Silicone emulsion composition and release film

Abstract

To provide a silicone emulsion composition which cures at relatively low temperatures and in a short time and has stably high adhesion to a plastic film substrate and a release film formed by a cured film of the silicone emulsion composition.SOLUTION: There is provided an addition reaction-curable silicone emulsion composition which comprises an organopolysiloxane (I) having at least two alkenyl groups in the molecule, an organohydrogen polysiloxane (II) having at least two hydrogen atoms directly bonded to silicon atoms in one molecule and a polyvinyl alcohol (IV), wherein the amount of sodium acetate contained in the composition is 450 ppm or less based on the total mass of the organopolysiloxane (I) and the organohydrogen polysiloxane (II).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an addition reaction curable silicone emulsion composition that exhibits good adhesion to plastic film substrates, and to a release film using the same. [Background technology]

[0002] A variety of silicone compositions for release paper have been known for use on substrates such as paper and plastics, of which solvent-based silicones have been widely used due to their excellent release properties and their ability to be used on a relatively wide range of substrates.

[0003] However, in recent years, measures have become necessary to reduce the amount of solvent used and to recover used solvents so that they are not discharged outside, in consideration of environmental pollution, safety, hygiene, etc. Among these, the use of solvent-free silicone is an effective method for reducing the amount of solvent used, and these are applied to paper, laminated paper, and plastic film substrates at a rate of 0.1 to 1.0 g / m 2 To apply a uniform coating at this thickness requires expensive coating equipment and techniques, and changing from solvent-based to solventless silicone is generally not an easy method to adopt.

[0004] Another effective method for reducing the amount of solvent used is the use of emulsion-type silicones. This type of silicone has been used for some time, and examples include a mixture of an emulsion of organovinylpolysiloxane, a platinum compound, an emulsifier, and water with an emulsion of organohydrogenpolysiloxane, an emulsifier, and water; a mixture produced by emulsion polymerization; and a mixture of an emulsion of organovinylsiloxane and organohydrogen with a specific emulsifier and an emulsion of a platinum compound. These silicones can be diluted with water as needed, eliminating the need for expensive coating equipment and techniques for thin-film coating, as with solventless silicones, and offering the advantage of being similar in usability to solvent-based silicones.

[0005] However, emulsion-type silicones are not widely used at present due to the drawbacks of using water as a dispersion medium. One drawback is that high-temperature curing is required due to the large latent heat of vaporization of water, resulting in poorer curing properties compared to solvent-based or solvent-free types. Another drawback is that the high surface tension of water results in poor wettability and poor adhesion to the substrate. These drawbacks are particularly serious when used with plastic film substrates, and are the reason why emulsion-type silicones are rarely used.

[0006] Many improvements have been proposed to address these issues, including the use of organopolysiloxanes with alkenyl groups at the molecular end and emulsions of non-silicone polymers. However, these improvements are mostly aimed at paper substrates, and do not provide sufficient adhesion when coated onto plastic film substrates. Methods using silane coupling agents to improve adhesion have also been reported. The use of glycidoxysilane produces films with low migration and high re-adhesion rates after 7 days, but these methods are primarily intended for in-line coating.

[0007] Japanese Patent Publication No. 2014-233913 (Patent Document 1) describes a method for improving adhesion by forming a primer layer using a coating liquid containing a silane coupling agent, but the number of steps increases because the primer layer is stretched after formation. Japanese Patent Publication No. 2006-348260 (Patent Document 2) describes a method using a silane containing an epoxycyclohexyl group, but this method is also primarily intended for in-line coating. Japanese Patent Publication No. 2017-504674 (Patent Document 3) describes a method for improving abrasion resistance by using as an anchor additive a reaction product of a liquid polyorganosiloxane containing at least one alkenyl group and at least one silanol group with a hydrolyzable silane containing at least one epoxide group, but does not disclose specific peel strength.

[0008] Japanese Patent Application Laid-Open No. 2020-070311 (Patent Document 4) describes an addition reaction curable silicone emulsion composition containing a water-soluble silane coupling agent having at least one of a succinic anhydride group, a quaternary ammonium group, and a ureido group. Japanese Patent Application Laid-Open No. 2003-192896 (Patent Document 5) describes a silicone emulsion composition containing RSiO 2 as a base polymer to improve adhesion. 3 / 2 Silicone emulsion compositions having branched structures containing units are described. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-233913 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-348260 [Patent Document 3] Special Publication No. 2017-504674 [Patent Document 4] Japanese Patent Publication No. 2020-070311 [Patent Document 5] Japanese Patent Application Laid-Open No. 2003-192896 Summary of the Invention [Problem to be solved by the invention]

[0010] However, the silicone emulsion composition described in Patent Document 4 requires a curing temperature of approximately 150°C to cure in a short period of time. Furthermore, the silicone emulsion composition described in Patent Document 5 adheres to various plastic substrates, but requires a curing temperature of 120°C or higher. Therefore, there is a need for a silicone emulsion release agent that can be cured at a lower temperature in a shorter period of time. Furthermore, the silicone cured product obtained by the method described in Patent Document 5 varies in the degree of adhesion, and a silicone emulsion release agent that provides stable and good adhesion is needed.

[0011] As described above, there have been few proposals for silicone emulsions that provide satisfactory adhesion when applied to plastic film substrates, and almost none are in practical use. There is a need for the development of silicone emulsion compositions that can be cured at low temperature and in a short time to give cured films that adhere well to plastic film substrates.

