Addition curable delivery silicone composition for silicone adhesive

Abstract

The present invention is an addition-curable mold-release silicone composition for a silicone adhesive, containing: (A) a fluorine-containing organopolysiloxane having, in one molecule, at least two alkenyl groups bonded to a silicon atom and at least one fluorine-containing substituent group bonded to a silicon atom, and having a fluorine content of 25-50 mass%; and the peak area of components having a molecular weight of 4,000 or less is 2-20% of the total peak area in a molecular weight distribution measurement based on gel permeation chromatography; (B) an organohydrogenpolysiloxane having, in one molecule, at least three hydrogen atoms (SiH groups) bonded to a silicon atom; (C) a platinum group metal catalyst; and (D) a non-fluorine solvent. As a result, it is possible to provide a silicone composition for a release agent, which can be diluted with a non-fluorine solvent, has high coatability and adhesion to a film substrate, and is capable of obtaining a cured coating film having a small release force and a small decrease in residual adhesion rate.

Description

Technical Field

[0001] The present invention relates to an addition-curable release silicone composition for silicone adhesives, which can be diluted with a non-fluorine solvent (i.e., an organic solvent without fluorine atoms in its molecule) headed by a non-halogen solvent (i.e., an organic solvent without halogen atoms in its molecule), exhibits good release properties for silicone adhesives, and is excellent in transparency and adhesion. Background Art

[0002] Conventionally, in order to prevent adhesion or fixation between a substrate such as paper or plastic film and a pressure-sensitive adhesive such as a silicone adhesive, a cured film of a silicone composition is formed on the outer surface of the substrate to impart releasability to the pressure-sensitive adhesive. This cured film is generally called release paper.

[0003] Among the above-mentioned pressure-sensitive adhesive materials, silicone adhesives with organopolysiloxane as the main component have been used in a wide range of applications due to their excellent heat resistance, cold resistance, chemical resistance, electrical insulation, low toxicity, etc. Since silicone adhesives have very strong adhesion, in order to easily peel off the adhesive tape (tape) or adhesive label coated with the silicone adhesive from the above-mentioned substrate, the silicone cured film formed on the above-mentioned substrate needs to be a film with excellent peelability.

[0004] Patent Document 1 discloses an organopolysiloxane composition as an organosilicone composition capable of obtaining an organosilicone cured film with excellent mold release properties. n F 2n+1 A fluorine-containing substituent represented by CH2CH2- (n is an integer greater than 1). In addition, Patent Document 2 proposes an organopolysiloxane composition having a fluorine-containing substituent represented by F-[CF(CF3)CF2O] n A fluorine-containing substituent represented by CF(CF3)CF2OCH2CH2CH2- (n is an integer of 1 to 5).

[0005] When these organopolysiloxane compositions are applied to a substrate, they are diluted with an organic solvent. In this case, a fluorinated solvent (i.e., an organic solvent having a fluorine atom in the molecule) is preferably used as the organic solvent from the viewpoint of the solubility of the fluorinated organopolysiloxane composition and the coating properties on the substrate.

[0006] However, although fluorinated solvents can sufficiently dilute fluorinated organopolysiloxanes, they are expensive and have problems of adversely affecting the natural environment when diffused into the atmosphere.

[0007] Patent Document 3 proposes a silicone composition for release paper having a fluorine-containing substituent as a silicone composition that can be diluted with a non-fluorine-containing solvent and can provide a cured silicone film having excellent releasability.

[0008] However, when the silicone composition for release agent is dissolved in a non-fluorine-based solvent, there is a tendency that the peeling force is higher than when diluted with a fluorine-based solvent. In addition, although there is no record of coating properties and adhesion in Patent Document 3, when the silicone composition for release paper is dissolved in a non-fluorine-based solvent, the coating properties on the substrate may be poorer than when diluted with a fluorine-based solvent. If the coating properties on the substrate are poor, the part of the substrate not covered by the silicone composition for release agent will contact the adhesive and the peeling force will be significantly increased.

[0009] In addition, the silicone composition coating for release paper obtained by dissolving the silicone composition in a non-fluorine-containing solvent may have low adhesion to the film substrate, and the release layer may peel off from the substrate over time.

[0010] Patent Document 4 proposes a method of adding a linear perfluoropolyether defoaming agent to a silicone composition for a release agent as a method for improving coating properties. However, the linear perfluoropolyether defoaming agent does not have a reactive functional group and therefore does not participate in crosslinking. Sometimes, the defoaming agent is transferred to the adhesive layer side when the adhesive is peeled off, thereby reducing the residual adhesion rate.

[0011] In order to improve the adhesion, it is known to add a functional compound that interacts with the substrate. However, the compatibility between the substrate functional compound and the silicone composition is low, so the composition formed by adding the substrate functional compound to the silicone composition will cause the substrate functional compound to separate during long-term storage and transportation. If the separated composition is used directly, there is a possibility that the original performance cannot be obtained. In addition, the substrate functional compound sometimes transfers to the adhesive layer side when the adhesive is peeled off, causing the residual adhesion rate to decrease.

[0012] As described above, there is no prior art known to provide a release silicone composition for adhesives that can be diluted with a non-fluorinated solvent and that has sufficient coating properties to completely cover a substrate, adhesion properties that prevent the substrate from falling off over time, release properties that allow easy release even from an adhesive with high adhesive strength, and residual adhesion rate.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Publication No. 5-7434

[0016] Patent Document 2: Japanese Patent Publication No. 4-76391

[0017] Patent Document 3: Japanese Patent Application Laid-Open No. 7-18185

[0018] Patent Document 4: Japanese Patent Application Publication No. 2004-300414 Summary of the invention

[0019] 1. Technical issues to be resolved

[0020] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silicone composition for a release agent which can be diluted with a non-fluorine-based solvent, has high coating properties and adhesion to a film substrate, and can obtain a cured film with low peeling force and a small decrease in residual adhesion rate.

