene laminated kraft paper, polyester, Examples include films, sheets, etc. obtained from synthetic resins such as polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, and polyimide, and metal foils such as aluminum. From the viewpoint of excellent adhesion to the film, a paper substrate The use of laminated paper is particularly suitable.

In order to apply the composition of the present invention to the substrate, a known method such as a gravure / offset three roll method or a multi-stage roll method such as five or six can be used. 0.05 to 5.0 g / ^{m 2} as a coating amount, in particular, is suitable in the range of 0.1 to 3.0 g / ^{m 2,} in part on the desired position of all or releasable substrate Apply. After apply | coating to a base material, it is made to harden | cure by heating for 1.5 to 60 second at 70-220 degreeC, and the release paper of this invention is obtained.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In addition, all the parts in each example are mass parts, and a viscosity is a value in 25 degreeC.
Further, the curability, peel strength, residual adhesion rate, and silicone migration of the silicone composition were measured by the following methods.

(Curable)
A predetermined amount of the silicone composition is applied to the surface of a thin film film or sheet substrate, heated in a hot air drier at a predetermined temperature, and the cured film formed is rubbed several times with a finger, without being cloudy or falling off. The time (seconds) until the state is reached is measured, and this is regarded as curable.

(Glue repellent)
A predetermined amount of the silicone composition is applied to the surface of a thin film film or sheet substrate, heated in a hot air drier at a predetermined temperature to form a cured film, and then separated at 25 ° C. for 1 day. After the ding, the acrylic emulsion type pressure sensitive adhesive / Olivein BPW-311OH (manufactured by Toyo Ink Manufacturing Co., Ltd.) was diluted with water on the surface of the cured film, applied with 130 μm with Wet, and heat-treated at 100 ° C. for 3 minutes. The repelling condition was evaluated by (1) the total distance (mm) of repelling from both sides of the substrate and (2) the number of pinholes.

(Peeling force)
After the evaluation of glue repelling, high-quality paper with a basis weight of 64 g / m ² was pasted and aged at 25 ° C. for 20 hours, then the sample was cut to a width of 50 mm, and a DSC-500 type tensile tester manufactured by Shimadzu Corporation was used. The laminated paper was pulled at an angle of 180 degrees and a peeling speed of 0.3 m / min, and the force (N) required for peeling was measured.

(Slippery)
A neoprene butadiene rubber (NBR) of 20 mm × 20 mm × 2 mm was attached to the lower surface of a 200 g weight. The force F (N when this is placed on the surface of the cured film of the silicone composition formed on the substrate surface and becomes stable using a tensile tester at a rate of 0.3 m / min in the horizontal direction. ).
The coefficient of dynamic friction: F / (200 × 0.0098) is used as the evaluation of slipperiness.

[Example 1]
As component (A), in formula (1), R is a methyl group, R ¹ is a vinyl group (hereinafter referred to as Vi), n = 146, a viscosity of 390 mPa · s, and both ends of the molecular chain are dimethylvinylsiloxy groups 60 parts of polydimethylsiloxane (A-1) blocked with, and R is a methyl group, R ¹ is a vinyl group, n = 216 and the viscosity is 990 mPa · s. Both ends of the molecular chain are blocked with dimethylvinylsiloxy groups Toluene of copolymer resin (D-1) in which the ratio of methyl group M units to Q units is 0.75 / 1 as component (D) in a mixture of 40 parts of the resulting polydimethylsiloxane (A-2) 7.1 parts of a solution (5 parts as an active ingredient of a copolymer resin) was added, and toluene was distilled off at 150 ° C. under reduced pressure of 1,100 Pa over 2 hours. As a component (B), polydimethylsiloxane (B-1) 3 in which R in the formula (2) is a methyl group, m = 8, the viscosity is 5 mPa · s, and both ends of the molecular chain are blocked with a dimethylsiloxy group. 0.0 parts, (SiH / SiVi = 0.52), methyl hydrogen polysiloxane (C-1) having a viscosity of 20 mPa · s with both ends of the molecular chain blocked with a trimethylsiloxy group as component (C) A mixture of 65 parts and 0.95 parts of methylhydrogenpolysiloxane (C-2) having a viscosity of 45 mPa · s, with both ends of the molecular chain having 25 mol% of dimethylsiloxane units blocked with trimethylsiloxy groups (SiH / SiVi) = 1.26), 0.2 parts of 1-ethynyl-1-cyclohexanol and 1,1-dimethyl-2-propenyloxytri as further optional components After adding 0.3 part of tilsilane and stirring until uniform, the complex of platinum and vinylsiloxane as component (E) is based on the sum of the dimethylpolysiloxanes of (A-1) and (A-2) above. It added so that it might be set to 100 ppm in conversion of platinum, and the silicone composition whose viscosity is 490 mPa * s was prepared.