[0012] Therefore, an object of the present invention is to provide a silicone emulsion composition that cures at a relatively low temperature in a short time to give a cured coating that has high adhesion to a plastic film substrate, and a release film on which a cured coating of the silicone emulsion composition has been formed. [Means for solving the problem]

[0013] The present inventors conducted extensive research to solve the above problems and discovered that sodium acetate contained in silicone emulsion compositions inhibits adhesion of cured coatings to plastic substrates. Sodium acetate is produced during the production process of polyvinyl alcohol, one of the raw materials for silicone emulsion compositions. The present inventors discovered that by controlling the amount of sodium acetate in the silicone emulsion composition to 450 ppm or less relative to the total mass of the alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane, the adhesion of the resulting cured coating to plastic substrates can be improved, leading to the completion of this research.

[0014] That is, the present invention provides: [1] Provided is an addition reaction curable silicone emulsion composition comprising an organopolysiloxane (I) having at least two alkenyl groups per molecule, an organohydrogenpolysiloxane (II) having at least two hydrogen atoms directly bonded to Si atoms per molecule, and polyvinyl alcohol (IV), wherein the amount of sodium acetate contained in the composition is 450 ppm or less relative to the total mass of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II).

[0015] Furthermore, the present invention provides the addition reaction curable silicone emulsion composition, which further comprises any one of the following features [2] to [5]: [2] The addition reaction curable silicone emulsion composition, wherein the organopolysiloxane (I) is an organopolysiloxane represented by the following general formula (I-1): [ka] (In formula (I-1), R 1 are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and having no aliphatic unsaturated bonds, and alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R 1 At least two of R are alkenyl groups; 2 are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bonds, alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, hydroxyl groups, and alkoxy groups, and p, q, r, and s are numbers which satisfy 2≦p≦100, 0≦q≦30,000, 0≦r, 0≦s, and 0≦r+s≦200. [3] The addition reaction curable silicone emulsion composition, wherein the amount of the polyvinyl alcohol is 1 to 30 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II). [4] The addition reaction curable silicone emulsion composition contains the following components (I) to (VI): (I) 100 parts by mass of an organopolysiloxane represented by the following general formula (I-1): [ka] (In formula (I-1), R 1are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and having no aliphatic unsaturated bonds, and alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R 1 At least two of R are alkenyl groups; 2 are each independently selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, an alkenyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, a hydroxyl group, and an alkoxy group, and p, q, r, and s are numbers which satisfy the relationship 2≦p≦100, 0≦q≦30,000, 0≦r, 0≦s, and 0≦r+s≦200; (II) an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to Si atoms per molecule: 1 to 60 parts by mass; (III) surfactant: 0.1 to 20 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II); (IV) polyvinyl alcohol: 1 to 30 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II); (V) a catalytic amount of a platinum group metal catalyst, and (VI) Water: 100 to 10,000 parts by mass. [5] Of 100 parts by mass of the organopolysiloxane (I), 15 parts by mass or more is represented by the following average composition formula (I-2): [ka] (In formula (I-2), R 3 are each independently an alkenyl group having 2 to 12 carbon atoms optionally interrupted by an oxygen atom, and R 4 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, and R 5are each independently a hydrogen atom or an alkyl group, t is a positive number of 2 or greater, m is a positive number, and n is 0 or a positive number, satisfying (m+n) / t=0.6 to 1.5 and 0≦n / (m+n)≦0.05, and t, m, and n are numbers such that the viscosity of the organopolysiloxane at 25°C is 5 to 200 mPa s. The addition reaction curable silicone emulsion composition is an organopolysiloxane represented by the formula:

[0016] The present invention also provides a release film comprising a plastic film and a cured coating of the above-described addition reaction curable silicone emulsion composition. [Effects of the Invention]

[0017] The addition reaction curable silicone emulsion composition of the present invention can be cured to provide a cured film that has good adhesion to plastic film substrates. Furthermore, since the cured film has appropriate release properties for pressure sensitive adhesives, it can be used as a release film. Furthermore, the addition reaction curable silicone emulsion composition of the present invention can be cured at low temperatures. Modes for Carrying Out the Invention

[0018] The present invention will be described in further detail below.

[0019] [Silicone emulsion composition] The silicone emulsion composition of the present invention is an addition reaction curable silicone emulsion composition comprising an organopolysiloxane (I) having at least two alkenyl groups per molecule, an organohydrogenpolysiloxane (II) having at least two hydrogen atoms directly bonded to Si atoms per molecule, and polyvinyl alcohol (IV), characterized in that the amount of sodium acetate contained in the composition is 450 ppm or less based on the total mass of the organopolysiloxane (I) and organohydrogenpolysiloxane (II).

[0020] The addition reaction curable silicone emulsion composition of the present invention is characterized by controlling the amount of sodium acetate contained in the composition to 450 ppm or less based on the total mass of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II), thereby enabling low-temperature curing to give a cured product that has good adhesion to conventional plastic film substrates.

[0021] The amount of sodium acetate contained in the addition reaction curable silicone emulsion composition is 450 ppm or less, based on the total mass of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II). It is preferably 400 ppm or less, more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, and particularly preferably 100 ppm or less. By ensuring that the amount of sodium acetate contained in the composition is within the above range, the cured coating obtained by curing the addition reaction curable silicone emulsion composition of the present invention can maintain sufficient adhesion to plastic substrates while also exhibiting appropriate releasability from pressure-sensitive adhesives. The lower limit of the amount of sodium acetate contained in the composition is not particularly limited; the lower limit is the better. Therefore, the lower limit is 0 ppm or greater. It may be, for example, 1 ppm or greater, for example, 2 ppm or greater, for example, 3 ppm or greater, even 4 ppm or greater, and particularly 5 ppm or greater.