[0021] (II) Technical solution

[0022] In order to solve the above technical problems, the present invention provides an addition-curable release silicone composition for a silicone adhesive, which comprises:

[0023] (A) a fluorine-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms in one molecule, wherein the fluorine content is 25 to 50% by mass, and in a molecular weight distribution measurement based on gel permeation chromatography, the peak area of ​​components having a molecular weight of 4,000 or less is 2 to 20% of the total peak area, wherein the (A) fluorine-containing organopolysiloxane is 100 parts by mass;

[0024] (B) an organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, wherein the molar ratio of the hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the alkenyl groups in the component (A) is 0.1 to 15;

[0025] (C) a platinum group metal catalyst, in an amount of 0.5 to 5,000 ppm based on the mass of the platinum group metal relative to the component (A);

[0026] (D) a non-fluorinated solvent in an amount of 100 to 20,000 parts by mass.

[0027] If it is such an addition-curable release silicone composition for a silicone adhesive, it is possible to provide a silicone composition for a release agent, which can be diluted with a non-fluorine-based solvent, has high coating properties and adhesion to a film substrate, and can obtain a cured film with low peeling force and a small decrease in residual adhesion rate.

[0028] Furthermore, the molar ratio of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to alkenyl groups in the component (A) is preferably 0.5 to 5.

[0029] Such an addition-curable release silicone composition for a silicone adhesive can provide a silicone composition for a release agent having better coating properties, adhesion, and releasability.

[0030] Furthermore, it is preferred that the component (D) is a non-fluorinated solvent having an SP value (solubility parameter) of 10.0 or less.

[0031] According to such an addition-curable release silicone composition for silicone adhesives, it is possible to provide a silicone composition for release agents in which the component (A) is more favorably dissolved.

[0032] Furthermore, it is preferred that the component (D) is at least one selected from the group consisting of hydrocarbon solvents, ketone solvents, ether solvents, and ester solvents.

[0033] According to such an addition-curable release silicone composition for silicone adhesives, it is possible to provide a silicone composition for release agents in which the component (A) is more favorably dissolved.

[0034] The present invention also provides a release film including a film substrate having a cured product layer of the addition-curable release silicone composition for a silicone adhesive formed on at least one outer surface thereof.

[0035] Such a release film can provide a release film having excellent releasability.

[0036] The present invention also provides a release paper having a cured product layer of the addition-curable release silicone composition for silicone adhesives formed on at least one outer surface of a paper substrate.

[0037] Such a release paper can provide a release paper having excellent releasability.

[0038] (III) Beneficial effects

[0039] As described above, according to the present invention, there can be provided a silicone composition for a release agent which can be diluted with a non-fluorinated solvent, has high coating properties and adhesion to a film substrate, and can obtain a cured film with low peeling force and little reduction in residual adhesion. DETAILED DESCRIPTION

[0040] The inventors of the present application have conducted intensive studies to achieve the above-mentioned purpose, and as a result, have found that by blending the following components in a specific ratio: (A) a fluorine-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms in one molecule, the fluorine content being 25 to 50% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the molecular weight distribution measurement based on gel permeation chromatography analysis being 2 to 20% of the total peak area; and (B) an organohydrogenpolysiloxane having at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms in one molecule. The present invention is completed by using a silicone composition for a release agent having at least three hydrogen atoms (SiH groups) bonded to silicon atoms; (C) a platinum group metal catalyst; and (D) a non-fluorine-based solvent. The silicone composition has high coating properties and adhesion to a film substrate, and can obtain a cured film with low peeling force and a small reduction in residual adhesion. Since the composition does not contain a fluorine-based solvent, it is low-cost and has no concerns about air pollution. A release silicone cured film can be produced, and the cured film has excellent hydrophobicity, oleophobicity, and heat resistance, thereby completing the present invention.

[0041] That is, the present invention is an addition-curable release silicone composition for a silicone adhesive, comprising:

[0042] (A) a fluorine-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms in one molecule, wherein the fluorine content is 25 to 50% by mass, and in a molecular weight distribution measurement based on gel permeation chromatography, the peak area of ​​components having a molecular weight of 4,000 or less is 2 to 20% of the total peak area, wherein the (A) fluorine-containing organopolysiloxane is 100 parts by mass;

[0043] (B) an organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, wherein the molar ratio of the hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the alkenyl groups in the component (A) is 0.1 to 15;

[0044] (C) a platinum group metal catalyst, in an amount of 0.5 to 5,000 ppm based on the mass of the platinum group metal relative to the component (A);

[0045] (D) a non-fluorinated solvent in an amount of 100 to 20,000 parts by mass.

[0046] The present invention will be described in more detail below, but the present invention is not limited thereto.

[0047] [(A) ingredient]

[0048] The fluorinated organopolysiloxane of the component (A) has at least two alkenyl groups bonded to silicon atoms and at least one fluorinated substituent bonded to silicon atoms in one molecule, has a fluorine content of 25 to 50% by mass, and in a molecular weight distribution measurement based on gel permeation chromatography, the peak area of ​​components having a molecular weight of 4,000 or less accounts for 2 to 20% of the total peak area, and the fluorinated organopolysiloxane functions as a main agent (base polymer) of the addition-curable release silicone composition for the silicone adhesive of the present invention.

[0049] The fluorinated organopolysiloxane as the component (A) may be either linear or branched, and a linear fluorinated organopolysiloxane represented by the following formula (1) is particularly suitable, wherein the main chain of the molecular chain is composed of a repetition of a difunctional diorganosiloxane unit, a part and / or all of the diorganosiloxane units in the main chain are diorganosiloxane units having a fluorinated substituent bonded to a silicon atom (i.e., a monovalent hydrocarbon group optionally containing an ether-bonded oxygen atom (—O—) in which a part or all of the hydrogen atoms bonded to a carbon atom are substituted with fluorine atoms), and both ends of the molecular chain are capped with a triorganosiloxy group having an alkenyl group (alkenyldiorganosiloxy, dienylorganosiloxy or trialenylsiloxy) and the molecule has at least two alkenyl groups bonded to silicon atoms at both ends of the molecular chain, or has at least two alkenyl groups bonded to silicon atoms at both ends of the molecular chain and silicon atoms not at the molecular chain end (in the molecular chain).

