Curable silicone composition, release coating agent for silicone adhesive, release film and lamination body thereof

Abstract

[Topic] This invention provides a curable polysiloxane composition for use as a release agent to form a release film with low peel force, even when it is a thin layer, from polysiloxane adhesives, especially polysiloxane adhesives with low storage modulus of elasticity at low temperatures. Furthermore, it provides a release film with low peel force and excellent smoothness of the adhesive layer surface after peeling, a laminate, and a method for manufacturing the laminate. [Solution] The present invention relates to the use of a curable polysiloxane composition, a release film having the cured form thereof, etc. The aforementioned curable polysiloxane composition contains (A) a mixture comprising (A1) a fluorinated (poly)ether modified organopolysiloxane having an alkenyl group and (A2) an organopolysiloxane having an alkenyl group and a fluorinated alkyl group, (B) an organohydrogen polysiloxane, (C) an organopolysiloxane having an organic group containing a fluorine atom and not containing a hydrosiliconization reactive group, (D) a catalyst for hydrosiliconization reaction, and (E) an organic solvent.

Description

Technical field

[0001] The present invention relates to a curable polysiloxane composition, a release coating agent comprising the composition, especially a polysiloxane adhesive (pressure-sensitive adhesive) with a low storage elastic modulus at low temperature ), a release film using the release coating agent, especially a release film for a silicone adhesive, and a laminate comprising the aforementioned release film, especially a release film and a silicone adhesive The laminate of the agent.

Prior technology

[0002] Polysiloxane adhesives (pressure-sensitive adhesives) have excellent heat resistance, cold resistance, weather resistance, chemical resistance and electrical insulation, etc., so they are widely used as industrial protection tapes and masking tapes etc., or adhesives for various functional tapes for medical use. In addition, in recent years, it has also been used in so-called assembly applications such as lamination of optical components for liquid crystal displays (display devices, functional films, lenses, etc.). Since the silicone adhesive will strongly adhere to the surface coated with silicone rubber and silicone-based materials, it is not possible to use the usual silicone-based release agents used in acrylic or organic rubber-based adhesives , various curable silicone release agent compositions have been proposed to form a release film capable of easily peeling off silicone adhesives. The composition is coated on a flexible substrate such as a plastic film as a release coating agent to form a release film, and then the release film is bonded with a silicone adhesive to form a sheet-like or roll-like tape of equal volume. Layers are used.

[0003] For example, in Patent Document 1, a curable coating composition is proposed as a silicone adhesive release agent, which includes an organopolysiloxane, an organohydrogenpolysiloxane, a catalyst for hydrosilylation And a hydrosilation reaction inhibitor, the organopolysiloxane containing at least 300 silicon atoms and having 0.5 to 2 mole % of vinyl-containing siloxane units and 30 mole % of fluoroalkyl-containing siloxane units , each molecule of the organohydrogenpolysiloxane has an average of at least 2 silicon atoms bonded to hydrogen atoms, and has compatibility with the aforementioned organopolysiloxane.

[0004] In addition, in Patent Document 2, a release agent composition for polysiloxane adhesives is proposed, which includes an organopolysiloxane, an organohydrogenpolysiloxane, and a catalyst for hydrosilation reaction, and the organopolysiloxane Alkanes have at least 2 silicon-bonded alkenyl-containing organic groups in one molecule, and at least one silicon-bonded fluorine-containing substituent (selected from various fluorine (poly) ethers) in one molecule group), the organohydrogenpolysiloxane has at least 3 silicon atoms bonded to hydrogen atoms in one molecule.

[0005] Furthermore, in Patent Document 3, a release agent for silicone adhesives containing two kinds of fluoroalkyl-modified polydimethylsiloxanes with different amounts of alkenyl groups for the purpose of light release is proposed. A composition, and a release sheet formed by applying the release agent composition for polysiloxane adhesive to a substrate.

[0006] Furthermore, in Patent Document 4, a polysiloxane composition for forming a differential release agent for a polysiloxane adhesive is proposed, which contains organopolysiloxane, organohydrogenpolysiloxane, and a platinum group Metal-based catalyst: The organopolysiloxane contains at least two alkenyl groups bonded to silicon atoms in one molecule, and has at least one fluoroalkyl group and fluoropolyether group as the two types bonded to silicon atoms Fluorine-containing substituents, the content of fluoropolyether groups relative to the total of fluoroalkyl groups and fluoropolyether groups is 1 to 99 mole%, and the organohydrogenpolysiloxane has at least 3 bonds with silicon atoms in one molecule The junction of the hydrogen atom. In addition, in its examples, the following two compositions were prepared and compared for release performance, one of which contained at least one fluoroalkyl group and fluoropolyether group as two kinds of fluorine-containing substituents bonded to silicon atoms organopolysiloxane, and another composition containing only 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl as fluorine-containing substitution Organopolysiloxanes with fluoropolyether groups and organopolysiloxanes with only fluoropolyether groups as fluorine-containing substituents.

[0007] In Patent Document 5, it is proposed to have an organosiloxane peeling control agent having an organic group containing a fluorine atom and not containing a hydrosilylation reactive group, a release agent composition comprising the organosiloxane peeling control agent, And a release sheet comprising a hardened layer containing the hardened product.

[0008] In patent documents 6 and 7, it is proposed that: a curable polysiloxane composition is characterized in that it contains fluoro(poly)ether having alkenyl and fluorine-containing (poly)ether organic groups in a specific ratio Modified organopolysiloxane, fluoroalkyl-containing organopolysiloxane having an alkenyl group and a fluoroalkyl group with 1 to 12 carbons; a peeling sheet comprising the curable polysiloxane composition A peeling layer of a cured product obtained by curing; a laminate comprising a structural unit in which a silicone adhesive layer is laminated on a peeling layer.

[0009] However, in these documents, there is no description or suggestion regarding the combination of a specific peel control agent and a specific curable polysiloxane composition. In particular, there is no record or hint about the technical relationship between the storage modulus of elasticity at low temperature and the oligomeric silicone adhesive, about exerting various remarkable effects and its industrial significance. Conventional Technical Documents Patent Documents

[0010] Patent Document 1: Japanese Patent Laid-Open Publication No. 2-245031 Patent Document 2: Japanese Patent Laid-Open Publication No. 1-74268 Patent Document 3: Japanese Patent Laid-Open Publication No. 2005-60554 Patent Document 4: Japanese Patent Laid-Open 2017-165893 Publication Patent Document 5: Patent WO2016-006252 Publication Patent Document 6: Patent WO2020-138399 Publication Patent Document 7: Patent WO2020-138417 Publication

Content of invention

[0011] The problem to be solved by the invention

[0012] The inventors and others discovered a new technical subject. That is, in order to improve the work efficiency and prevent the The surface of polysiloxane adhesive is rough, etc., and requires lower and stable peeling force. However, in recent years, the demand for silicone-based optically transparent pressure-sensitive adhesives (OCA) in the lamination or construction of display devices such as flexible displays / touch panels has increased. Adhesive layer with sufficient viscoelasticity and low storage elastic modulus at low temperature (-20°C, etc.).

[0013] However, when a previously known composition is used as a release coating to form a release film and then a laminate, the adhesion of polysiloxane with a low storage modulus of elasticity cannot be sufficiently reduced at such a low temperature. The release force between the adhesive layer and the release layer, and even when the release film is peeled off, there will be defects such as roughness or wrinkles on the surface of the silicone adhesive after the release film is peeled off, and sometimes transparency or Visibility is compromised, or yield or performance is adversely affected. If it is possible to maintain a sufficiently small peeling force and a good and smooth bonding surface for the polysiloxane adhesive having such new characteristics to realize a peelable release agent layer, the polysiloxane adhesive with excellent low-temperature characteristics can be used more effectively in industry. Silicone adhesive.

[0014] That is, the object of the present invention is to provide a release film, a release agent for this release film, and a curable polysiloxane composition that can be used as a release agent, and a composition comprising a substrate, a polysiloxane A laminate made of an adhesive layer and a release agent layer. Even if the release layer is a thin layer, the release film can be self-adhering to the silicone adhesive on the release layer, especially those with a low storage modulus of elasticity at low temperatures. The silicone adhesive peels off with a low peeling force, and has a stable peeling force against the silicone adhesive. Furthermore, the release film generally has a release layer formed by coating a release agent on a flexible substrate such as a plastic film. technical means to solve problems

[0015] The present inventors have found that the above-mentioned problems can be solved by a hydrosilylation reaction-curable polysiloxane composition, which comprises (A)( A1) A fluoro(poly)ether-modified organopolysiloxane having at least 2 alkenyl groups and an organic group of a fluoro(poly)ether in one molecule of the fluorine-containing organopolysiloxane and (A2) a molecule Mixture of fluoroalkyl-containing organopolysiloxanes having at least 2 alkenyl groups and fluoroalkyl groups having 1 to 12 carbons, and (C) having organic groups containing fluorine atoms and not containing hydrosilylation reactivity Combination of organopolysiloxane based.

[0016] That is, the curable polysiloxane composition of the present invention is characterized in that it is hydrosilation reaction curable and uses a mixture of organopolysiloxanes having specific fluorine-containing organic groups and alkenyl groups as the main agent , and then add an organopolysiloxane with a fluorine-containing organic group that does not contribute to the hydrosilylation reaction. Furthermore, it is characterized in that the peeling layer obtained by curing the curable silicone composition is used as a peeling layer of a silicone adhesive, especially a silicone adhesive having a low storage elastic modulus at low temperature. Non-toxic coating agents, release films, and laminates.