[0022] The organopolysiloxane (I) contained in the addition reaction curable silicone emulsion composition of the present invention is preferably represented by the following general formula (I-1): [ka] (In formula (I-1), R 1 are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and having no aliphatic unsaturated bonds, and alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R 1At least two of R are alkenyl groups; 2 are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bonds, alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, hydroxyl groups, and alkoxy groups, and p, q, r, and s are numbers which satisfy the following conditions: 2≦p≦100, 0≦q≦30,000, 0≦r, 0≦s, and 0≦r+s≦200. By using an organopolysiloxane represented by the above general formula (I-1) as the organopolysiloxane, it is possible to impart more desirable properties to the release film obtained from the silicone emulsion composition of the present invention.

[0023] The addition reaction curable silicone emulsion composition of the present invention may further contain a surfactant (III), a catalytic amount of a platinum group metal catalyst (V), and water (VI).

[0024] That is, a more preferred embodiment of the addition reaction curable silicone emulsion composition of the present invention is an addition reaction curable silicone emulsion composition containing the components shown in (I) to (VI) below. (I) 100 parts by mass of an organopolysiloxane represented by the following general formula (I-1): [ka] (In formula (I-1), R 1 are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and having no aliphatic unsaturated bonds, and alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R 1 At least two of R are alkenyl groups; 2are each independently selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, an alkenyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, a hydroxyl group, and an alkoxy group, and p, q, r, and s are numbers which satisfy the relationship 2≦p≦100, 0≦q≦30,000, 0≦r, 0≦s, and 0≦r+s≦200; (II) an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to Si atoms per molecule: 1 to 60 parts by mass; (III) surfactant: 0.1 to 20 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II); (IV) polyvinyl alcohol: 1 to 30 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II); (V) a catalytic amount of a platinum group metal catalyst, and (VI) Water: 100 to 10,000 parts by mass.

[0025] Each of the above components will be described in detail below.

[0026] [Organopolysiloxane (I)] The organopolysiloxane (I) contained in the addition reaction curable silicone emulsion composition of the present invention is preferably an organopolysiloxane represented by the above general formula (1-1). By using an organopolysiloxane represented by the above general formula (I-1) as the organopolysiloxane, it is possible to impart more desirable properties to the release film obtained from the silicone emulsion composition of the present invention.

[0027] In the above formula (I-1), R 1 are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and having no aliphatic unsaturated bonds, and alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R 1 At least two of R are alkenyl groups. 2are each independently selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and not having an aliphatic unsaturated bond, an alkenyl group having 2 to 12 carbon atoms which may contain an oxygen atom, a hydroxyl group, and an alkoxy group.

[0028] Preferable examples of unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bonds include alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and butyl; cycloalkyl groups having 5 to 8 carbon atoms such as cyclohexyl; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl; and aralkyl groups having 7 to 10 carbon atoms such as benzyl. Examples of substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bonds include substituted hydrocarbon groups in which some or all of the hydrogen atoms bonded to carbon atoms of the above-mentioned monovalent hydrocarbon groups have been substituted with hydroxy groups, alkoxy groups, polyether groups, alkoxyalkyl groups, epoxy groups, cyano groups, halogen atoms, or the like, such as hydroxypropyl, chloropropyl, and 3,3,3-trifluoropropyl. In particular, from the viewpoint of releasability, an alkyl group or an aryl group is preferred, and a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferred.

[0029] The alkenyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom is —(CH2) x A group represented by -CH=CH2 (x is 0 or an integer of 1 to 10) is preferred. Examples include vinyl, propenyl, butenyl, hexenyl, octenyl, and decenyl groups. The methylene chain may contain an ether bond. There are no particular restrictions on the position at which the oxygen atom is present (the position of the ether bond), but examples include -(CH2)2-O-CH2-CH=CH2 and -(CH2)3-O-CH2-CH=CH2. Of these, a vinyl group is preferred. In organopolysiloxane (I-1), R 1 At least two of the R are alkenyl groups, and more preferably 2 to 1000 R 1is an alkenyl group, and more preferably 2 to 500 R 1 is preferably an alkenyl group.

[0030] The viscosity of the organopolysiloxane (I) is preferably 5 mPa·s or more at 25°C and 50,000 mPa·s or less when diluted with 30% toluene, more preferably 10 mPa·s or more at 25°C and 50,000 mPa·s or less when diluted with 30% toluene, and even more preferably 50 mPa·s or more at 25°C and 30,000 mPa·s or less when diluted with 30% toluene. If the viscosity of the organopolysiloxane (I) is equal to or greater than the lower limit mentioned above, the storage stability of the silicone emulsion composition is improved. Furthermore, if the viscosity of the organopolysiloxane (I) is equal to or less than the upper limit mentioned above, the silicone emulsion composition is easily emulsified. In the present invention, the viscosity of the organopolysiloxane (I) is measured at 25°C using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.).