[0050] [Chemical formula 1]

[0051]

[0052] Among them, R 1 It is an alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and cyclohexenyl.

[0053] R 2 The unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an aliphatic unsaturated group, specifically, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; and hydroxypropyl and cyanoethyl groups obtained by replacing a part or all of the hydrogen atoms of these groups with hydroxyl, cyano, and the like.

[0054] In the above formula, a is 1, 2 or 3, x, y, and z are respectively an integer of x≥1, an integer of y≥0, and an integer of z≥0, preferably x is an integer of 10 to 150, y is an integer of 50 to 400, and z is an integer of 0 to 10, more preferably x is an integer of 50 to 130, y is an integer of 100 to 350, and z is an integer of 0 to 5, and the value of x+y+z is appropriately controlled so that the fluorine content in the molecule is 25 to 50% by mass.

[0055] In formula (1), the fluorine-containing substituent represented by Rf (i.e., a monovalent hydrocarbon group optionally containing an ether-bonded oxygen atom (-O-) in which a part or all of the hydrogen atoms bonded to the carbon atom are substituted by fluorine atoms) can be exemplified by a monovalent fluorine-containing substituent represented by the following formula (2) (i.e., a perfluoroalkyl group, a polyfluoroalkyl group, a perfluorooxyalkyl group (monovalent perfluoropolyether group) or a polyfluorooxyalkyl group (monovalent polyfluoropolyether group)).

[0056] Formula (2):

[0057] F(CH n1 F 2-n1 O) b1 (CH n2 F 2-n2 CH n3 F 2-n3 O) b2 (CH n4 F 2-n4 CH n5 F 2-n5 CH n6 F 2-n6 ) b3 [CF(CF3)CH n7 F 2-n7 O] b4 [CH n8 F 2-n8 CF(CF3)O] b5 (CH n9 F 2-n9 CH n10 F 2-n10 CH n11 F 2-n11 CH n12 F 2-n12 ) b6 [CF(CF3)CH n13 F 2-n13 CH n14 F 2-n14 ] b7 [CH n15 F 2-n16 CF(CF3)CH n17 F 2-n17 ] b8 [CH n18 F2-n18 CH n19 F 2-n19 CF(CF3)] b9 (CH n20 F 2-n20 CH n21 F 2-n21 CH n22 F 2-n22 CH n23 F 2-n23 CH n24 F 2-n24 ) b10 [CF(CF3)CH n25 F 2-n25 CH n26 F 2- n26 CH n27 F 2-n27 ] b11 [CH n28 F 2-n28 CF(CF3)CH n29 F 2-n29 CH n30 F 2-n30 ] b12 [CH n31 F 2-n31 CH n32 F 2-n32 CF(CF3)CH n33 F 2-n33 ] b13 [CH n34 F 2-n34 CH n35 F 2-n35 CH n36 F 2-n36 CF(CF3)] b14 (CH n37 F 2-n37 CH n38 F 2-n38 CH n39 F 2- n39 CH n40 F 2-n40 CH n41 F 2-n42 CH n43 F 2-n43 ) b15 [CF(CF3)CH n44 F 2-n44 CH n45 F 2-n45 CH n46 F 2-n46 CH n47 F 2-n47 O]b16 [CH n48 F 2-n48 CF(CF3)CH n49 F 2-n49 CH n50 F 2-n50 CH n51 F 2-n51 O] b17 [CH n52 F 2-n52 CH n53 F 2-n53 CF(CF3)CH n54 F 2-n54 CH n55 F 2-n55 O] b18 [CH n56 F 2-n56 CH n57 F 2-n57 CH n58 F 2-n58 CF(CF3)CH n59 F 2-n59 O] b19 [CH n60 F 2- n60 CH n61 F 2-n61 CH n62 F 2-n62 CH n63 F 2-n63 CF(CF3)O] b20 [CF(CF3)] b21 (CH n64 F 2-n64 ) b22 -X-[CF(CF3)] b23 (CH n65 F 2-n65 ) b24 -

[0058] In formula (2), b1 to b24 are integers greater than 0; wherein at least one of b1 to b22 is an integer greater than 1; the total of b1 to b22 is preferably less than 25, and the total of b23 and b24 is preferably less than 8; n1 to n65 are each independently 0, 1 or 2; and X is an oxygen atom or a single bond.

[0059] In the above formula, the repeating units on the left side of "-X-" are optionally randomly bonded to each other, and the [CF(CF3)] unit as the repeating unit on the right side of "-X-" is bonded to (CH n65 F 2-n65 ) units are also optionally randomly bonded.

[0060] The fluorine-containing (poly)ether organic group (perfluorooxyalkyl group or polyfluorooxyalkyl group) in the fluorine-containing substituent represented by Rf is more preferably a group represented by any of the following formulas (3), (4) or (5).

[0061] Formula (3): F[CF(CF3)CF2O] c1 [CF(CF3)CH2O] c2 (CF2) c3 (CH2) c4 -

[0062] In formula (3), c1 to c4 are integers greater than 0, c1+c2 is an integer greater than 1, and c3+c4 is an integer greater than 0; c1+c2 is preferably less than 25, more preferably less than 15, and further preferably less than 9. c3+c4 is preferably less than 8; in addition, F[CF(CF3)CF2O] c1 [CF(CF3)CH2O] c2 (CF2) c3 (CH2) c4 -repeating units in are optionally randomly bonded.