[0017] Specifically, the curable polysiloxane composition of the present invention contains: (A) a fluorine-containing organic compound mixed with the following (A1) and (A2) components in a mass ratio of 1 / 99 to 99 / 1 Polysiloxane mixture; (A1) Fluoro(poly)ether-modified organopolysiloxane with at least 2 alkenyl groups in one molecule and organic groups containing fluorine(poly)ether; (A2) Fluoroalkyl-containing organopolysiloxanes having at least 2 alkenyl groups and fluoroalkyl groups with 1 to 12 carbons; (B) Organohydrogenpolysiloxanes having at least 3 silicon-bonded hydrogen atoms in one molecule (C) an organopolysiloxane having an organic group containing a fluorine atom and not containing a hydrosilylation reactive group; (D) a catalyst for hydrosilylation reaction; and (E) an organic solvent.

[0018] In addition, the above-mentioned problem can be solved by using the peeling layer formed by curing the curable silicone composition as a peeling layer for a silicone adhesive having a storage modulus of elasticity at -20°C of 5 MPa or less. The release coating agent, release film, and laminate are solved. Invention effect

[0019] By using the curable polysiloxane composition of the present invention as a release coating agent, it is possible to form a release film that can adhere to the silicone on the release layer even if the thickness of the release layer is thin. Adhesives, especially polysiloxane adhesives with low storage modulus of elasticity at low temperature, are peeled off from the release layer with low peeling force. In addition, the release film and laminate of the present invention can place the silicone adhesive disposed on the release layer (including the adhesive formed by the hardening reaction of the release layer on the release layer, and the adhesive formed on the release layer). Bonding) can be peeled stably from the peeling layer with low peeling force, which can maintain the surface of the peeled polysiloxane adhesive with a rough or uniform adhesive surface with few wrinkles, so it can be better used for the uniformity of the adhesive surface. components of display devices or electronic materials.

[0020] In particular, by using the release layer formed by hardening the curable polysiloxane composition of the present invention, it is possible to provide a -20°C solution that is difficult to handle and manufacture release laminates with conventional release agents. Silicone adhesives with a storage elastic modulus of 5 MPa or less, especially sheet / film adhesives, release films and release laminates that exhibit low release force and good release characteristics, can therefore be realized. Polysiloxane adhesive with good viscoelasticity at low temperature and the expansion of its industrial application range.

Implementation

[0022] First, the curable silicon composition of the present invention will be described in detail.

[0023] [Curable polysiloxane composition] The curable silicon composition of the present invention is characterized in that it contains at least: (A) The following (A1) component is mixed in a mass ratio of 1 / 99 to 99 / 1 and (A2) a mixture of fluorine-containing organopolysiloxanes; (A1) a fluoro(poly)ether-modified organopolysiloxane having at least 2 alkenyl groups in one molecule and an organic group of a fluorine-containing (poly)ether (A2) Fluoroalkyl-containing organopolysiloxanes having at least 2 alkenyl groups and fluoroalkyl groups with 1 to 12 carbons in one molecule; (B) having at least 3 silicon atom bonds in one molecule Organohydrogenpolysiloxanes with hydrogen atoms; (C) organopolysiloxanes having organic groups containing fluorine atoms and not containing hydrosilylation reactive groups; (D) catalysts for hydrosilylation reactions; and (E) organopolysiloxanes a solvent; (F) a hydrosilylation reaction controller and other optional components may also be included arbitrarily. Hereinafter, these essential components and other components are demonstrated.

[0024] [(A) component] (A) component is a fluorine-containing organopolysiloxane mixture mixed with the following (A1) component and (A2) component in a mass ratio of 1 / 99 to 99 / 1: (A1 ) Fluoro(poly)ether-modified organopolysiloxane having at least 2 alkenyl groups in the molecule and organic groups containing fluorine (poly)ether; (A2) having at least 2 alkenyl groups in the molecule and having CsF2s+1 Fluoroalkyl-containing organopolysiloxane represented by a fluoroalkyl group represented by -R- (where R is independently a divalent hydrocarbon group, and s is an integer from 1 to 20). Component (A) contains component (A1) and component (A2) at a mass ratio of 1 / 99 to 99 / 1, preferably component (A1) and component (A2) at a mass ratio of 1.5 / 98.5 to 80 / 20 , preferably comprising (A1) component and (A2) component with a mass ratio of 2 / 98 to 70 / 30, especially preferably comprising (A1) component and (A2) component with a mass ratio of 2 / 98 to 45 / 55 . If component (A1) and component (A2) are used in combination, the release force to the silicone adhesive can be obtained based on the arithmetic mean estimated based on the results of using component (A1) or component (A2) separately Low peeling force, and by using in combination with the (C) component described later, the peeling force between the silicone adhesive layer and the peeling layer with a low storage modulus of elasticity at low temperature can be sufficiently reduced, and the peeling after peeling can be made The surface of the silicone adhesive maintains a rough or uniform adhesive surface with few wrinkles.

[0025] The molecular structure of the (A1) component and (A2) component is not limited, and examples include linear, branched, linear, resinous, and cyclic, preferably linear, Or a linear chain with some branches.

[0026] As such (A1) component, preferably the following average composition formula (I): (R13SiO1 / 2)a(R12SiO2 / 2)b(R1SiO3 / 2)c(SiO4 / 2)d(I) (wherein, R1 is the same or different and is independently an alkyl group with 1 to 12 carbons, an alkenyl group with 2 to 12 carbons, an aryl group with 6 to 12 carbons, an aralkyl group with 7 to 12 carbons, or The organic group of fluorine-containing (poly)ether with 2 to 30 carbons, wherein at least two R1 in one molecule are alkenyl groups, at least one is the organic group of fluorine-containing (poly)ether, a is a positive number, and b is positive number, c is 0 or a positive number, d is 0 or a positive number) the organopolysiloxane represented. In addition, regarding a to d in the above formula (I), a is an integer of 2 or more, preferably 2 to 6, b is 1 or more, preferably an integer of 1 to 5,000, and more preferably an integer of 30 to 3,000. Integer, c is 0 or a positive number, d is 0 or a positive number. If the degree of polymerization of the siloxane is less than the lower limit of the aforementioned range, it may be difficult to form a release layer when the curable polysiloxane composition obtained by using the component is used as a release coating agent. If the degree of polymerization of the siloxane exceeds At the upper limit of the above range, the coatability (especially film coatability) of the obtained curable silicone composition may decrease. Furthermore, in formula (I), R1 can also be a small amount of hydroxyl and alkoxy groups within the range that does not impair the purpose of the present invention.

[0027] In the formula (I), the alkyl group having 1 to 12 carbons represented by R1 can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl base, decyl, undecyl and dodecyl, preferably methyl.

[0028] In formula (I), the alkenyl group having 2 to 12 carbon atoms represented by R1 can be exemplified by vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octyl Alkenyl, nonenyl, decenyl, undecenyl and dodecenyl are preferably vinyl or hexenyl, especially vinyl. Furthermore, in formula (I), at least two R1 are alkenyl groups, and the content of the alkenyl groups in terms of vinyl groups is not particularly limited as long as it can form a hardenable composition, but is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, further preferably 0.5% by mass or less. The reason for this is that when the content of the alkenyl group is more than necessary, when the release layer for the silicone adhesive is formed using the curable silicone composition of the present invention as a release coating agent, the release layer may self-destruct. The release force of the silicone adhesive layer becomes higher. In addition, the content in terms of vinyl groups refers to the content calculated by converting alkenyl groups other than vinyl groups into the mass of vinyl groups equivalent in moles.

[0029] In formula (I), the aryl group having 6 to 12 carbon atoms represented by R1 can be exemplified by phenyl, tolyl, and xylyl, preferably phenyl.

[0030] In the formula (I), as the aralkyl group having 7 to 12 carbon atoms represented by R1, benzyl and phenethyl can be exemplified.

[0031] In the formula (I), as the organic group of the fluorine-containing (poly)ether of R1, a group represented by the following formula (1) can be exemplified. Formula (1): F(CF2O)a1(CF2CF2O)a2(CF2CH2O)a3[CF(CF3)CF2O]a4[CF(CF3)CH2O]a5(CF2CF2CF2O)a6(CF2CF2CH2O)a7(CF(CF3))a8( CF2)a9(CH2)a10-O-[CF(CF3)]a11(CF2)a12(CH2)a13- (wherein, a1 to a13 are integers of 0 or more. Among them, at least one of a1 to a9 is 1 The above integer. The total of a1 to a10 is preferably 21 or less, and the total of a11 to a13 is preferably 6 or less. In addition, (CF2O)a1(CF2CF2O)a2(CF2CH2O)a3[CF(CF3)CF2O]a4[CF Repeating units among (CF3)CH2O]a5(CF2CF2CF2O)a6(CF2CF2CH2O)a7[CF(CF3)]a8(CF2)a9(CH2)a10, and (CH(CF3))a11(CF2)a12(CH2) The repeating units in a13 can be randomly bonded respectively)

[0032] As the organic group of the fluorine-containing (poly)ether of R1, it is more preferably a group represented by any one of the following formulas (2), (3), or (4). Formula (2): F[CF(CF3)CF2O]b1[CF(CF3)CH2O]b2-[CF(CF3)]b3(CF2)b4(CH2)b5- (wherein, b1 to b5 are 0 or more b1+b2 is an integer of 1 or more, b3+b4+b5 is an integer of 0 or more. b1+b2 is preferably 21 or less, more preferably 11 or less, and more preferably 6 or less. b3+b4+b5 Preferably less than 6. In addition, the repeating units in (CF(CF3))b3(CF2)b4(CH2)b5 can be randomly bonded respectively) Formula (3): F(CF2CF2CF2O)c1(CF2CF2CH2O)c2- [CF(CF3)]c3(CF2)c4(CH2)c5- (wherein, c1 to c5 are integers above 0, c1+c2 are integers above 1, and c3+c4+c5 are integers above 0. c1 +c2 is preferably 21 or less, more preferably 11 or less, further preferably 6 or less. c3+c4+c5 is preferably 6 or less. In addition, (CF(CF3))c3(CF2)c4(CH2)c5 The repeating units can be randomly bonded respectively) Formula (4): F(CF2)d1(CH2)d2-O-(CH2)d3- (wherein, d1 and d2 are integers above 1, and d3 is 0 The above integers. d1 is preferably less than 10, and d2 and d3 are preferably less than 6 respectively)

[0033] Particularly preferable organic groups of fluorine-containing (poly)ether include the following groups. F[CF(CF3)CF2O]nCF(CF3)CF2O(CH2)3- F[CF(CF3)CF2O]nCF(CF3)CH2O(CH2)3- F[CF(CF3)CF2O]n+1CF(CF3) (CH2)2- F(CF2)m(CH2)2O(CH2)3- In the above formulas, n is preferably 1-20, more preferably 1-10, most preferably 1-5. In addition, m is preferably 1-6.