[0031] The organopolysiloxane represented by the general formula (I-1) above may be linear, branched, or network-like, but is preferably linear or branched. In the formula (I-1), p, q, r, and s are numbers satisfying 2≦p≦100, 0≦q≦30,000, 0≦r, and 0≦s. p is preferably 2≦p≦50, and more preferably 2≦p≦40. q is preferably 0≦q≦20,000, more preferably 0≦q≦15,000, or even more preferably 1≦q≦15,000. r and s are in the range of 0≦r+s≦200, preferably 0≦r+s≦100, more preferably 0≦r+s≦50, or even more preferably 1≦r+s≦50. r may be 0, and s may be 0. The values ​​of p, q, r, and s may be within the above ranges, and may be values ​​that allow the organopolysiloxane (I) to have the above-mentioned viscosity. In particular, it is preferable that r+s is 200 or less, since this can prevent the product from gelling during the synthesis of the organopolysiloxane (I).

[0032] The organopolysiloxane (I) is the component in the silicone emulsion composition of the present invention that has a significant effect on the release force. By varying the structure and substituents of the organopolysiloxane (I), it is possible to change the release properties of the cured coating of the silicone emulsion composition.

[0033] In the present invention, the organopolysiloxane (I) does not need to be a single composition, and two or more organopolysiloxanes having different structures represented by the above general formula (I-1) may be used in combination. When two or more organopolysiloxanes are used in combination, the blending composition is not particularly limited, as long as the average of the two or more organopolysiloxanes satisfies the requirements represented by the above general formula (I-1).

[0034] Examples of organopolysiloxane (I) represented by general formula (I-1) above include, but are not limited to, the compounds shown below, where Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

[0035] [ka] (50≦q1≦2,500) [ka] (50≦q1≦10,000) [ka] (50≦q1≦19,000, 2≦q2≦500) [ka] (50≦q1≦19,000, 1≦q2≦500) [ka] (50≦q1≦19,000, 1≦q2≦500, 1≦q3≦500) [ka] (50≦q1≦10,000, 0≦q4≦500, 1≦r≦20) [ka] (50≦q1≦5,000, 1≦q3≦500, 0≦q4≦500, 1≦q5≦500, 1≦r≦20) [ka] (50≦q1≦5,000, 1≦q2≦500, 0≦q4≦500, 0≦q6≦500, 1≦r≦20) [ka] (50≦q1≦10,000, 0≦q4≦500, 0≦q7≦500, 0≦q8≦500, 1≦r, 1≦r+s≦20) [ka] (200≦q1≦10,000, 1≦q3≦500, 0≦q4≦500, 0≦q7≦500, 0≦q8≦500, 1≦r and / or s, 1≦r+s≦20)

[0036] Preferably, of 100 parts by mass of the organopolysiloxane (I) of the present invention, at least 15 parts by mass is a branched organopolysiloxane represented by the following average compositional formula (I-2). By containing 15 parts by mass or more of the organopolysiloxane represented by the following average compositional formula (I-2), the adhesion of the resulting cured coating to plastic film substrates is improved. Preferably, of 100 parts by mass of the organopolysiloxane (I), at least 15 parts by mass and at most 80 parts by mass, more preferably at least 20 parts by mass and at most 70 parts by mass, is the organopolysiloxane represented by the following average compositional formula (I-2). That is, the organopolysiloxane (I) of the present invention is preferably a combination of a branched organopolysiloxane (a) represented by the following average composition formula (1-2) and at least one linear, branched, or network organopolysiloxane represented by the above general formula (I-1) and having a structure different from that of the branched organopolysiloxane (a). [ka] In the above formula (I-2), R 3 are each independently an alkenyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R 4 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, and R 5 are each independently a hydrogen atom or an alkyl group, t is a positive number of 2 or greater, m is a positive number, and n is 0 or a positive number, and are values ​​that satisfy (m+n) / t=0.6 to 1.5 and 0≦n / (m+n)≦0.05, and t, m, and n are values ​​that give the organopolysiloxane a viscosity at 25°C of 5 to 200 mPa s.

[0037] In the above formula (I-2), R 3 is an alkenyl group having 2 to 12 carbon atoms which may be interposed by an oxygen atom, and is 1 Among them, vinyl groups are preferred. 4 As mentioned above, 1 and R 2 Among them, alkyl groups and aryl groups are preferred, and methyl groups, ethyl groups, propyl groups, and phenyl groups are more preferred. 5 The alkyl group preferably has 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include a methyl group and an ethyl group.

[0038] In the formula (I-2), t is a positive number of 2 or greater, m is a positive number, and n is 0 or a positive number, and the numbers satisfy (m+n) / t = 0.6 to 1.5. Preferably, the numbers satisfy (m+n) / t = 0.7 to 1.4. It is preferable that (m+n) / t is equal to or greater than the lower limit, because the resulting cured coating has improved adhesion to plastic films. It is also preferable that (m+n) / t is equal to or less than the upper limit, because this facilitates the synthesis of the organopolysiloxane represented by formula (I-2). n / (m+n) is in the range of 0≦n / (m+n)≦0.05, preferably 0≦n / (m+n)≦0.04. It is preferable that n / (m+n) is equal to or less than the upper limit, because the curability of the resulting silicone emulsion composition is not impaired, even if the organopolysiloxane (I-2) contains alkoxy groups or hydroxyl groups.

[0039] The organopolysiloxane (I) of the present invention can be obtained by a known method for producing organopolysiloxanes. For example, it can be produced by co-hydrolyzing a trialkoxymethylsilane with a dialkenyltetramethyldisiloxane or hexamethyldisiloxane in an alcohol solvent using an acid catalyst. Examples of acid catalysts include sulfuric acid, hydrochloric acid, phosphoric acid, activated clay, iron chloride, boric acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. After neutralizing the reaction mixture, the by-product alcohol is removed, followed by washing with water and removal of unreacted materials to obtain the desired organopolysiloxane. Alternatively, an alkali catalyst may be used. Examples of alkali catalysts include KOH, CsOH, NaOH, (CH3)4NOH, (n-C4H9)4POH, and metal siliconates such as potassium and phosphorus siliconates.