[0063] Formula (4): F(CF2O) d1 (CF2CF2O) d2 (CF2CF2CF2O) d3 [CF(CF3)CF2O] d4 (CF2) d5 -O-(CH2) d6 -

[0064] In formula (4), d1 to d6 are integers greater than 0, d1+d2+d3+d4 are integers greater than 1; d1+d2+d3+d4 is preferably 25 or less, more preferably 15 or less, and further preferably 9 or less. d6 is preferably 8 or less; in addition, F(CF2O) d1 (CF2CF2O) d2 (CF2CF2CF2O) d3 [CF(CF3)CF2O] d4 (CF2) d5 The repeating units in are optionally randomly bonded.

[0065] Formula (5): F(CF2) e1 (CH2) e2 -O-(CH2) e3 -

[0066] In formula (5), e1 and e2 are each an integer greater than or equal to 1, and e3 is an integer greater than or equal to 0. e1 is preferably 8 or less, and e2 and e3 are each preferably 6 or less.

[0067] As particularly preferred examples of the fluorine-containing (poly)ether organic group, the following groups can be exemplified.

[0068] F[CF(CF3)CF2O] f CF(CF3)CF2O(CH2)3-

[0069] F[CF(CF3)CF2O] f CF(CF3)CH2O(CH2)3-

[0070] F[CF(CF3)CF2O] f (CF2)2(CH2)2-

[0071] F(CF2O) g [CF(CF3)CF2O] h CF2-O-(CH2)3-

[0072] F(CF2O) g (CF2CF2O] h CF2-O-(CH2)3-

[0073] F(CF2) i (CH2)2O(CH2)3-

[0074] F(CF2) i (CH2)2-

[0075] In the above formula, f is preferably 1 to 20, more preferably 2 to 12, and most preferably 3 to 9. g+h is preferably 1 to 20, more preferably 2 to 12, and most preferably 3 to 9. i is preferably 15 or less, more preferably 10 or less, and most preferably 6 or less.

[0076] Specific examples of the fluorine-containing organopolysiloxane of the component (A) include those represented by the following formula.

[0077] [Chemical formula 2]

[0078]

[0079] In the formula, Rf, x, y and z respectively have the same meanings as those described above, Me represents a methyl group, and Vi represents a vinyl group.

[0080] The fluorine-containing organopolysiloxane of component (A) needs to have a fluorine content in the molecule of 25 to 50% by mass, preferably 30 to 48% by mass, and more preferably 35 to 46% by mass. If the fluorine content in component (A) is less than 25% by mass, the peel strength of the obtained cured film to the silicone adhesive becomes high, and if it is more than 50% by mass, it becomes insoluble in non-fluorine-containing solvents.

[0081] Furthermore, the fluorinated organopolysiloxane of the component (A) needs to be one in which the peak area of ​​components having a molecular weight of 4,000 or less (e.g., components having a molecular weight of greater than 0 and 4,000 or less) accounts for 2 to 20% (area %) of the total peak area (i.e., the peak area of ​​the entire component (A)) in a molecular weight distribution measurement based on gel permeation chromatography (GPC) analysis. A substance in which the peak area of ​​components having a molecular weight of 4,000 or less accounts for less than 2% of the total peak area in a GPC analysis has poor solubility in non-fluorinated solvents and poor coating properties on substrates, and a substance in which the peak area exceeds 20% has poor adhesion to substrates and a greater decrease in residual adhesion.

[0082] In the present invention, the peak area ratio of components having a molecular weight of 4,000 or less refers to, for example, the ratio (area %) of the peak area of ​​components in the lower molecular weight region with the peak corresponding to a molecular weight of 4,000 as the boundary (i.e., components having a molecular weight of greater than 0 and 4,000 or less) to the peak area (total peak area) of all components contained in the fluorinated organopolysiloxane of the component (A) in a molecular weight distribution measurement based on gel permeation chromatography (GPC) analysis using a fluorinated solvent such as hydrochlorofluorocarbon (HCFC)-225 as an elution solvent and polymethyl methacrylate (PMMA) as a standard sample.

[0083] The fluorinated organopolysiloxane of the component (A) may be used alone or in combination of two or more.

[0084] [(B) ingredient]

[0085] The organohydrogenpolysiloxane of the component (B) has at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and the SiH groups undergo a hydrosilylation addition reaction with the alkenyl groups in the component (A) to crosslink and cure to form a cured film.

[0086] The organohydrogenpolysiloxane as the component (B) may be any of a linear, cyclic, branched, or three-dimensional network structure, and may also be a substance (fluorinated organohydrogenpolysiloxane) having in its molecule a fluorine-containing substituent (i.e., a monovalent hydrocarbon group optionally containing an ether-bonded oxygen atom (-O-) in which a part or all of the hydrogen atoms bonded to the carbon atom are substituted with fluorine atoms) the same as Rf in the formula (1) of the component (A). For example, a linear organohydrogenpolysiloxane represented by the following formula (i.e., an organo(hydrogen)polysiloxane terminated with triorganosiloxy groups at both ends of the molecular chain, a diorganosiloxane-organo(hydrogen)siloxane copolymer terminated with triorganosiloxy groups at both ends of the molecular chain, a diorganopolysiloxane terminated with diorgano(hydrogen)siloxy groups at both ends of the molecular chain, or a diorganopolysiloxane terminated with diorgano(hydrogen)siloxy groups at both ends of the molecular chain) is preferably used. An organo(hydrogen)siloxane terminated with an organo(hydrogen)siloxane alkoxy group, or a diorganosiloxane-organo(hydrogen)siloxane copolymer terminated with diorgano(hydrogen)siloxane alkoxy groups at both ends of the molecular chain, wherein the main molecular chain is composed of a repetitive structure of a difunctional organo(hydrogen)siloxane unit or a copolymer of a difunctional organo(hydrogen)siloxane unit and a difunctional diorganosiloxane unit, and both ends of the molecular chain are terminated with triorganosiloxane or diorgano(hydrogen)siloxane alkoxy groups, and the molecule has at least 3 hydrogen atoms (SiH groups) bonded to silicon atoms not at the ends of the molecular chain (in the molecular chain), or a total of at least 3 hydrogen atoms (SiH groups) bonded to silicon atoms not at the ends of the molecular chain (in the molecular chain) and hydrogen atoms (SiH groups) bonded to silicon atoms at both ends of the molecular chain in one molecule.