[0034] In addition, a small amount of the organic group of the following fluorine-containing (poly)ether may be bonded to the silicon atom. F[CF(CF3)CF2O]oCF(CF3)CF2O- F[CF(CF3)CF2O]oCF(CF3)CH2O- F(CF2)p(CH2)2O- In the above formula, o is preferably 1 to 20, More preferably 1-10, most preferably 1-5. In addition, p is preferably 1-6.

[0035] In the case where the organopolysiloxane of formula (I) has two or more fluorine-containing (poly)ether organic groups in each molecule, these may be the same or different from each other.

[0036] Specific examples of the component (A1) include the following fluorine (poly)ether group-containing organopolysiloxanes, but are not limited thereto. In the following formulae, Me and Vi represent a methyl group and a vinyl group, respectively, and F1a, F1b, F1c, F1d, and F1e represent groups shown below, respectively. F1a: CF3CF2CF2O-CF(CF3)CH2O(CH2)3- F1b: F[CF(CF3)CF2O]2CF(CF3)CH2O(CH2)3- F1c: F[CF(CF3)CF2O]3CF(CF3)CH2O( CH2)3- F1d: F[CF(CF3)CF2O]5CF(CF3)CH2O(CH2)3- F1e: F[CF(CF3)CF2O]2CF(CF3)CF2O(CH2)3- with the average composition formula: ( Organopolysiloxane represented by Me2ViSiO1 / 2)2(Me2SiO2 / 2)240(Me(F1a)SiO2 / 2)120; average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 / 2)245(Me(F1b )SiO2 / 2)120 represented by organopolysiloxane; with the average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 / 2)240(Me(F1b)SiO2 / 2)120(MeViSiO2 / 2)3 represented by organic polysiloxane Polysiloxane; the organopolysiloxane represented by the average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)240(Me(F1b)SiO2 / 2)120(MeViSiO2 / 2)6; the average composition formula : (Me2ViSiO1 / 2)2(Me2SiO2 / 2)660(Me(F1b)SiO2 / 2)330(MeViSiO2 / 2)6 The organopolysiloxane represented by the average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 Organopolysiloxane represented by / 2)300(Me(F1c)SiO2 / 2)100(MeViSiO2 / 2)3; with the average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 / 2)240(Me(F1d) Organopolysiloxanes represented by SiO2 / 2)120(MeViSiO2 / 2)3; silicone.

[0037] These polysiloxanes can be produced by previously known methods. For example, the method proposed in Japanese Patent Publication No. 4-28273 is used to manufacture dichlorosilane with fluoro (poly) ether groups, and the method proposed in Japanese Patent Publication No. 3-197484 is used to prepare dichlorosilane from dimethylsilane. Bis(hydrosiloxy)silane with fluorine (poly)ether group is produced by substituting the chlorine atom of dichlorosilane with fluorine (poly)ether group, by using the method proposed in Japanese Patent Application Laid-Open No. 6-321968 to carry out intramolecular dehydrogenation Condensation to produce cyclotrisiloxane substituted with fluorine (poly) ether group, by carrying out equilibrium polymerization with vinyl-containing siloxane using the method disclosed in Japanese Patent Laid-Open No. 64-74268 Manufactured, or produced by non-equilibrium polymerization using the method proposed in Japanese Patent Laid-Open No. 11-246772.

[0038] In addition, the alkenyl functional fluoro(poly)ether-modified organopolysiloxane used as the component (A1) of the present invention can also be produced by making a silicon-containing atom bonded to a hydrogen atom After the hydrosilylation reaction of the polysiloxane with the alkenyl ether containing fluorine (poly) ether groups below the stoichiometric amount and the introduction of fluorine (poly) ether groups, there is a large excess of hydrogen atoms bonded to the unreacted residual silicon atoms Acetylene or terminal dienes such as 1,5-hexadiene and 1,3-butadiene undergo hydrosilylation reaction, and the following polysiloxanes can be exemplified.

[0039] Specific examples of the component (A1) produced in this method include the following fluorine (poly)ether group-containing organopolysiloxanes, but are not limited thereto. In the following formulae, Me, Vi, and Hex each represent a methyl group, vinyl group, and n-hexenyl group, and F1b, F1f, and F1g each represent a group shown below.

[0040] F1b: F[CF(CF3)CF2O]2CF(CF3)CH2O(CH2)3- F1f: contains F[CF(CF3)CF2O]3CF(CF3)CH2O(CH2) in a molar ratio of 1:1 3-, and F[CF(CF3)CF2O]4CF(CF3)CH2O(CH2)3- F1g: F[CF(CF3)CF2O]10CF(CF3)CH2O(CH2)3- with the average composition formula: (Me3SiO1 / 2) Organopolysiloxane represented by 2(Me2SiO2 / 2)200(Me(F1b)SiO2 / 2)100(MeHexSiO2 / 2)4; average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)250 (Me(F1f)SiO2 / 2)110(MeHexSiO2 / 2)4 The organopolysiloxane represented by the average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)190(Me(F1g)SiO2 / 2) Organopolysiloxane represented by 30(MeHexSiO2 / 2)2; represented by the average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)230(Me(F1g)SiO2 / 2)35(MeHexSiO2 / 2)4 organopolysiloxane.

[0041] Furthermore, the content of fluorine atoms in the organic group of the fluorine-containing (poly)ether in one molecule is preferably at least 30% by mass, more preferably at least 35% by mass, and still more preferably at least 40% by mass. The reason is that when the content of fluorine atoms in the component (A1) is 30% by mass or more, the peelable coating obtained by crosslinking the curable silicone composition exhibits good peeling force against the silicone adhesive. . Furthermore, the upper limit of the content of the fluorine atoms in the (A1) component is not particularly limited, but if it is too high, the solubility of the (A1) component itself in the solvent will be reduced, resulting in a reduction in operability, so it is preferably at most 60 % by mass or at most 55% by mass.

[0042] In addition, as the component (A1), one type of organopolysiloxane containing fluorine (poly)ether groups can be used, or two or more types of organic polysiloxanes containing fluorine (poly)ether groups with different average composition formulas can be used. Mixture of siloxanes. In this case, two or more fluorine (poly)ether group-containing organopolysiloxanes may or may not be compatible with each other at 25° C. when mixed without a solvent.

[0043] In addition, as (A2) component, the average composition formula (II) can be exemplified: (R23SiO1 / 2)w(R22SiO2 / 2)x(R2SiO3 / 2)y(SiO4 / 2)z(II) (formula wherein, R2 is the same or different alkyl group with 1 to 12 carbons, alkenyl group with 2 to 12 carbons, aryl group with 6 to 12 carbons, aralkyl group with 7 to 12 carbons or aralkyl group with 1 to 12 carbons 12 fluoroalkyl groups, at least two R2 in one molecule are alkenyl groups, at least one R2 is a fluoroalkyl group with 1 to 12 carbon atoms, w is a positive number, x is a positive number, y is 0 or a positive number, z is 0 or a positive number) represented by organopolysiloxane.

[0044] Regarding w to z in the above formula (II), w is more than 2, preferably an integer of 2 to 6, x is more than 1, preferably an integer of 1 to 5,000, and more preferably 30 to An integer of 4,000, y is 0 or a positive number, and z is 0 or a positive number. If the degree of polymerization of the siloxane is less than the lower limit of the aforementioned range, it may be difficult to form a release layer when the curable polysiloxane composition obtained by using the component is used as a release coating agent. If the degree of polymerization of the siloxane exceeds At the upper limit of the above range, the coatability (especially film coatability) of the obtained curable silicone composition may decrease.

[0045] As the alkyl group, alkenyl group, aryl group, and aralkyl group as R2, the same groups as those listed as R1 can be exemplified.

[0046] As R2, the fluoroalkyl group with carbon atoms of 1 to 12 is preferably CsF2s+1-R-(wherein, R is independently a divalent hydrocarbon group, and s is an integer of 1 to 20) represented by fluorine In the alkyl group, s is an integer ranging from 2 to 6, and R is particularly preferably an alkylene group having 2 to 6 carbon atoms. From the viewpoint of the technical effect of the present invention, at least a part of the fluoroalkyl group in the component (A2) is preferably a fluoroalkyl group represented by C4F9-CH2CH2-, that is, 3,3,4,4,5,5 , 6,6,6-nonafluorohexyl, especially preferably all the fluoroalkyl groups in component (A2) are fluoroalkyl groups represented by C4F9-CH2CH2-.