[0040] In organopolysiloxane (I-2), it is preferred that 30 to 60 mol %, preferably 40 to 55 mol %, of all siloxane units are trifunctional siloxane units (T units), and that at least 20 mol %, more preferably 20 to 80 mol %, and even more preferably 20 to 60 mol % of all organic groups are vinyl groups. When the proportion of trifunctional siloxane units is at or above the above-mentioned lower limit, the resulting cured coating has improved adhesion to plastic film substrates. Furthermore, when the proportion of trifunctional siloxane units is at or below the above-mentioned upper limit, the silicone emulsion composition is easily emulsified, and a stable emulsion is obtained, which is preferred. Furthermore, when the amount of vinyl groups is at or above the above-mentioned lower limit of all organic groups, the resulting cured coating has improved adhesion to plastic film substrates, which is preferred.

[0041] The organopolysiloxane (I-2) may further contain a monofunctional siloxane unit, a difunctional siloxane unit, or a tetrafunctional siloxane unit that does not contain an alkenyl group, as long as the effects of the present invention are not impaired.

[0042] The organopolysiloxane (I-2) has a viscosity at 25°C of 5 to 200 mPa·s, preferably 10 to 100 mPa·s. A viscosity at or above the lower limit mentioned above ensures that the curability of the silicone emulsion composition is maintained. A viscosity at or below the upper limit mentioned above facilitates improved adhesion of the resulting cured coating. Therefore, in formula (I-2), t, m, and n are numbers selected so that the organopolysiloxane (I-2) has the above viscosity.

[0043] More preferably, the organopolysiloxane (I) of the present invention comprises a combination of a branched organopolysiloxane (a) represented by the average composition formula (I-2) above and a linear or branched organopolysiloxane (b) represented by the general formula (I-1) above, where p = 2, 1 ≦ q ≦ 20,000, preferably 1 ≦ q ≦ 15,000, and 0 ≦ r + s ≦ 50. Even more preferably, the organopolysiloxane (I) of the present invention comprises a combination of a branched organopolysiloxane (a) represented by the average composition formula (I-2) above and a linear organopolysiloxane (b) represented by the general formula (I-1) above, where p = 2, 1 ≦ q ≦ 20,000, preferably 1 ≦ q ≦ 15,000, and r = s = 0. The organopolysiloxane (a) and the organopolysiloxane (b) may each be a single type or a combination of two or more types. The mass ratio of the organopolysiloxane (a) is preferably 15 to 80 parts by mass, more preferably 20 to 70 parts by mass, per 100 parts by mass of the total of the organopolysiloxane (a) and the organopolysiloxane (b).

[0044] [Organohydrogenpolysiloxane (II)] The addition reaction curable silicone emulsion composition of the present invention contains an organohydrogenpolysiloxane (II). The organohydrogenpolysiloxane (II) has at least two hydrogen atoms (SiH groups) directly bonded to Si atoms per molecule. The SiH groups of the organohydrogenpolysiloxane undergo an addition reaction with alkenyl groups in the organopolysiloxane (I). In other words, the organohydrogenpolysiloxane acts as a crosslinking agent to form a cured coating.

[0045] The organohydrogenpolysiloxane (II) is not particularly limited as long as it is a siloxane that does not interfere with emulsification or the stability of the resulting emulsion. In order to impart more desirable properties to the resulting cured coating, linear, branched, or network organohydrogenpolysiloxanes represented by the following general formula (II) are preferred. [ka] In the above formula (II), R 6 is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond, and a, b, c, d, e, f are such that 1 ≦ a, 0 ≦ b, 2 ≦ a + b, 0 ≦ c ≦ 150, 0 < d ≦ 200, and 0 < c + d ≦ 350, 0 ≦ e, 0 ≦ f, which are positive numbers satisfying these conditions.

[0046] In the above formula (II), R 6 is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and no aliphatic unsaturated bond. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, or a monovalent hydrocarbon group selected from hydroxypropyl group, cyanoethyl group, 1-chloropropyl group, and 3,3,3-trifluoropropyl group, etc., in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a hydroxyl group, a cyano group, a halogen atom, etc. Among them, an alkyl group and an aryl group are preferred, and a methyl group is particularly preferred.

[0047] In the above formula (II), a and b are preferably positive numbers satisfying 1 ≦ a ≦ 50, 0 ≦ b ≦ 50, 2 ≦ a + b ≦ 100, more preferably 1 ≦ a ≦ 20, 0 ≦ b ≦ 10, 2 ≦ a + b ≦ 20. c, d, e, f are positive numbers satisfying 0 ≦ c ≦ 150, 0 < d ≦ 200, and 0 < c + d ≦ 350, 0 ≦ e, 0 ≦ f. Preferably, they are positive numbers satisfying 10 ≦ c ≦ 100, positive numbers satisfying 10 ≦ d ≦ 100, positive numbers satisfying 0 ≦ e ≦ 20, and positive numbers satisfying 0 ≦ f ≦ 20. Preferably, it is a linear organohydrogenpolysiloxane with a + b = 2 and e = f = 0.