[0087] [Chemical formula 3]

[0088]

[0089] In the above formula, R 3 is selected from R in the above formula (1) 2 and at least one group in the same group as Rf, j is 0 or 1, p and q are respectively an integer of p≥1 and an integer of q≥0, preferably p is an integer of 3 to 150 and q is an integer of 0 to 150, more preferably p is an integer of 10 to 100 and q is an integer of 10 to 100; wherein p is a number that makes the number of hydrogen atoms (SiH groups) bonded to silicon atoms in the molecule be 3 or more.

[0090] Specific examples of the organohydrogenpolysiloxane of the component (B) include those represented by the following formula.

[0091] [Chemical formula 4]

[0092]

[0093] In the formula, Me represents a methyl group, p represents the same meaning as above, q' is an integer of 1 to 100, r is an integer of 1 to 100, and q'+r is an integer of 2 to 150.

[0094] The amount of the organohydrogenpolysiloxane of the component (B) is such that the molar ratio of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the alkenyl groups in the component (A) is 0.1 to 15 (mol / mol), preferably 0.3 to 10, and more preferably 0.5 to 5. When the molar ratio of the SiH groups in the component (B) to the alkenyl groups in the component (A) is less than 0.1 or greater than 15, the curability of the desired addition-curable release silicone composition for silicone adhesives is reduced or the physical properties of the cured product are reduced.

[0095] The organohydrogenpolysiloxane of the component (B) may be used alone or in combination of two or more.

[0096] [(C) ingredient]

[0097] The platinum group metal catalyst of component (C) is a catalyst for promoting the hydrosilylation addition reaction of the alkenyl group in component (A) and the SiH group in component (B), and a substance known as a reaction catalyst can be used. As such a platinum group metal catalyst, catalysts such as platinum, palladium, and rhodium can be listed, among which platinum catalysts are particularly preferred. As such a platinum catalyst, complexes of chloroplatinic acid, alcohol solutions of chloroplatinic acid, chloroplatinic acid and various olefins or vinyl siloxanes can be listed.

[0098] The amount of these platinum group metal catalysts added is only a catalytic amount. From the perspective of reactivity and economic efficiency when obtaining a cured film, the amount is 0.5 to 5,000 ppm, preferably 1 to 1,000 ppm, and more preferably 5 to 300 ppm, based on the mass of the platinum group metal relative to the component (A). If it is less than 0.5 ppm, the curability is reduced or the adhesion to the substrate is reduced. If it is more than 5,000 ppm, the pot life of the treatment bath is shortened.

[0099] [(D) ingredient]

[0100] (D) component is a fluorine-free solvent (i.e., an organic solvent having no fluorine atoms in the molecule), and the SP value of the fluorine-free solvent is preferably 10.0 or less, more preferably 9.5 or less, and further preferably 9.0 or less. If the SP value of the fluorine-free solvent of component (D) is 10.0 or less, the fluorine-containing organopolysiloxane of component (A) can be fully dissolved. In addition, the lower limit of the SP value is not particularly limited, and can be, for example, 5.0 or more, preferably 6.0 or more, and further preferably 7.0 or more.

[0101] The non-fluorinated solvent of component (D) is preferably a hydrocarbon solvent, a ketone solvent, an ether solvent or an ester solvent, and specific examples thereof include hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane, naphtha, aliphatic hydrocarbon solvents such as benzine), petroleum ether (ligroin), industrial gasoline, and naphtha solvents; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, and methyl propionate; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane, etc., which can be used alone or in combination of two or more.

[0102] The amount of the non-halogen solvent as component (D) is preferably such an amount that the viscosity of the silicone composition after dilution is 100 cp or less, from the viewpoint of workability when applying the silicone composition dissolved using the component and ease of controlling the coating amount, and is 100 to 20,000 parts by mass, preferably 500 to 15,000 parts by mass, more preferably 800 to 12,000 parts by mass, and even more preferably 1,000 to 3,000 parts by mass based on 100 parts by mass of component (A).

[0103] [Other ingredients]

[0104] The addition-curable release silicone composition for silicone adhesive of the present invention is obtained by blending a certain amount of the above-mentioned components (A) to (D), but in addition to the above-mentioned components, other arbitrary components can be added. For example, in order to control the catalytic activity of the platinum group metal catalyst, various organic nitrogen compounds, organic phosphorus compounds, organic silicon compounds, acetylene compounds, oxime compounds and other activity control agents can be added. Among the activity control agents, acetylene compounds such as 3-methyl-1-butyn-3-ol and their silylates, divinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane and other silicon compounds are suitable.

[0105] The amount of the activity control agent added is preferably 0.05 to 3 parts relative to 100 parts of component (A). If it is 0.05 parts or more, the target silicone composition will not gel, and if it is 3 parts or less, it will not hinder the curing of the silicone composition. In addition, the amount of other optional components added can be set to a conventional amount according to the purpose.

[0106] [Preparation of addition-curable release silicone composition for silicone adhesive]

[0107] When preparing the addition-curable release silicone composition for silicone adhesive of the present invention, it is preferred to uniformly mix the components (A), (B) and (D) in advance and then add the component (C) just before use. Each component may be used alone or in combination of two or more.

[0108] [Silicon oxide cured film]

[0109] As the substrate for coating the addition-curing release silicone composition for the silicone adhesive of the present invention, paper, plastic film, metal, cloth, glass, etc. can be selected. As plastic film, polyester, polypropylene, polyethylene, polystyrene, polycarbonate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyimide, polyamide, polyphenylene sulfide, etc. can be listed. As paper, paper substrates such as glass paper, kraft paper, and clay-coated paper can be listed; laminated paper substrates such as polyethylene laminated high-grade paper and polyethylene laminated kraft paper can be listed. As metal, aluminum foil, copper foil, gold foil, silver foil, etc. can be listed. As cloth, natural fiber cloth, synthetic fiber cloth, artificial leather, etc. can be listed. Glass has no special restrictions on thickness or type, and can be glass that has been subjected to chemical strengthening treatment, surface treatment, etc., and glass fiber can also be applied.