[0047] Examples of the component (A2) include the following organopolysiloxanes. In addition, in the following formulae, Me, Vi, Hex, and F2a represent methyl, vinyl, n-hexenyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl, respectively. The organopolysiloxane represented by the average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 / 2)750(Me(F2a)SiO2 / 2)750(MeViSiO2 / 2)20; the average composition formula: (Me3SiO1 / 2 )2(Me2SiO2 / 2)440(Me(F2a)SiO2 / 2)330(MeViSiO2 / 2)10 The organopolysiloxane represented by the average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)440( Organopolysiloxane represented by Me(F2a)SiO2 / 2)330(MeHexSiO2 / 2)10; average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 / 2)1450(Me(F2a)SiO2 / 2)1100 Organopolysiloxane represented by (MeViSiO2 / 2)8; organic polysiloxane represented by the average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)1450(Me(F2a)SiO2 / 2)1100(MeViSiO2 / 2)10 Polysiloxane; the organopolysiloxane represented by the average composition formula: (Me2ViSiO1 / 2)2(Me2SiO2 / 2)1250(Me(F2a)SiO2 / 2)1250(MeViSiO2 / 2)10; the average composition formula Organopolysiloxane represented by (Me2ViSiO1 / 2)2(Me2SiO2 / 2)900(Me(F2a)SiO2 / 2)450(MeViSiO2 / 2)10. These can be used by 1 type or in combination of 2 or more types selected from these.

[0048] Furthermore, the content of fluorine atoms in the organic group containing a fluoroalkyl group in one molecule is preferably at least 30% by mass, more preferably at least 35% by mass, and still more preferably at least 40% by mass. The reason for this is that when the content of fluorine atoms in the component (A2) is 30% by mass or more, the peelable coating obtained by crosslinking the curable silicone composition exhibits good peeling force against the silicone adhesive. Furthermore, the upper limit of the content of fluorine atoms in the (A2) component is not particularly limited, but if it is too high, the solubility of the (A2) component itself in the solvent will be reduced, resulting in reduced operability, so it is preferably at most 60 mass % or at most 55% by mass.

[0049] The component (A1) and the component (A2) are preferably a combination of components that are not completely compatible at 25° C. when these components are mixed without a solvent. The meaning of "not completely compatible at 25°C when mixed without a solvent" means that a mixture of two or more fluorine-containing organopolysiloxanes is put into a transparent glass vial with a lid at a mass ratio of 1:1, and Immediately after stirring well at 25°C and visually observing after 24 hours, the mixture became cloudy or separated into two phases, instead of showing a uniform and transparent liquid state. Furthermore, when the fluorine-containing organopolysiloxane is in liquid form such as rubber or paste at 25°C, it refers to heating the mixture to the temperature at which it becomes liquid, stirring it thoroughly and cooling it to 25°C immediately and 24°C. After one hour, the mixture became cloudy or separated into two phases when visually observed, instead of being a uniform and transparent liquid.

[0050] In addition, as the component (A2), one type of fluoroalkyl-containing organopolysiloxane may be used, or a mixture of two or more types of fluoroalkyl-containing organopolysiloxane having different average composition formulas may be used. In this case, two or more kinds of fluoroalkyl group-containing organopolysiloxanes may be compatible with each other at 25°C when mixed without a solvent, or may not be compatible.

[0051] [(B) component] (B) component is an organopolysiloxane having at least 3 silicon atoms bonded to hydrogen atoms (Si-H) in one molecule, and is formed between the component (A) A component that hardens the composition of the present invention by an addition reaction of a hydrosilylation reaction. In particular, component (B) may have a certain amount of fluorine-containing organic groups selected from fluoroalkyl groups with 1 to 12 carbons and fluorine-containing (poly)ether organic groups, and from the viewpoint of the technical effect of the present invention Words are better.

[0052] As the group other than the hydrogen atom bonded to the silicon atom in the (B) component, an alkyl group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, and an aralkyl group having 7 to 12 carbons can be exemplified , a fluoroalkyl group having 1 to 12 carbons, and an organic group of a fluorine-containing (poly)ether having 2 to 100 carbons. Furthermore, a small amount of hydroxyl and alkoxy groups may be bonded to the silicon atom in the component (B) within the range that does not impair the object of the present invention.

[0053] (B) The molecular structure of the component is not limited, and can be exemplified as linear, branched, linear with partial branching, resinous and cyclic, preferably linear or partially branched. Straight chain.

[0054] As such (B) component, an organic polymer represented by the following average composition formula: (R33SiO1 / 2)aa(R32SiO2 / 2)ab(R3SiO3 / 2)ac(SiO4 / 2)ad(III) can be exemplified. silicone.

[0055] In the formula, R3 are the same or different and are independently a hydrogen atom, an alkyl group with 1 to 12 carbons, an aryl group with 6 to 12 carbons, an aralkyl group with 7 to 12 carbons, an aralkyl group with 1 to 12 carbons A fluoroalkyl group or an organic group containing fluorine (poly)ether, wherein at least 3 of R3 are hydrogen atoms. Also, aa is a positive number, ab is a positive number, ac is 0 or a positive number, and ad is 0 or a positive number. Among them, when aa is set to 2, the total of aa to ad is preferably in the range of 5 to 200, the lower limit is 10 or 15, and the upper limit is 150, 120, 100, 80, 70, 60, 50 or 40 Within the range of any combination of upper and lower limits. The reason is that when aa is set to 2, if the total of aa to ad is more than the lower limit of the above-mentioned range, the crosslinking of this composition can be sufficiently advanced, on the other hand, if it is not more than the upper limit of the above-mentioned range, this composition can be fully crosslinked. The operability of the composition is good.

[0056] The alkyl group having 1 to 12 carbon atoms represented by R3 can be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, deca Monoalkyl and dodecyl, preferably methyl.

[0057] In addition, the aryl group having 6 to 12 carbon atoms represented by R3 may be exemplified by phenyl, tolyl and xylyl, preferably phenyl.

[0058] In addition, examples of the aralkyl group having 7 to 12 carbon atoms represented by R3 include benzyl and phenethyl.

[0059] Furthermore, as a fluoroalkyl group having 1 to 12 carbon atoms represented by R3, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3 ,3,4,4,5,5,5-Heptafluoropentyl, 3,3,4,4,5,5,6,6,6-Nafluorohexyl, 3,3,4,4,5, 5,6,6,7,7,7-undecafluoroheptyl, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl, preferably selected from 3,3,4,4,5 ,5,5-heptafluoropentyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 3,3,4,4,5,5,6,6,7, 7,7-Undecafluoroheptyl and 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl, especially 3,3,4 ,4,5,5,6,6,6-Nafluorohexyl.

[0060] In addition, as the organic group of the fluorine-containing (poly)ether represented by R3, the organic group of the fluorine-containing (poly)ether exemplified by the aforementioned R1 can be preferably used.

[0061] The component (B) of the present invention may or may not have a group selected from fluoroalkyl groups and organic groups containing fluorine-containing (poly)ether. Even without using an organohydrogenpolysiloxane having a group containing a fluorine atom as the component (B), by combining it with the above-mentioned component (A), when the composition of the present invention is used as a coating agent and cured, it is possible to obtain The peeling layer has excellent peelability, especially excellent peelability for silicone adhesives, but from the viewpoint of the technical effect of the present invention, it is especially preferable to have a certain amount of these groups containing fluorine atoms. As component (B), it is especially preferred to be represented by the above-mentioned average composition formula (III) and R3 is a hydrogen atom, an alkyl group (especially a methyl group), and a fluoroalkyl group and / or an organic group containing fluorine (poly)ether. Combination of organopolyhydrogensiloxanes.

[0062] When the component (B) of the present invention has a group selected from the group consisting of fluoroalkyl groups and fluorine-containing (poly)ether organic groups, the molecules in the molecule are derived from fluoroalkyl groups and / or The content of fluorine atoms in the organic group of the fluoro(poly)ether is not particularly limited, but is preferably at least 20 mass%, at least 25 mass%, at least 30 mass%, or at least 35 mass%. In addition, the upper limit of the content of fluorine atoms in the component (B) is preferably at most 60% by mass or at most 50% by mass.

[0063] Specific examples of the component (B) include organopolysiloxanes listed below, but are not limited thereto. In the following formula, Me, F2a and F1b respectively represent methyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and the following formula: F[CF(CF3)CF2O] A group represented by 2CF(CF3)CH2O-(CH2)3-. The organopolysiloxane represented by the average composition formula: (Me3SiO1 / 2)2(Me(F2aSiO2 / 2)12(MeHSiO2 / 2)27; the average composition formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)55 (Me(F1bSiO2 / 2)25(MeHSiO2 / 2)25 Represented organopolysiloxane; with an average composition formula: (Me3SiO1 / 2)2(MeHSiO2 / 2)50 Represented organopolysiloxane; with an average composition Formula: (Me3SiO1 / 2)2(Me2SiO2 / 2)30(MeHSiO2 / 2)30 The organopolysiloxane represented by the average composition formula: (Me2HSiO1 / 2)2(Me2SiO2 / 2)30(MeHSiO2 / 2) Organopolysiloxane represented by 30. As (B) component, one kind or a combination of two or more kinds selected from these can be used.