Polydimethylsiloxane (A-1)

Polydimethylsiloxane (A-2)

Polydimethylsiloxane (B-1)

Methyl hydrogen polysiloxane (C-1)

Methyl hydrogen polysiloxane (C-2)

Copolymer resin (D-1)

Next, the number of seconds until the resulting silicone composition Polyethylene laminated paper (basis weight 100 g / ^{m 2)} to 0.6~0.7g / ^{m 2} was coated and cured at 120 ° C. As for cured test Sought. Further, as a sample for glue repelling, peeling force, and slipperiness, a heat treatment was performed at 140 ° C. for 30 seconds to form a cured film. The pressure-sensitive adhesive was added with 15 parts of water to 85 parts, mixed uniformly, and applied to a silicone-coated paper cut to a length of 30 cm and a width of 12 cm. These measurement results are shown in Table 1.

[Example 2]
A silicone composition having a viscosity of 510 mPa · s was prepared in the same manner as in Example 1 except that the active ingredient of (D) was changed to 12 parts in Example 1, and the same physical property test as in Example 1 was performed. . The results are also shown in Table 1.

[Example 3]
(A) Toluene solution of the same copolymer resin (D-1) used in Example 1 as component (D) to 100 parts of the same polydimethylsiloxane (A-1) used in Example 1 as component (A) 1.7 parts (1.2 parts as an active ingredient of the copolymer resin) and, as an optional additional ingredient, both ends of the molecular chain represented by the following formula are blocked with dimethylvinylsiloxy groups to give 0.05 parts of methylvinylsiloxane units. 1.8 parts of dimethylpolysiloxane having a mol% of 10,000 degree of polymerization was added and uniformly dissolved, and toluene was distilled off over 2 hours under reduced pressure at 150 ° C. and 1,100 Pa. The same polydimethylsiloxane (B-1) 3.3 parts used in Example 1 as the component (B), (SiH / SiVi = 0.5), and the component (C) used in Example 1 as the component (B). 1.8 parts of the same methyl hydrogen polysiloxane (C-1) (SiH / SiVi = 1.5), 0.2 parts of 1-ethynyl-1-cyclohexanol as an optional component and 1,1-dimethyl- After adding 0.3 parts of 2-propenyloxytrimethylsilane and stirring until uniform, a complex of platinum and vinylsiloxane as component (E) in terms of platinum relative to the dimethylpolysiloxane of (A-1) above. A silicone composition having a viscosity of 430 mPa · s was prepared by adding 100 ppm, and the same physical property test as in Example 1 was performed. The results are also shown in Table 1.

Optional additional ingredients

[Comparative Example 1]
100 parts of the same polydimethylsiloxane (A-1) used in Example 1 as the component (A), 2.2 parts of the same methyl hydrogen polysiloxane (C-1) used in Example 1 as the component (C) Parts (SiH / SiVi = 1.9), the component (B) and (D) were not used, and as an optional component, except that 0.3 part of 1-ethynyl-1-cyclohexanol was used as Example 1. Similarly, a silicone composition having a viscosity of 350 mPa · s was prepared, and the same physical property test as in Example 1 was performed. The results are also shown in Table 1.

[Comparative Example 2]
A silicone composition having a viscosity of 460 mPa · s was prepared in the same manner as in Example 1 except that the component (D) was not used in Example 1, and the same physical property test as in Example 1 was performed. The results are also shown in Table 1.

[Comparative Example 3]
In Example 1, the component (B) was not used, and as the component (C), 1.0 part of the same methyl hydrogen polysiloxane (C-1) used in Example 1 and the same as that used in Example 1 were used. A silicone composition having a viscosity of 510 mPa · s was prepared in the same manner as in Example 1 except that 1.4 parts of methylhydrogenpolysiloxane (C-2) (SiH / SiVi = 1.9) was used. The same physical property test as in Example 1 was performed. The results are also shown in Table 1.