[0110] As a method for coating these substrates with the addition-curable release silicone composition for silicone adhesives of the present invention, known methods such as a bar coater, a roll coater, a gravure coater, a knife coater, a blade coater, a spin coater, dip coating, and cast coating can be used.

[0111] As the curing conditions of the addition-curable release silicone composition for the silicone adhesive of the present invention, there are methods such as heating the substrate coated with the silicone composition at a temperature of 80 to 250° C. for 1 to 120 seconds, or curing it by irradiating it with ultraviolet rays from an ultraviolet irradiation device such as a high-pressure mercury lamp for more than 0.2 seconds after the non-halogen solvent is volatilized, but it is not limited to this.

[0112] The addition-curable release silicone composition for silicone adhesives of the present invention can obtain a cured film having excellent coating properties, adhesion and release properties to a substrate, and is therefore suitable for use in adhesive tapes and release papers for adhesive labels. It can also be suitable for use in release properties for molds for molding rubber, plastics, etc., fiber treatment agents for paper, cloth, etc., water-repellent agents, oil-repellent agents, and heat-resistant coatings for food packaging, etc.

[0113] Example

[0114] The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. In addition, "parts" means "parts by mass".

[0115] [Molecular weight distribution measurement]

[0116] The molecular weight distribution of the fluorinated organopolysiloxane of the component (A) was measured using gel permeation chromatography (GPC) under the following conditions, and for each fluorinated organopolysiloxane, the ratio (%) of the peak area of ​​the component having a molecular weight of greater than 0 and less than 4,000 in the molecular weight distribution measurement by GPC to the total peak area was calculated.

[0117] [Measurement conditions]

[0118] Elution solvent: Hydrochlorofluorocarbon (HCFC)-225

[0119] Flow rate: 1mL / min

[0120] Detector: Evaporative light scattering detector

[0121] Chromatographic columns: 2 TSKgel Multipore HXL-M (7.8 mm φ × 30 cm) manufactured by TOSOH CORPORATION

[0122] Column temperature: 35°C

[0123] Sample injection volume: 100 μL (0.1 mass % solution)

[0124] Standard sample: PMMA CALIBRATION KIT ML-10 manufactured by Agilent Technologies

[0125] (Synthesis Example 1) Synthesis of fluorinated organopolysiloxane (A-1)

[0126] [Chemical formula 5]

[0127]

[0128] Me represents a methyl group.

[0129] [Chemical formula 6]

[0130]

[0131] Vi represents vinyl.

[0132] [Chemical formula 7]

[0133]

[0134] 100 parts of cyclotrisiloxane (6) having a fluorine-containing substituent, 0.27 parts of cyclomethylvinyltrisiloxane (7), and 0.21 parts of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (8) were mixed and stirred, and 0.01 parts of trifluoromethanesulfonic acid were added, and the mixture was reacted (equilibrated) at 50°C for 7 hours. Then, 0.2 parts of 28% ammonia water was added and stirred at room temperature for 1 hour, and the generated salt was filtered with filter paper, and after washing (stripping) at 200°C and 3 mmHg for 30 minutes, GPC measurement was performed. If the peak area of ​​the component with a molecular weight greater than 0 and less than 4,000 in the GPC measurement does not fall within the range of 2 to 20% of the total peak area, washing was performed again under the same conditions and GPC measurement was performed. This operation was repeated until the area of ​​the component having a molecular weight of greater than 0 and 4,000 or less in the GPC measurement fell within the range of 2 to 20% of the total peak area, thereby obtaining the fluorinated organopolysiloxane (A-1) shown in Table 1. The fluorine content of this fluorinated organopolysiloxane was 44.0% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the total peak area in the GPC measurement was 14%.

[0135] (A-1)

[0136] [Chemical formula 8]

[0137]

[0138] (Synthesis Example 2) Synthesis of fluorinated organopolysiloxane (A-2)

[0139] [Chemical formula 9]

[0140]

[0141] A fluorinated organopolysiloxane (A-2) was synthesized in the same manner as in Synthesis Example 1 except that 100 parts of cyclotrisiloxane (6) having a fluorinated substituent, 0.36 parts of cyclomethylvinyltrisiloxane (7), 0.28 parts of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (8), and 10.2 parts of cyclodimethyltrisiloxane (9) were used. The fluorine content of the fluorinated organopolysiloxane was 40.0% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the total peak area measured by GPC was 8%.

[0142] (A-2)

[0143] [Chemical formula 10]

[0144]

[0145] (Synthesis Example 3) Synthesis of fluorinated organopolysiloxane (A-3)

[0146] A fluorinated organopolysiloxane (A-3) was synthesized in the same manner as in Synthesis Example 1 except that 100 parts of cyclotrisiloxane (6) having a fluorinated substituent, 0.49 parts of cyclomethylvinyltrisiloxane (7), 0.39 parts of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (8), and 25.4 parts of cyclodimethyltrisiloxane (9) were used. The fluorine content of the fluorinated organopolysiloxane was 35.0% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the total peak area measured by GPC was 16%.

[0147] (A-3)

[0148] [Chemical formula 11]

[0149]

[0150] (Synthesis Example 4) Synthesis of fluorinated organopolysiloxane (A-4)

[0151] [Chemical formula 12]

[0152]

[0153] A fluorinated organopolysiloxane (A-4) was synthesized in the same manner as in Synthesis Example 1 except that 100 parts of the cyclotrisiloxane (10) having a fluorinated substituent, 0.22 parts of the cyclomethylvinyltrisiloxane (7), 0.17 parts of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (8), and 11.8 parts of the cyclodimethyltrisiloxane (9) were used. The fluorine content of the fluorinated organopolysiloxane was 52.0% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the total peak area measured by GPC was 8%.