[0064] The content of the (B) component in the curable polysiloxane composition of the present invention is that, relative to the alkenyl group in the (A) component, the molar ratio of silicon atoms bonded to hydrogen atoms is 1 to 20 (silicon Atoms bonded to hydrogen atoms / alkenyl groups), preferably with a lower limit of 0.5, 0.8 or 1 and an upper limit of 18, 17, 16, 15, 14, 13 or 12 of any upper and lower limit within the scope of the combination. The reason for this is that when the content of component (B) is not less than the lower limit of the above range, the crosslinking of the present curable polysiloxane composition can sufficiently proceed. On the other hand, when the content of component (B) is not more than the upper limit of the above range , which can stabilize the properties of the peelable coating obtained.

[0065] [(C) Component] (C) Component is an organopolysiloxane that has an organic group containing a fluorine atom in the molecule and does not contain a hydrosilylation reactive group. A peeling control agent component that imparts excellent peelability to the coating obtained by curing the composition. The release agent layer obtained by the curable polysiloxane composition of the present invention and its effects can not only achieve simple low release characteristics, but also achieve Silicone adhesives that cannot achieve sufficient release characteristics from previous release agents, especially silicone adhesives that have a low storage elastic modulus at low temperatures, have sufficiently low release force and can maintain a uniform surface of the adhesive after peeling state.

[0066] (C) The molecular structure of the component is not limited, and can be exemplified as linear, branched, linear, resinous, and cyclic, preferably linear, or partially branched. Straight chain. As such (C) component, it is preferable to be an organic polymer represented by the average composition formula (IV): (R43SiO1 / 2)ba(R42SiO2 / 2)bb(R4SiO3 / 2)bc(SiO4 / 2)bd(IV). silicone.

[0067] In the formula (IV), R4 is identical or different and is independently an alkyl group with 1 to 12 carbons, an aryl group with 6 to 12 carbons, an aralkyl group with 7 to 12 carbons, an aralkyl group with 1 to 12 carbons Fluoroalkyl groups, or organic groups containing fluorine (poly) ethers. In addition, ba is a positive number, bb is a positive number, bc is 0 or a positive number, and bd is 0 or a positive number. However, when ba is set to 2, the total of ba to bd is preferably in the range of 1 to 5,000, and more preferably an integer of 30 to 3,000.

[0068] The alkyl group represented by R4 having 1 to 12 carbon atoms is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl and dodecyl.

[0069] In addition, as the aryl group having 6 to 12 carbon atoms represented by R4, phenyl, tolyl and xylyl can be exemplified, and phenyl is preferred.

[0070] Examples of the aralkyl group having 7 to 12 carbon atoms represented by R4 include benzyl and phenethyl.

[0071] Furthermore, as the fluoroalkyl group having 1 to 12 carbons that can be represented by R4, the fluoroalkyl group having 1 to 12 carbons exemplified for R2 above can be preferably used.

[0072] In addition, as the organic group of the fluorine-containing (poly)ether represented by R4, the organic group of the fluorine-containing (poly)ether exemplified above for R1 can be preferably used.

[0073] Furthermore, the content of fluorine atoms in the organic group containing fluorine atoms in the component (C) is preferably 20 to 40% by mass, more preferably 23 to 35% by mass, and especially preferably 27 to 34% by mass %. On the other hand, when content of the organic group containing a fluorine atom in 1 molecule is less than the said minimum or exceeds the said upper limit, excellent peelability may not be acquired.

[0074] The aforementioned organopolysiloxane is characterized in that it does not contain a hydrosilylation reactive group in the molecule except for the content of organic groups containing fluorine atoms. In the case where the organopolysiloxane contains a hydrosilylation reactive group, especially in a polysiloxane release agent composition hardened by a hydrosilylation reaction, the organopolysiloxane in the release polysiloxane In the cured product, it is easy to form a covalent bond with a crosslinking agent or a main ingredient, and it may not be possible to achieve excellent peelability as a peeling control agent.

[0075] In addition, the molecular chain terminals of the organopolysiloxane are preferably trimethylsiloxy groups or silanol groups, and more preferably one or more molecular chain terminals are trimethylsilyl groups.

[0076] As such an organopolysiloxane, specifically, methyl (3,3,3-trifluoropropyl)polysiloxane whose molecular chain ends are terminated by trimethylsiloxy groups can be exemplified. Alkane, methyl (3,3,3-trifluoropropyl) siloxane-dimethylsiloxane copolymer terminated by trimethylsiloxy at both ends of the molecular chain, trimethylsiloxane copolymer at both ends of the molecular chain Silaneoxy-terminated methyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl) siloxane-dimethylsiloxane copolymer, the two ends of the molecular chain are composed of three Methylsilyloxy-terminated methyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)siloxane-dimethyl Siloxane copolymer, methyl (3,3,3-trifluoropropyl) siloxane-dimethylsiloxane copolymer with silanol groups at both ends of the molecular chain, and silane at both ends of the molecular chain Alcohol-terminated methyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl) siloxane-dimethylsiloxane copolymer, with silanol at both ends of the molecular chain Group-terminated methyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)siloxane-dimethylsiloxane copolymer and methyl (3,3,4,4,5,5,6,6,6-nonafluoro Hexyl) siloxane-dimethylsiloxane copolymer.

[0077] With respect to 100 parts by mass of component (A), the content of component (C) is within the range of 0.01 to 20 parts by mass, preferably within the range of 0.1 to 10 parts by mass. When content of (C) component is less than 0.01 mass part with respect to 100 mass parts of (A) components, the light peelability with respect to the adhesive substance of the coating (peelable cured coating) obtained by hardening may fall remarkably. Moreover, when content of (C)component exceeds 20 mass parts, the strength of the coating layer obtained by hardening may fall remarkably, and it may become difficult to obtain the target release agent composition.

[0078] In addition, as the component (C) of the present invention, one of these organopolysiloxanes may be used alone or in combination of two or more.

[0079] [(D) Component] (D) Component is a catalyst for hydrosilylation reaction that promotes the hardening of the curable polysiloxane composition based on the hydrosilylation reaction, and examples include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. The catalyst is preferably a platinum-based catalyst. Examples of the platinum-based catalyst include platinum fine powder, platinum black, platinum-carrying silicon dioxide fine powder, platinum-carrying activated carbon, chloroplatinic acid, an alcohol solution of chloroplatinic acid, and complexes of platinum and olefins. compounds, and complexes of platinum and alkenyl siloxane.

[0080] The content of component (D) is the amount used to promote the hardening of the curable polysiloxane composition, specifically the metal atoms in the catalyst relative to the curable polysiloxane composition in mass units, relatively Preferably, the amount of platinum atoms is in the range of 0.1 to 1,000 ppm. The reason is that when the content of component (D) is more than the lower limit of the above-mentioned range, the obtained curable polysiloxane composition will be fully cured. On the other hand, when the content of component (D) is below the upper limit of the above-mentioned range, The obtained hardened product is less likely to be colored. [(E) Component] The (E) component is an arbitrary organic solvent capable of uniformly dissolving the fluorine-containing organopolysiloxane mixture as the (A) component, and capable of compatibilizing the entire composition. Here, "compatibility" refers to a uniform and transparent liquid that does not appear cloudy at 25°C.

[0082] In addition, by adding an organic solvent, the viscosity of the curable polysiloxane composition can be reduced, and the coating workability or wettability to the substrate can be improved.

[0083] As (E) component, preferably selected from diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, di-secondary butyl ether, di-tertiary butyl ether, methyl Base-tertiary butyl ether, ethyl-tertiary butyl ether, pentane, hexafluoro-m-xylene, methyl heptafluoropropyl ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, and 3-methoxy One solvent in the group consisting of 1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluorohexane or two or more solvents Mixed media.

[0084] On the condition that the appearance of the curable polysiloxane composition can be kept transparent and uniform at 25° C. from preparation to use, other organic solvents may be used in addition to the above-mentioned organic solvents. Such additional organic solvents are not particularly limited, and examples include: aromatic hydrocarbon solvents such as toluene and xylene; hexane, heptane, octane, isooctane, decane, cyclohexane, and methylcyclohexane , isoparaffin and other aliphatic hydrocarbon solvents; industrial gasoline (rubber volatile oil, etc.), petroleum ether, solvent naphtha and other hydrocarbon solvents; acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone and other ketone solvents; ethyl acetate, propyl acetate, isoacetic acid Propyl, butyl acetate, isobutyl acetate and other ester solvents; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, 2-butoxyethyl acetate Solvents with ester and ether moieties; hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tri(trimethylsiloxane) base) methyl silane, tetrakis (trimethylsiloxy) silane and other siloxane solvents; the aforementioned hexafluoro-m-xylene, methyl heptafluoropropyl ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether , and fluorine-modified solvents other than 3-methoxy-1,1,1,2,2,3,4,4,5,5,6,6,6-tridecafluorohexane, such as trifluorotoluene Other fluorine-modified aromatic hydrocarbon solvents, perfluoro(2-butyltetrahydrofuran) and other fluorine-modified ether-based solvents, perfluoro-tributylamine, perfluoro-tripentylamine and other fluorine-modified alkylamine-based solvents; And a mixed solvent of two or more selected from these.

[0085] The content of component (E) is the amount required to make the curable polysiloxane composition uniformly dissolve as a whole, and is 10,000 parts by mass or less, preferably 20 parts by mass, relative to 100 parts by mass of component (A). to within the range of 5,000 parts by mass.