[0048] The organohydrogenpolysiloxane represented by formula (II) may be used alone or in combination of two or more. The organohydrogenpolysiloxane preferably has an average SiH group content (i.e., the amount of SiH groups per 100 g of organohydrogenpolysiloxane) in the range of 0.001 to 3.5 mol / 100 g, more preferably 0.01 to 2.50 mol / 100 g, and even more preferably 0.02 to 2.00 mol / 100 g. If the SiH group content is within the above range, sufficient curability can be obtained, and the shelf life of the emulsion composition product can be maintained.

[0049] The organohydrogenpolysiloxane (II) preferably has 2 to 300 SiH groups per molecule, preferably 3 to 200, more preferably 4 to 200, and even more preferably 5 to 100. If the number of SiH groups is equal to or greater than the lower limit, good curability can be obtained, and if the number is within the upper limit, an appropriate release force can be obtained.

[0050] The organohydrogenpolysiloxane (II) has a viscosity at 25°C of 1 Pa·s or less, preferably 5 mPa·s to 1 Pa·s, and more preferably 5 mPa·s to 500 mPa·s. When the viscosity is equal to or less than the upper limit, an emulsion composition is easily obtained. The viscosity of the organohydrogenpolysiloxane (II) is measured at 25°C using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.).

[0051] The amount of organohydrogenpolysiloxane (II) blended is adjusted by the amount of alkenyl groups contained in organopolysiloxane (I). Preferably, the ratio of the number of moles of SiH groups in organohydrogenpolysiloxane (II) to the number of moles of alkenyl groups in organopolysiloxane (I) (H / Vi ratio) is 0.40 to 11.0, more preferably 1.0 to 3.0, and even more preferably 1.20 to 2.00. In consideration of cured film formation and its release properties, the amount of organohydrogenpolysiloxane (II) is preferably 1 to 60 parts by mass per 100 parts by mass of organopolysiloxane (I). It is more preferably 2 to 40 parts by mass, and even more preferably 20 to 40 parts by mass. If the content is equal to or greater than the above lower limit, the curability of the addition reaction curable silicone emulsion composition is improved, whereas if the content is equal to or less than the above upper limit, the peel strength of the resulting cured coating does not exceed practical limits, which is preferable.

[0052] [Surfactant (III)] The addition reaction curable silicone emulsion composition of the present invention can contain a surfactant (III). Examples of the surfactant (III) of the present invention include nonionic surfactants, such as polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene propylene alkyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of polyoxyethylene alkyl phenyl ethers include polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, and polyoxyethylene styrenated phenyl ether. Examples of polyoxyethylene propylene alkyl ethers include polyoxyethylene propylene decyl ether, polyoxyethylene propylene lauryl ether, and polyoxyethylene propylene tridecyl ether. Among these, polyoxyethylene lauryl ether and polyoxyethylene styrenated phenyl ether are preferred.

[0053] The nonionic emulsifiers can be used alone or in combination of two or more. To obtain a stable silicone emulsion composition, it is desirable that the HLB of these nonionic emulsifiers, either alone or after mixing, is 10 to 15. HLB is calculated using the following formula: N=N1×W1+N2×W2 N: HLB value when using two surfactants with different HLB values N1, N2: HLB of each surfactant W1, W2: weight fraction of each surfactant (W1 + W2 = 1)

[0054] Although anionic surfactants and cationic surfactants can also be used, it is desirable to use them in combination with nonionic surfactants in terms of the stability of the silicone emulsion and wettability to the substrate. Examples of anionic surfactants include higher alcohol sulfate salts, alkylphenyl ether sulfate salts, alkylbenzene sulfonates, higher alcohol phosphate salts, ethoxylated higher alcohol sulfate salts, and ethoxylated higher alcohol phosphate salts. Examples of cationic surfactants include alkyltrimethylammonium chloride, alkylamine hydrochlorides, alkylamine acetates, and alkylbenzenedimethylammonium chloride.

[0055] The amount of surfactant blended is desirably the minimum amount necessary to achieve sufficient silicone emulsion stability and substrate wettability. Preferably, the amount is 0.1 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, even more preferably 0.3 to 10 parts by weight, even more preferably 0.3 to 8 parts by weight, even more preferably 0.5 to 5 parts by weight, and particularly preferably 0.7 to 3 parts by weight, per 100 parts by weight of the total of organopolysiloxane (I) and organohydrogenpolysiloxane (II). If the amount of surfactant blended is equal to or greater than the lower limit, emulsification becomes easier, and if it is equal to or less than the upper limit, the curing properties of the silicone emulsion are improved.

[0056] [Polyvinyl alcohol (IV)] The addition reaction curable silicone emulsion composition of the present invention contains polyvinyl alcohol. Polyvinyl alcohol can function as a thickener. Preferably, a surfactant and polyvinyl alcohol are used in combination to aid in emulsification of the composition, improve stability, and improve the properties of the cured film.

[0057] As with the surfactant, the amount of polyvinyl alcohol blended is desirably the minimum amount necessary to provide sufficient stability of the silicone emulsion and sufficient wettability to the substrate. The amount of polyvinyl alcohol blended is preferably 1 to 30 parts by mass, more preferably 2 to 22 parts by mass, and even more preferably 3 to 15 parts by mass, per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II).

[0058] The degree of polymerization of polyvinyl alcohol is preferably 500 to 6000, more preferably 1000 to 3000. If the degree of polymerization is higher than 500, the emulsion stability is improved, and if it is lower than 6000, the peel force is not too strong. Furthermore, the degree of saponification of polyvinyl alcohol is preferably 80.0 to 99.0, more preferably 85.0 to 90.0. If the degree of saponification is within this range, the emulsion stability is improved.