[Comparative Example 4]
(A) Polydimethylsiloxane as component (1) in which R is a methyl group, R ¹ is a vinyl group, n = 68 and the viscosity is 99 mPa · s and both ends of the molecular chain are blocked with dimethylvinylsiloxy groups (A-3) 100 parts by weight R as a component (D) is a methyl group or a vinyl group, and the ratio of M units and Q units having 0.07 mol% of vinyl groups bonded to silicon atoms per 100 g is 0.00. Add 21.4 parts of a toluene solution of copolymer resin (D-2) of 85/1 (15 parts as an active ingredient of the copolymer resin) and dissolve uniformly, at 150 ° C. under a reduced pressure of 1,100 Pa. Toluene was distilled off over 2 hours. The same polydimethylsiloxane (B-1) 9.0 parts used in Example 1 as the (B) component, (SiH / SiVi = 0.48), and the (C) component used in Example 1 Add 4.7 parts of the same methyl hydrogen polysiloxane (C-1) (SiH / SiVi = 1.40) and 0.45 part of 1-ethynyl-1-cyclohexanol as an optional component until uniform After stirring, a complex of platinum and vinylsiloxane as component (E) was added to 100 ppm in terms of platinum with respect to the dimethylpolysiloxane, and a silicone composition having a viscosity of 330 mPa · s was prepared and carried out. The same physical property test as in Example 1 was performed. The results are also shown in Table 1.

Polydimethylsiloxane (A-3)

Copolymer resin (D-2)

[Comparative Example 5]
The amount of the copolymer resin component (D) in Comparative Example 4 is 50 parts, the amount of (B) is 10.0 parts, (SiH / SiVi = 0.34), and the amount of (C) is 8.0. A silicone composition having a viscosity of 530 mPa · s was prepared in the same manner as in Comparative Example 4 except that the parts (SiH / SiVi = 1.51) were used, and the same physical property test as in Example 1 was performed. The results are also shown in Table 1.

[Comparative Example 6]
The composition of Comparative Example 1 is blended with the same amount of the component (D) in Example 1 as in Example 1, to prepare a silicone composition having a viscosity of 390 mPa · s, and the same physical property test as in Example 1 Went. The results are also shown in Table 1.

Claims (2)

(A) The following general formula (1)

(Wherein R ¹ is an alkenyl group, R is the same or different monovalent hydrocarbon group not containing an aliphatic unsaturated bond, 45 ≦ n ≦ 350), and the viscosity at 25 ° C. is 50-1 100 mass of a diorganopolysiloxane having an alkenyl group bonded to a silicon atom at the end of a molecular chain of .500 mPa · s,
(B) The following general formula (2)

(Wherein H is a hydrogen atom, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, 2 ≦ m ≦ 20), and the viscosity at 25 ° C. is 2 to 30 mPa · diorganopolysiloxane having a hydrogen atom bonded to a silicon atom at the molecular chain terminal, and having a molar ratio of the hydrogen atom to the amount of the alkenyl group of component (A) in the range of 0.3 to 0.8 0.5 to 15.0 parts by mass,
(C) The molecule has at least three hydrogen atoms bonded to silicon atoms, and the amount of hydrogen atoms with respect to the amount of alkenyl groups in component (A) is in the range of 0.4 to 3.0 in terms of molar ratio. 0.3 to 10.0 parts by mass of organohydrogenpolysiloxane,
(D) consisting of general formula R ₃ SiO _1/2 (M unit) and SiO _4/2 (Q unit) (wherein R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond) The ratio of M units to Q units is in the range of 0.6 / 1 to 1.2 / 1) 0.1-20.0 parts by weight of a resinous copolymer soluble in toluene,
(E) The platinum group metal catalyst is 1 to 1,000 ppm in terms of platinum group metal amount with respect to 100 parts by weight of component (A).
A solvent-free curable silicone release agent composition having a viscosity at 25 ° C. of 50 to 1,000 mPa · s.   A release paper on which a cured film of the composition according to claim 1 is formed.