[0086] [Component (F)] In order to control the cross-linking reaction, (F) a hydrosilylation reaction control agent may be contained in the curable polysiloxane composition. Examples of the (F) component include: 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyne-3-ol Alkynols such as alcohol, 2-phenyl-3-butyn-2-ol, etc.; 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne, etc. Enynes; 1,3,5,7-Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-Tetramethyl-1,3,5 , 7-tetrahexenyl cyclotetrasiloxane and other methylalkenyl siloxane oligomers; dimethylbis(3-methyl-1-butyne-3-oxy)silane, methylvinylbis (3-Methyl-1-butyne-3-oxy)silane and other alkynyloxysilanes; methyltris(1-methyl-1-phenyl-propynyloxy)silane, dimethylbis(1- Methyl-1-phenyl-propynyloxy)silane, methyltris(1,1-dimethyl-propynyloxy)silane, dimethylbis(1,1-dimethyl-propynyloxy) alkynyloxysilane compounds such as base) silane; and benzotriazole; diallyl maleate, diallyl fumarate, tris((1,1-dimethyl-2-propane Alkynyl)oxy)methylsilane.

[0087] The content of component (F) is not limited, and in consideration of giving sufficient pot life to the curable polysiloxane composition, when using component (F), its amount is relative to 100% by mass of component (A) parts, preferably within the range of 0.01 to 5 parts by mass, within the range of 0.05 to 5 parts by mass, or within the range of 0.05 to 3 parts by mass. [Other additives] In this curable polysiloxane composition, it is also possible to use a photopolymerization initiator, an antioxidant, a reactive diluent, and a leveling agent within the range that can achieve the purpose of the present invention. , fillers, antistatic agents, defoamers and additives in pigments, etc.

[0089] [Use] The curable polysiloxane composition of the present invention is preferably used as a release coating agent, and is suitable for use as a release coating agent for silicone adhesives. In particular, it is most suitable as a release coating agent for silicone adhesives with a low storage modulus of elasticity at low temperatures. Specifically, for polysiloxane adhesives with a storage elastic modulus at -20°C of 5 MPa or less, preferably 2.5 MPa or less, and more preferably 1.0 MPa or less, it is possible to maintain a low peeling force and uniform adhesiveness after peeling. In terms of the surface of the adhesive layer, it greatly expands its industrial applicability to silicone adhesive films / sheets that cannot ensure sufficient operability with conventional release agents.

[0090] The present invention also relates to a release film comprising: a base material, especially a film-like base material; and a release layer comprising a cured product obtained by curing the release coating agent of the present invention. Such a release film can be produced, for example, by applying the curable silicone composition of the present invention to a film-like substrate and curing the curable silicone composition. The release film of the present invention is especially suitable for use as a silicone adhesive.

[0091] As the base material for the release film, a film-like base material selected from paper or plastic film, glass, and metal can be used. When using the product provided with the release layer on the substrate as a release film, the substrate is preferably a plastic film, more preferably a polyester film. More preferably, both the base material and the peeling layer are light-transmitting.

[0092] The thickness of the release layer is preferably 2.0 µm or less, 1.0 µm or less, or 0.5 µm or less, more preferably 0.4 µm or less, and even more preferably 0.3 µm or less. In addition, it is preferably at least 0.05 µm, more preferably at least 0.1 µm. This is because when the film thickness is not less than the lower limit of the above range, the peeling force of the obtained release layer is sufficiently reduced, and on the other hand, when the film thickness is not more than the upper limit of the above range, the light transmittance of the release layer is particularly excellent. [Laminate] The present invention also relates to a laminate comprising a structure comprising at least a release layer comprising a cured product obtained by curing the curable polysiloxane composition of the present invention, and the The adhesive layer disposed opposite to the release layer, especially the polysiloxane adhesive layer. In this case, the curable silicone composition may also be called a release coating agent. In this case, "opposite" means that the release layer and the adhesive layer are directly in contact with each other. Therefore, in general, in the present invention, the release layer and the adhesive layer are arranged to face each other. In the following description, the structure of the laminate of the present invention will be described by citing a silicone adhesive as an adhesive, but the adhesive is not limited to the silicone adhesive.

[0094] The laminate of the present invention may be a laminate of any structure as long as it includes the above-mentioned structure in which the release layer and the silicone adhesive layer are opposed to each other. An example of a specific laminate will be described below.

[0095] The constitution of the laminate of the present invention includes, for example, (a) to (d) shown below. These specific structures are, for example, the same as those disclosed by the applicant in the aforementioned Patent Document 6 and Patent Document 7, and the release layer is replaced by a hardened layer formed by hardening the curable polysiloxane composition of the present invention. A silicone adhesive layer having a storage elastic modulus at -20°C of 5 MPa or less can be preferably used as the silicone adhesive layer. (a) Consisting of 1st base material / peeling layer / polysiloxane adhesive layer / 2nd base material; (b) Consecutive lamination of two or more structural units comprising base material / peeling layer / polysiloxane adhesive layer The resulting composition; (c) Composition comprising the first base material / first release layer / polysiloxane adhesive layer / second release layer / second base material; (d) comprising base material / first release layer / A configuration in which two or more constituent units of the silicone adhesive layer / second release layer are stacked in succession. In configurations (b) and (d), the base material can be discontinuous or continuous. Generally speaking, in the case of discontinuity, the laminate becomes a sheet, and in the case of continuous substrate, the laminate become a roll.

[0096] The base material is preferably a sheet or a film, especially a film base, and the same base material as that used for the above-mentioned release film can be used. In addition, any one of translucency and non-translucency may be used for the substrate, and when a plurality of substrates are used, both may be combined arbitrarily according to the purpose.

[0097] The laminate of the present invention can be a laminated sheet formed by laminating a plurality of sheet-shaped members of the base material / peeling layer / polysiloxane adhesive layer in the vertical direction, and can also be in the shape of a roll , For example, the shape of a roll wound around an appropriate cylindrical or cylindrical core.

[0098] In the laminate of the present invention, the polysiloxane adhesive layer is configured such that the first release layer is arranged facing one of its two sides, and the second release layer is arranged facing the other face. In the case (e.g. corresponding to configuration (c) or (d)), at least one of the first peeling layer and the second peeling layer must be a peeling layer containing a hardened product obtained by curing the peeling coating agent of the present invention, However, here, the peeling force (F1) when peeling the silicone adhesive from the first release layer is preferably different from the peeling force (F2) when peeling the silicone adhesive from the second release layer.

[0099] When the difference in peeling force between F1 and F2 is small, after the operation of peeling one peeling layer from the silicone adhesive layer (peeling of the first facing surface), the operation of peeling the other peeling layer (the first peeling layer) 2 facing surface), sometimes when the first facing surface is peeled off, the second facing surface is partially peeled off unintentionally, and the polysiloxane adhesive layer is destroyed, making it difficult to use as an adhesive originally intended. The peel strength is poor, for example, preferably at least 10 gf / inch, more preferably at least 20 gf / inch.

[0100] As a method for realizing the above-mentioned difference in peeling force, a method of selecting the method of forming the facing surface as described below, or a method of making the types of the two peeling layers different, etc. may be mentioned.

[0101] In the laminate of the present invention, the thickness of the release layer is independently preferably 2.0 µm, 1.0 µm, or 0.5 µm or less, more preferably 0.4 µm or less, and even more preferably 0.3 µm or less. In addition, it is preferably at least 0.05 µm, more preferably at least 0.1 µm. The reason is that when the film thickness of the release layer is more than the lower limit of the above-mentioned range, the release force of the release layer from the silicone adhesive becomes sufficiently low. On the other hand, if it is below the upper limit of the above-mentioned range, the light transmission of the release layer It is particularly excellent in performance, and also excellent in economical efficiency.

[0102] The silicone adhesive composition or curable silicone adhesive composition that can be used in the laminate of the present invention is not limited to specific ones, and can be used for the purpose of the laminate, for example, as an adhesive It is optional according to the application of the tape, but it is especially preferable to use a silicone adhesive with a low storage modulus of elasticity at low temperature.

[0103] The hardening mechanism of the curable polysiloxane adhesive is not particularly limited. Hydrosilication curable, peroxide curable, photocurable polysiloxane adhesives, etc. can be used, and the following hydrosilicone adhesives can be preferably used. Curable polysiloxane adhesive can be cured at a relatively low temperature and can reduce the impact of heat on the substrate or applied materials. On the other hand, it also has excellent economical efficiency including the simplicity of the manufacturing process.

[0104] In addition, the release layer of the present invention is very useful for silicone adhesives with low storage elastic modulus at low temperatures. In assembly applications, especially OCA applications, sometimes high adhesion and high flexibility are required in a wider temperature range including low temperatures. Therefore, it is preferable to use the following polysiloxane adhesives, which can be cured The glass transition temperature of the adhesive composition is low, for example, it is designed to be below room temperature, and the storage elastic modulus at low temperature is suppressed to be low, and it has a sufficiently large elongation at break. For example, the silicone adhesive composition proposed by the applicant in International Publication No. 2017 / 188308, International Publication No. 2020 / 32285, International Publication No. 2020 / 32286, etc. is hardened and- A polysiloxane adhesive layer having a storage elastic modulus at 20° C. of 5 MPa or less, preferably 2.5 MPa or less, more preferably 1.0 MPa or less can be particularly preferably used in the present invention. Here, the peeling layer of the present invention does not hinder the application of polysiloxane adhesives with high storage elastic modulus at low temperatures, and can maintain a sufficiently reduced peeling force for polysiloxane adhesives and a uniform adhesive layer surface after peeling .

[0105] The thickness of the polysiloxane adhesive layer of the laminate of the present invention is not particularly limited, preferably 0.1 to 300 µm, more preferably 0.5 to 200 µm.