[0059] The polyvinyl alcohol used in the present invention may be a commercially available product. Typical polyvinyl alcohols contain approximately 0.01 to 2.0% by mass of sodium acetate, which is generated during the production process and remains after purification. In the present invention, the amount of polyvinyl alcohol blended is adjusted within the above-mentioned range so that the amount of sodium acetate contained in the addition reaction curable silicone emulsion composition is 450 ppm or less, preferably 400 ppm or less, more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, and particularly preferably 100 ppm or less, relative to the total mass of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II). The sodium acetate content in the polyvinyl alcohol blended in the addition reaction curable silicone emulsion composition of the present invention is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, with the lower limit being the better. Polyvinyl alcohol having a sodium acetate content of 0.01 to 0.92% by mass is more preferred, and polyvinyl alcohol having a sodium acetate content of 0.01 to 0.45% by mass is particularly preferred. The amount of sodium acetate in polyvinyl alcohol can be measured by dissolution titration based on JIS K6726-1994.

[0060] [Platinum group metal catalyst (V)] The addition reaction curable silicone emulsion composition of the present invention can contain a platinum group metal catalyst (V). The platinum group metal catalyst (V) is a catalyst for accelerating the addition reaction, and known addition reaction catalysts can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, with platinum-based catalysts being particularly preferred. Examples of platinum catalysts include chloroplatinic acid, alcohol solutions or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and complexes of platinum with various olefins or vinylsiloxanes.

[0061] The amount of platinum group metal catalyst added is a catalytic amount, and from an economical standpoint as well as to obtain a good cured coating, the amount is preferably such that the amount of platinum group metal relative to the total mass of the organopolysiloxane (I) and organohydrogenpolysiloxane (II) is 1 to 1000 ppm, more preferably 10 to 300 ppm, and even more preferably 50 to 200 ppm.

[0062] Water (VI) The addition reaction curable silicone emulsion composition of the present invention can contain water (VI). The amount of water (VI) is adjusted to achieve a viscosity suitable for the coating device actually used and to achieve the desired amount of silicone to be coated on the substrate. Preferably, the amount of water is 100 to 10,000 parts by mass, more preferably 100 to 8,000 parts by mass, and even more preferably 500 to 3,000 parts by mass, per 100 parts by mass of organopolysiloxane (I). If the amount of water is at least the lower limit, an O / W emulsion can be easily obtained, and if it is at most the upper limit, the stability of the emulsion can be maintained.

[0063] The water that can be incorporated into the addition reaction curable silicone emulsion composition of the present invention is sufficient if it has an impurity concentration similar to that of tap water, but water that does not contain strong acids, strong alkalis, large amounts of alcohol, salts, etc. is preferred, as this will help maintain emulsion stability.

[0064] The pH of the addition reaction curable silicone emulsion composition of the present invention is preferably 2.5 to 6.0, more preferably 3.0 to 5.0. A pH of 2.5 or higher provides good coatability, while a pH below 6.0 facilitates curing.

[0065] [Other ingredients] The addition reaction curable silicone emulsion composition of the present invention can contain other optional components in addition to the above-mentioned components (I) to (VI). These optional components include a catalyst activity inhibitor (controller), a water-soluble resin, a preservative, an inorganic or organic acid, a silicone resin, silica, an organopolysiloxane that does not have a silicon-bonded hydrogen atom or an alkenyl group, a leveling agent, an antifoaming agent, a water-soluble polymer, and a thickener other than the polyvinyl alcohol. Therefore, the present invention is more preferably an addition reaction curable silicone emulsion composition that consists essentially of the above-mentioned components (I) to (VI) and may further contain at least one other optional component selected from the above.

[0066] Examples of catalyst activity inhibitors (control agents) for the purpose of suppressing the catalytic activity of platinum group metal catalysts include various organic nitrogen compounds, organic phosphorus compounds, acetylenic compounds, oxime compounds, organic chloro compounds, etc. Examples include acetylenic alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, and 2-phenyl-3-butyn-2-ol, acetylenic compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne, reaction products of these acetylenic compounds with alkoxysilanes, siloxanes, or hydrogensilanes, vinylsiloxanes such as tetramethylvinylsiloxane cyclics, organic nitrogen compounds such as benzotriazole, and other organic phosphorus compounds, oxime compounds, and organic chloro compounds.

[0067] In addition to polyvinyl alcohol, the addition reaction curable silicone emulsion composition of the present invention can contain a water-soluble resin to aid emulsification and improve stability. Examples of water-soluble resins include cellulose derivatives, carboxyvinyl polymers, acrylic polymers, sodium polyacrylate, and dextrin. This water-soluble resin may also function as a thickener. It is preferable to select a resin that has as little catalytic poisoning as possible for the platinum group metal catalyst (V). As with surfactants, the amount of resin to be added should be the minimum necessary to ensure sufficient silicone emulsion stability and substrate wettability.

[0068] The addition reaction curable silicone emulsion composition of the present invention may contain a preservative, such as sorbic acid, oxazoline compounds, isothiazolinone compounds, or aromatic carboxylates.

[0069] In order to improve emulsion stability, an inorganic acid or an organic acid can be added. Specific examples of inorganic acids or organic acids include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, stearic acid, lactic acid, and citric acid. The amount of inorganic acid or organic acid added can be set arbitrarily, but is preferably an amount that adjusts the pH of the emulsion composition of the present invention to 2.5 to 6.0.