[0154] (A-4)

[0155] [Chemical formula 13]

[0156]

[0157] (Synthesis Example 5) Synthesis of fluorinated organopolysiloxane (A-5)

[0158] A fluorinated organopolysiloxane (A-5) was synthesized in the same manner as in Synthesis Example 1 except that 100 parts of cyclotrisiloxane (6) having a fluorinated substituent, 1.52 parts of cyclomethylvinyltrisiloxane (7), 1.21 parts of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (8), and 141.9 parts of cyclodimethyltrisiloxane (9) were used. The fluorine content of the fluorinated organopolysiloxane was 18.0% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the total peak area measured by GPC was 14%.

[0159] (A-5)

[0160] [Chemical formula 14]

[0161]

[0162] (Synthesis Example 6) Synthesis of fluorinated organopolysiloxane (A-6)

[0163] A fluorinated organopolysiloxane (A-6) was synthesized in the same manner as in Synthesis Example 1 except that the operation was repeated until the peak area of ​​the component having a molecular weight of 4,000 or less in the GPC measurement was less than 2% of the total peak area. The fluorine content of the fluorinated organopolysiloxane was 44.0% by mass, and the peak area of ​​the component having a molecular weight of 4,000 or less in the total peak area in the GPC measurement was 0.5%.

[0164] (Synthesis Example 7) Synthesis of fluorinated organopolysiloxane (A-7)

[0165] A fluorinated organopolysiloxane (A-7) was synthesized in the same manner as in Synthesis Example 1 except that the washing conditions were set to 100° C. and 30 mmHg for 30 minutes. The fluorine content of the fluorinated organopolysiloxane was 44.0% by mass, and the peak area of ​​components having a molecular weight of 4,000 or less in the total peak area measured by GPC was 28%.

[0166] (Synthesis Example 8) Synthesis of fluorinated organohydrogenpolysiloxane (B-1)

[0167] [Chemical formula 15]

[0168]

[0169] [Chemical formula 16]

[0170]

[0171] 100 parts of organohydrogenpolysiloxane (11) and 194 parts of allyl ether of perfluoropolyether (12) were mixed and stirred, and an addition reaction was carried out using platinum vinylsiloxane complex CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) as a catalyst. The mixture was treated with activated carbon, filtered, and washed to obtain a fluorine-containing organohydrogenpolysiloxane (B-1) represented by the following molecular formula.

[0172] [Chemical formula 17]

[0173]

[0174] (Examples and Comparative Examples)

[0175] Organohydrogenpolysiloxane (B-1) was mixed with each of the organopolysiloxanes containing alkenyl substituents and fluorine-containing substituents represented by (A-1) to (A-7) above so that the molar ratio of hydrogen atoms bonded to silicon atoms in the component (B) to the vinyl groups in the component (A) (molar ratio of Si-H groups / Si-CH=CH2 groups) was 3.0, 100 parts of the resulting mixture was diluted with 1,900 parts of a non-halogen solvent (isooctane:isobutyl acetate=1:1), and a complex of chloroplatinic acid and vinylsiloxane was added thereto in an amount of 30 ppm based on the mass of platinum relative to the component (A) (Tables 1 and 2).

[0176] The solubility of the silicone composition solution obtained in the above manner in non-fluorine-containing solvents, coating properties on film substrates, adhesion, peel strength, and residual adhesion ratio were measured by the following methods.

[0177] (a) Solubility

[0178] 50 g of the samples (solid content concentration 5%) prepared in the above Examples and Comparative Examples were placed in a 100 mL glass bottle with a transparent cap, shaken for 5 minutes using a shaker, and the appearance of the samples was observed.

[0179] ○: Transparent △: Slightly turbid ×: White turbidity or separation

[0180] (b) Coating properties on film substrates

[0181] A bar coater was used so that the coating amount was 0.3 g / m 2 The sample prepared in the above example (dilution solvent: isooctane / isobutyl acetate = 50:50) was coated on a PET film having a thickness of 50 μm in a manner of 1:1. The appearance of the coated film was observed.

[0182] ○: No liquid shrinkage or uneven coating

[0183] △: There is a little liquid shrinkage or uneven coating

[0184] ×: Liquid shrinkage or uneven coating

[0185] (c) Adhesion to substrate

[0186] The film obtained in (b) was heat-cured in a hot air dryer at 150° C. for 60 seconds to form a release layer. After the film formed with the release layer was stored at room temperature for 24 hours, the release layer was rubbed 10 times with fingers to visually observe whether it fell off.

[0187] ○: Not falling off

[0188] △: The color of the film has changed but has not fallen off

[0189] ×: Falling off

[0190] (d) Peel force

[0191] A 25 mm wide silicone adhesive tape (Kapton tape 650S, manufactured by Teraoka Seisakusho Co., Ltd.) was attached to the release film obtained in (c) at a pressure of 20 g / cm 2 The laminated tape was bonded at 25°C and 70°C for 20 hours under a load to allow aging. The bonded tape was peeled off at an angle of 180 degrees and a peeling speed of 0.3 m / min using a tensile tester, and the force required for peeling (N / 25 mm) was measured.

[0192] ○: less than 0.2N / 25mm

[0193] △: 0.2N / 25mm or more and less than 1.0N / 25mm

[0194] ×: 1.0N / 25mm or more

[0195] (e) Residual bonding rate

[0196] The same adhesive tape as used in the peeling test was attached to the release film obtained in (c) and the mixture was stirred at 20 g / cm 2 The adhesive tape was peeled off and pasted on a SUS plate under a load of 25°C for 20 hours to allow it to mature. After aging, the adhesive tape was peeled off using a tensile testing machine at an angle of 180 degrees and a peeling speed of 0.3m / min, and the force required for peeling (N / 25mm) was measured. On the other hand, the force required for peeling off the adhesive tape not pasted on the peeling film from the SUS plate was measured (N / 25mm), and their ratio was taken and expressed as a percentage.