[0106] In addition, in the laminate of the present invention, the silicone adhesive layer may be formed on the entire surface constituting the layer, or may be formed on only a part of the surface. The aspect in which the silicone adhesive layer is formed on only a part of the surface is not particularly limited, for example, one or more dots, one or more straight lines or curves, concentric circles, etc., and any shape can be applied. Cloth silicone adhesive. The peeling layer may be formed on the entire surface constituting the peeling layer, or the peeling layer may be formed according to the shape made by the silicone adhesive formed on the silicone adhesive layer.

[0107] [Manufacturing method of laminated body] The method for manufacturing the above-mentioned laminated body of the present invention is not particularly limited, and some preferred methods are listed below. First, when producing the laminate of the present invention, the following two methods can be exemplified as methods for preparing the facing surfaces of the silicone adhesive layer and the release layer.

[0108] <Preparation method (1) of the opposite surface of the polysiloxane adhesive layer and the release layer> The first preparation method of the opposite surface includes: Process (1), which is coated on a film-shaped substrate by the present invention A release coating agent composed of a curable polysiloxane composition is cured to form a first release film with a first release layer; on the same film base as the above film base or with the above film Process (2) of forming a polysiloxane adhesive layer by applying a curable polysiloxane adhesive composition on a second film-like substrate with a different substrate and hardening it; and process (3) by The release layer of the first release film obtained by the above process (1) is pasted on the silicone adhesive layer obtained by the above process (2).

[0109] <Preparation method (2) of the opposite surface of the silicone adhesive layer and the peeling layer> This preparation method is to make the hardened peeling layer and the hardened silicone adhesive layer contact to form a pair of two layers. face-to-face approach. The second preparation method of the opposite surface includes: Process (1), which is to apply a peeling coating agent composed of the curable polysiloxane composition of the present invention on the film substrate and harden it, thereby forming a The first peeling film of the first peeling layer; process (2), which is formed by applying a curable silicone adhesive composition on the first peeling film obtained by the above process (1) and curing it Polysiloxane adhesive layer; and process (3), which is to attach the same film-shaped substrate as the above-mentioned film-shaped substrate or the same film-shaped substrate as the above-mentioned Film substrates with different film substrates. This preparation method is a method of coating a curable polysiloxane adhesive on the hardened peeling layer and making it harden to form the opposite surface of the two layers. Generally speaking, in most cases, the difference in peeling force between the silicone adhesive and the release agent in the second method is higher than that in the first method.

[0110] Regarding the configuration examples (a) to (d) of the above-mentioned laminated body of the present invention, for example, it can be carried out by the same manufacturing method as that disclosed by the applicant of the present application in the aforementioned Patent Document 6 and Patent Document 7. Manufacturing, at this time, replace the peeling layer with a hardened layer formed by hardening the curable polysiloxane composition of the present invention, preferably with a storage modulus of elasticity at -20°C of 5 MPa or less, preferably The polysiloxane adhesive layer is below 2.5 MPa, more preferably below 1.0 MPa, as the polysiloxane adhesive layer. Furthermore, the facing surface of the polysiloxane adhesive and the release agent is suitable to use a method corresponding to the above-mentioned preparation method (1) or (2) of the facing surface. Example

[0111] The curable polysiloxane composition and release film of the present invention will be described in detail through examples, but the present invention is not limited by these examples. In addition, in the average composition formula shown below, the symbol Me represents a methyl group, and Vi represents a vinyl group. In addition, the measuring method of the peeling force when peeling a silicone adhesive from a peeling film is as follows.

[0112] <Reference Example 1> Preparation of "Hydrosilication Curable Polysiloxane Adhesive Composition Solution 1" Vinyl functional polydimethylsiloxane (rubber-like (plasticity degree 152), vinyl content 0.013% by mass) 36.4 parts by weight, MQ polysiloxane resin containing (CH3)3SiO1 / 2 units and SiO4 / 2 units and hydroxyl groups (molecular weight 3300, hydroxyl content 3.5 mol% (0.8% by mass) xylene solution ( Solid content 75.5%)) 84.3 parts by weight, toluene 101.6 parts by weight, dimethylsiloxane-methylhydrogensiloxane copolymer (molecular weight 1600, SiH content 0.73%) 0.807 parts by weight, 0.577 parts by weight of 1-ethynyl-1-cyclohexanol (20% toluene solution) are fully mixed at room temperature, and the platinum-based hydrosilation reaction catalyst (containing 0.62 mass % of Platinum) 0.484 parts by weight to prepare a homogeneous solution. Relative to the amount of alkenyl groups in vinyl-functional polydimethylsiloxane, in dimethylsiloxane-methylhydrogensiloxane copolymers whose molecular chain ends are terminated by trimethylsiloxy groups The SiH-based molar ratio (SiH / Vi ratio) was 33.7, and the content of platinum metal relative to the solid content was 30 ppm.

[0113] <Reference Example 2> Adhesion measurement of "hydrosiliconation-curable polysiloxane adhesive composition solution 1" Use an applicator to apply the "hydrosiliconation-curable polysiloxane adhesive composition solution 1" of the above-mentioned reference example Coated on a polyethylene terephthalate (hereinafter referred to as PET) film (manufactured by Toray Co., Ltd., product name: Lumirror (registered trademark) S10, thickness 50 µm) so that the film thickness after curing became 50 µm µm), heated at 150°C for 3 minutes to harden to form a polysiloxane adhesive layer. After standing for 1 day, the sample was cut into a width of 20 mm, and the adhesive layer was bonded to a PMMA plate (manufactured by PALTEK, Acrylite L001, 50×120×2 mm) using a roller, and used as a test piece. The test piece using the PMMA plate was measured using the RTC-1210 tensile testing machine manufactured by ORIENTEC, according to JIS Z0237, using the 180°peel test method at a tensile speed of 300 mm / min to measure the adhesion (measured value of 20 mm wide) Converted to display unit gf / inch), the result is 1490gf / inch.

[0114] <Reference Example 3> Determination of storage elastic modulus of "hydrosiliconation-curable polysiloxane adhesive composition solution 1" Use an applicator to apply the "hydrosiliconation-curable polysiloxane adhesive composition solution" of the above-mentioned reference example 1" Coated on a release liner coated with a fluorine-modified organopolysiloxane release agent so that the cured film thickness becomes 100 µm, heated at 150°C for 3 minutes to harden to form polysiloxane Adhesive layer. This adhesive layer is stacked on 5 or more sheets to obtain a film sample with a thickness of 500 µm or more and both sides sandwiched by a release liner. The film was punched out to a diameter of 8 mm, and attached to a parallel plate probe of a dynamic viscoelasticity device (manufactured by Anoton Paar, MCR301). The storage modulus of elasticity at -20°C was measured and found to be 0.52 MPa. It should be noted that the measurement temperature is in the range of -70°C to 200°C, and the frequency is 1 Hz, and the temperature increase rate is 3°C / min.

[0115] <Measurement method of release force> Use a Mayer bar to apply a curable silicone release agent composition on polyterephthalic acid in such a way that the thickness of the release agent layer after hardening becomes 0.2 µm Ethylene glycol ester (hereinafter, abbreviated as PET) film (manufactured by Toray Co., Ltd., product name: Lumirror (registered trademark) S10, thickness 50 µm), heated at 150°C for 3 minutes to produce a hardened polysiloxane peel The "peeling film" of the layer. Use an applicator to apply the "hydrosiliconation-curable silicone adhesive composition solution 1" of the above-mentioned reference example on the peeling layer of the "peeling film" so that the film thickness after hardening becomes 50 µm, and set the temperature at 150°C Heat for 3 minutes to harden to form a polysiloxane adhesive layer. Using a 2 kg hand pressure roller, the aforementioned PET film was attached to the obtained silicone adhesive layer. The obtained film was cut into a width of 1 inch, and the "peeling film 1" was stretched at a speed of 0.3 m / min in the direction of 180° by using a tensile testing machine (RTC-1210 manufactured by Orientec Co., Ltd.), and measured at 25 The force (peeling force) required to peel off the "peeling film" from the silicone adhesive layer at ℃.

[0116] <Surface state of the silicone adhesive layer after peeling off the release liner> After the above-mentioned measurement of the peeling force, the surface state of the silicone adhesive layer after peeling off the release liner was observed visually. The results are defined as follows. ○: The surface of the adhesive is uniform without roughness or wrinkles ×: The surface of the adhesive is rough and / or wrinkled

[0117] [Examples 1 to 5] and [Comparative Examples 1 to 3] Using the following ingredients, mix the ingredients uniformly according to the composition shown in Table 1, thereby preparing Examples 1 to 5 and Comparative Examples 1 to 3 hardening polysiloxane composition. Furthermore, in the formula, Me, Vi, Fp and Pf respectively represent methyl, vinyl, F(CF(CF3)CF2O)2(CF(CF3))(CH2)O(CH2)3-base, and 3, 3,4,4,5,5,6,6,6-Nafluorohexyl.

[0118] As (A) component, the following components were used. (A1) Average composition formula: organopolysiloxane represented by (Me2ViSiO1 / 2)2(Me2SiO2 / 2)245(MeFpSiO2 / 2)120 with a vinyl group content of 0.06% by mass and a fluorine atom content of 44% by mass The average composition formula of alkane (A2): (Me2ViSiO1 / 2)2(Me2SiO2 / 2)900(MePfSiO2 / 2)450(MeViSiO2 / 2)10 and the content of vinyl group is 0.16% by mass and the content of fluorine atom is 38 mass% organopolysiloxane

[0119] As the (B) component, the following components were used. Average composition formula: organopolysilicon represented by (Me3SiO1 / 2)2(MePfSiO2 / 2)12(MeHSiO2 / 2)27 with a fluorine atom content of 38% by mass and a fluorine atom-bonded hydrogen atom content of 0.50% by mass Oxane

[0120] As the (C) component, the following components were used. Organopolysiloxane represented by (Me3SiO1 / 2)2(Me2SiO2 / 2)900(MePfSiO2 / 2)300 and containing 32% by mass of fluorine atoms

[0121] As (D) component, (D) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (relative to hardened The amount of solid content in the active composition becomes 270 ppm).