[0197] ○:More than 90%

[0198] △: 75% or more and less than 90%

[0199] ×: Less than 75%

[0200] [Table 1]

[0201]

[0202] [Table 2]

[0203]

[0204] [Table 3]

[0205]

[0206] Since Comparative Example 1 was not dissolved in a non-fluorine solvent, the coating property, adhesion, peeling force, and residual adhesion rate could not be measured. Since the fluorine content of Comparative Example 2 was less than 25% by mass, the peeling force became larger and the residual adhesion rate also decreased. Since the peak area of ​​the components with a molecular weight of less than 4,000 in the GPC measurement was less than 2% relative to the total peak area, the solubility and coating property of Comparative Example 3 were poor, and the peeling force and residual adhesion rate could not be measured. Since the peak area of ​​the components with a molecular weight of less than 4,000 in the GPC measurement was greater than 20% relative to the total peak area, the adhesion of Comparative Example 4 was poor and the residual adhesion rate was reduced.

[0207] Compared with these comparative examples, the results of the samples of the examples are excellent in solubility in non-fluorinated solvents, coating properties on substrates, and adhesion, and are easy to peel off from silicone adhesives, and the residual adhesion rate is also high. The results of the addition-curable release silicone composition for silicone adhesives of the present invention are that the fluorine content of the component (A) as the base polymer and the amount of the component with a molecular weight of 4,000 or less are extremely important for the release agent for silicone adhesives.

[0208] This specification contains the following protocols.

[0209] [1] An addition-curable release silicone composition for a silicone adhesive, comprising:

[0210] (A) a fluorine-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms in one molecule, wherein the fluorine content is 25 to 50% by mass, and in a molecular weight distribution measurement based on gel permeation chromatography, the peak area of ​​components having a molecular weight of 4,000 or less is 2 to 20% of the total peak area, wherein the (A) fluorine-containing organopolysiloxane is 100 parts by mass;

[0211] (B) an organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, wherein the molar ratio of the hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the alkenyl groups in the component (A) is 0.1 to 15;

[0212] (C) a platinum group metal catalyst, in an amount of 0.5 to 5,000 ppm based on the mass of the platinum group metal relative to the component (A);

[0213] (D) a non-fluorinated solvent in an amount of 100 to 20,000 parts by mass.

[0214] [2] The addition-curable release silicone composition for silicone adhesives according to [1] above, wherein the molar ratio of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the alkenyl groups in the component (A) is 0.5 to 5.

[0215] [3] The addition-curable release silicone composition for silicone adhesives according to [1] or [2], wherein the component (D) is a non-fluorinated solvent having an SP value of 10.0 or less.

[0216] [4] The addition-curable release silicone composition for silicone adhesives as described in [1], [2] or [3] above, wherein the component (D) is at least one selected from hydrocarbon solvents, ketone solvents, ether solvents and ester solvents.

[0217] [5] A release film having a cured product layer of the addition-curable release silicone composition for silicone adhesives described in [1], [2], [3] or [4] formed on at least one outer surface of a film substrate.

[0218] [6] A release paper having a cured product layer of the addition-curable release silicone composition for silicone adhesives described in [1], [2], [3] or [4] formed on at least one outer surface of a paper substrate.

[0219] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and all solutions having substantially the same configuration and exerting the same effects as the technical concept described in the claims of the present invention are included in the technical scope of the present invention.

[0220] Industrial Applicability

[0221] The addition-curable release silicone composition for silicone adhesives of the present invention can be suitably used as a release agent because it has both high handling properties and good release performance. A sheet-like substrate having a cured film composed of the silicone composition is useful for adhesive tapes, adhesive labels, engineering papers, and the like.

Claims

1. An addition-curable release silicone composition for a silicone adhesive, comprising: (A) a fluorine-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms in one molecule, wherein the fluorine content is 25 to 50% by mass, and in a molecular weight distribution measurement based on gel permeation chromatography, the peak area of ​​components having a molecular weight of 4,000 or less is 2 to 20% of the total peak area, wherein the (A) fluorine-containing organopolysiloxane is 100 parts by mass; (B) an organohydrogenpolysiloxane having at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, wherein the molar ratio of the hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to the alkenyl groups in the component (A) is 0.1 to 15; (C) a platinum group metal catalyst, in an amount of 0.5 to 5,000 ppm based on the mass of the platinum group metal relative to the component (A); (D) a non-fluorinated solvent in an amount of 100 to 20,000 parts by mass.

2. The addition-curable release silicone composition for silicone adhesive according to claim 1, wherein: The molar ratio of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) to alkenyl groups in the component (A) is 0.5 to 5.

3. The addition-curable release silicone composition for silicone adhesive according to claim 1, wherein The component (D) is a non-fluorinated solvent having an SP value of 10.0 or less.

4. The addition-curable release silicone composition for silicone adhesive according to claim 2, wherein: The component (D) is a non-fluorinated solvent having an SP value of 10.0 or less.

5. The addition-curable release silicone composition for silicone adhesive according to claim 1, wherein The component (D) is at least one selected from hydrocarbon solvents, ketone solvents, ether solvents and ester solvents.

6. The addition-curable release silicone composition for silicone adhesive according to claim 2, wherein: The component (D) is at least one selected from hydrocarbon solvents, ketone solvents, ether solvents and ester solvents.

7. The addition-curable release silicone composition for silicone adhesive according to claim 3, wherein: The component (D) is at least one selected from hydrocarbon solvents, ketone solvents, ether solvents and ester solvents.

8. The addition-curable release silicone composition for silicone adhesive according to claim 4, wherein: The component (D) is at least one selected from hydrocarbon solvents, ketone solvents, ether solvents and ester solvents. 9 . A release film comprising a film substrate having a cured product layer formed on at least one outer surface of the addition-curable release silicone composition for a silicone adhesive according to claim 1 . 10 . A release paper comprising a paper substrate having a cured product layer of the addition-curable release silicone composition for a silicone adhesive according to claim 1 formed on at least one outer surface thereof.

Images