[0122] As the component (E), diisopropyl ether was used.

[0123] Component (F): 2-methyl-3-butyn-2-ol was used.

[0124] Prepare a curable silicone composition according to the composition shown in the following table 1, use it as a release coating agent, prepare a release film according to the above method, and measure the release film from the silicone adhesive layer Peel force during peeling. Moreover, the surface state of the silicone pressure-sensitive adhesive layer after peeling off the peeling film was visually observed.

[0125] [Table 1] Element unit of quantity Example 1 Example 2 Example 3 Example 4 Example 5 (A) (A1) parts by mass 4.5 9.5 19.5 29.5 19.8 (A2) parts by mass 94.5 89.5 79.5 69.5 79.7 (B) parts by mass 5.7 5.5 5.3 4.8 5.3 (C) parts by mass 1.0 1.0 1.0 1.0 0.5 (D) ppm 250 250 250 250 250 (E) parts by mass 2665 2665 2665 2665 2665 (F) parts by mass 3.0 3.0 3.0 3.0 3.0 The measurement results Peel force gf / inch 20 18 twenty one 26 20 Surface state of silicone adhesive layer - ○ ○ ○ ○ ○ Element unit of quantity Comparative example 1 Comparative example 2 Comparative example 3 (A) (A1) parts by mass 99.0 - 20.0 (A2) parts by mass - 99.0 80.0 (B) parts by mass 2.4 6.0 5.2 (C) parts by mass 1.0 1.0 - (D) ppm 250 250 250 (E) parts by mass 2665 2665 2665 (F) parts by mass 3.0 3.0 3.0 The measurement results Peel force gf / inch 84 49 72 Surface state of silicone adhesive layer - x x x [Reference Examples 4 to 7] Furthermore, as mentioned above, the release layer of the present invention is preferably a polysiloxane adhesive with a low storage modulus of elasticity applied at low temperatures, but it can also be applied to Silicone adhesives with high storage elastic modulus are shown in Reference Examples 4 to 7.

[0127] <Reference Example 4> Preparation of "hydrosilylation-curable polysiloxane adhesive composition solution 2" The hydrosilylation-curable adhesive DOWSIL(TM) 7657ADHESIVE (solid content 56% by mass) manufactured by Dow Chemical Company was used. 100.0 parts by mass, 0.42 parts by mass of 4000 CATALYST (platinum metal-containing hydrosilylation catalyst) manufactured by Dow Chemical Co., Ltd., and 33.3 parts by mass of toluene were thoroughly mixed to prepare a uniform solution.

[0128] <Reference Example 5> Adhesion measurement of "hydrosiliconation-curable polysiloxane adhesive composition solution 2" In the above-mentioned reference example 2, "hydrosiliconation-curable polysiloxane adhesive composition solution 1" was measured. It was changed to "hydrosiliconation-curable polysiloxane adhesive composition solution 2", and the heat curing condition was changed from 150°C for 3 minutes to 140°C for 5 minutes. The adhesive force was measured by the same method, and the result was 1450gf / Inches.

[0129] <Reference Example 6> The storage elastic modulus of "hydrosiliconation-curable polysiloxane adhesive composition solution 2" was measured in the above-mentioned reference example 3, the "hydrosiliconation-curable polysiloxane adhesive composition solution 1" was changed to "hydrosiliconation-curable polysiloxane adhesive composition solution 2", and the heat curing condition was changed from 3 minutes at 150°C to 5 minutes at 140°C, and the temperature at -20°C was measured using the same method The modulus of elasticity was stored and the result was 9.5 MPa.

[0130] <Reference Example 7> Prepare the curable polysiloxane composition of the above-mentioned Example 3, use it as a release coating agent, prepare a release film according to the above method, and measure the separation of the release film from the silicone adhesive layer. Peeling force. Moreover, the surface state of the silicone pressure-sensitive adhesive layer after peeling off the peeling film was visually observed. As a result, the peeling force was 9 gf / inch, and the surface state of the silicone adhesive was uniform without roughness or wrinkles, so it was evaluated as "○".

[0131] [Summary] The curable polysiloxane compositions of Examples 1 to 5 of the present invention achieved much lower peeling forces than those of Comparative Examples 1 to 3. In addition, the surface of the silicone adhesive layer after peeling off the release liner containing the curable composition of Examples 1 to 5 was in a uniform state, and no roughness or wrinkles were observed. On the other hand, when component (A) is used alone or when component (C) is not used, it is not possible to achieve a sufficient reduction in peeling force for a silicone adhesive with a low storage elastic modulus at low temperature, especially The polysiloxane adhesive layer after peeling is in a non-uniform state, and there is a serious concern that the scope of industrial application will be limited. [Comparative Examples 1 to 3] Furthermore, as confirmed in Reference Example 7, the curable polysiloxane composition of the embodiment of the present invention can also be sufficiently used for storage of polysiloxane with an elastic modulus exceeding 5 MPa at low temperature. Adhesive. Industrial availability

[0132] As shown in the examples, the release film having a release layer formed by using the curable polysiloxane composition of the present invention as a release coating agent for a silicone adhesive can peel off the silicone adhesive with weak force , especially the polysiloxane adhesive with a low storage modulus of elasticity at low temperature, and can evenly maintain the surface of the polysiloxane adhesive after the release film is peeled off, preventing roughness or wrinkles. Therefore, the curability of the present invention The polysiloxane composition can be used not only as a previously commercially available polysiloxane adhesive, but also as a release coating agent for a release film for a polysiloxane adhesive having a low storage elastic modulus at low temperature. In addition, silicone adhesives with low storage elastic modulus at low temperature are contrary to their excellent performance, and there are few release agents with good compatibility, so their application development is often limited, but by using the release coating of the present invention It is easy to provide in the form of a polysiloxane adhesive film / sheet with good peeling properties and low peeling property, and it is strongly expected to expand its industrial use. [Simple description of the diagram]

[0021] none

Claims

1. A release coating agent for polysiloxane adhesives, wherein the polysiloxane adhesive has a storage modulus of elasticity of 1.0 MPa or less at -20°C, the release coating agent comprising a curable polysiloxane composition, the curable polysiloxane composition containing: (A) a mixture of fluorinated organic polysiloxanes containing (A1) and (A2) in a mass ratio of 1 / 99 to 99 / 1; (A1) a fluorinated (poly)ether modified organic polysiloxane having at least two alkenyl groups and a fluorinated (poly)ether organic group in one molecule; (A2) an organic polysiloxane having at least two alkenyl groups and a fluorinated alkyl group having 1 to 12 carbon atoms in one molecule; (B) an organic hydrogen polysiloxane having at least three silicon atoms bonded to hydrogen atoms in one molecule; (C) (A) An organopolysiloxane having an organic group containing fluorine atoms and not containing a hydrosiliconization reactive group; (D) A catalyst for hydrosiliconization reaction; and (E) An organic solvent.

2. The polysiloxane adhesive release coating of claim 1, wherein at least a portion of the fluoroalkyl group of component (A2) is a fluoroalkyl group represented by CsF2s+1-R-, wherein each R is independently a divalent hydrocarbon group, and the s is an integer from 1 to 20.

3. The polysiloxane adhesive release coating as claimed in claim 1 or 2, wherein component (A) is a fluorinated organic polysiloxane mixture containing components (A1) and (A2) in a mass ratio of 2 / 98 to 45 / 55.

4. The polysiloxane adhesive release coating as claimed in claim 1 or 2, wherein component (C) has one or more trimethylsilyl groups at the end of its molecular chain, and the fluorine-containing organic group is one or more groups selected from fluoroalkyl groups having 1 to 12 carbon atoms and fluorine-containing (poly)ether organic groups, and the content of fluorine atoms in the fluorine-containing organic group within the molecule is in the range of 20 to 40% by mass of the organic polysiloxane.

5. The polysiloxane adhesive release coating as claimed in claim 1 or 2, wherein component (B) is an organohydrogen polysiloxane having an organic group having a fluoroalkyl group having a carbon number of 1 to 12 or a fluoro(poly)ether group.

6. The polysiloxane adhesive release coating of claim 1 or 2 contains, relative to 100 parts by weight of component (A), 0.1 to 40 parts by weight of component (B), 0.01 to 20 parts by weight of component (C), 0.1 to 500 ppm of platinum metal in component (D), and 20 to 10,000 parts by weight of component (E).

7. A release film for polysiloxane adhesives, comprising: a film-like substrate; and a release layer comprising a cured material obtained by curing a polysiloxane adhesive release coating as claimed in any one of claims 1 to 6.

8. A laminate comprising a structure in which a polysiloxane adhesive having a storage elastic modulus of 1.0 MPa or less at -20°C is disposed opposite to at least one release layer, wherein the release layer comprises a hardened release layer formed by curing the polysiloxane adhesive as claimed in any one of claims 1 to 6 with a release coating agent.

9. The laminate as claimed in claim 8, wherein the laminate as a whole is at least one shape selected from i) laminated sheet and ii) roll.