[0070] Furthermore, for the purpose of controlling the releasability, silicone resin, silica, organopolysiloxane having no hydrogen atoms or alkenyl groups bonded to silicon atoms, leveling agents such as fluorine-based surfactants, antifoaming agents, water-soluble polymers, thickeners other than the polyvinyl alcohol, such as methyl cellulose, etc. may be added as needed. The amount of any optional component added may be set as needed.

[0071] [Method for producing silicone emulsion composition] The addition reaction curable silicone emulsion composition of the present invention can be produced by known methods. When the composition contains the above components (I) to (VI), for example, predetermined amounts of the above components (I) to (IV) and a portion of the water (VI) can be emulsified by phase inversion, and the remaining water (VI) can be added for dilution. Each component can be used alone or in combination of two or more types.

[0072] The emulsification temperature is not particularly limited, but is preferably 0 to 80° C., and more preferably 10 to 60° C. At a temperature of 10 to 60° C., emulsification is easy, and the produced emulsion tends to be more stable.

[0073] The emulsifier used for emulsification is not particularly limited as long as it can stir the raw materials and emulsion composition. Examples of suitable emulsifiers include colloid mills (IKA, PUC, Nippon Seiki, Iwaki) with a rotor-stator stirring section, high-shear mixers (Silverson, Primix), Homomixer (Primix), Homodisper (Primix), Ajihomomixer (Primix), Combimix (Primix), a three-screw dispersion mixer combining a Homomixer, Homodisper, and anchor mixer, and twin-screw mixers with co-rotating or counter-rotating screws, such as HAAKE Mini Lab II (Thermo Scientific), MC15, and MC5 (Leo Lab).

[0074] The silicone emulsion composition of the present invention desirably has an average particle size of 2.5 μm or less. If the average particle size is 2.0 μm or less, the emulsion is more likely to be stable over the long term. To obtain a stable emulsion, an average particle size of 1.5 μm or less is more preferable, and an average particle size of 1.3 μm or less is even more preferable. There is no particular restriction on the lower limit, but it is, for example, an average particle size of 100 nm or more. The average particle size of the silicone emulsion composition is the median diameter measured by laser diffraction / scattering method.

[0075] The platinum group metal catalyst (V) is preferably not emulsified simultaneously with the other components, but is added after the above (I) to (IV) are made into an emulsion and immediately before use. The platinum group metal catalyst is preferably made water-dispersible before addition, and for example, it is effective to mix it with the surfactant (III) in advance or to make it into an emulsion by the above-mentioned method.

[0076] [Release film] A release film can be provided by applying the silicone emulsion composition of the present invention to a plastic film and then thermally curing it.

[0077] Examples of plastic films include polyolefin films such as polypropylene film, polyethylene film, and ethylene-propylene copolymer film, and polyester films such as polyethylene terephthalate. The thickness of the film substrate is not particularly limited, but generally, a film substrate having a thickness of about 5 to 100 μm is sufficient.

[0078] The plastic film can also be subjected to a corona discharge treatment before coating with the silicone emulsion composition. The silicone emulsion composition of the present invention has high adhesion to plastic films even without corona treatment, but in some cases corona treatment can further improve adhesion.

[0079] The silicone emulsion composition of the present invention adheres well not only to plastic films but also to paper substrates, including fine paper, coated paper, art paper, glassine paper, polyethylene-laminated paper, and kraft paper.

[0080] To apply the composition of the present invention to a substrate, a gravure coater, an air knife coater, a roll coater, a wire bar, etc. may be used. There are no particular restrictions on the amount of coating, but the amount is usually 0.1 to 2.0 g / m2 in terms of silicone solid content. 2 It is sufficient if it is about 0.1 to 1.0 g / m 2 is more preferred.

[0081] After applying the composition of the present invention, the coated substrate is heated, for example, using a hot air circulation dryer or the like, at 80°C to 160°C for about 3 minutes to 5 seconds to form a cured silicone coating on the substrate and impart release properties. The coating can also be cured by irradiation with infrared or ultraviolet light, and the curing efficiency can be improved by using these methods in combination. [Example]

[0082] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0083] In the following examples and comparative examples, parts are by mass, and physical property values ​​are measured values ​​obtained by the following test methods. In the following, viscosity was measured at 25° C. using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.), and the average particle size is the median diameter measured using a Partica LA-960 (manufactured by HORIBA Corporation).

[0084] [Curing conditions] Immediately after preparing the silicone emulsion composition, 0.60 g / m of the silicone emulsion composition was applied to a PET film (Diafoil 38 μm, product name, manufactured by Mitsubishi Chemical Corporation) substrate. 2 The mixture was then heated in a hot air dryer at 110°C for 30 seconds.

[0085] [Initial adhesion] Immediately after preparation of the silicone emulsion composition, 0.60 g / m of the silicone emulsion composition was applied to a PET film substrate. 2 The coating was heated in a hot air dryer at 110°C for 30 seconds, and the resulting cured coating was immediately rubbed with a finger 10 times and visually inspected for cloudiness and peeling. In the table below, the notation for the adhesion evaluation means the following. No fall-off even after 10 rubs: Yes It fell off after rubbing it 10 times: △ Falls off after 1 to 10 rubs: ×

[0086] [Adhesion] Immediately after preparing the silicone emulsion composition, 0.60 g / m of the silicone emulsion composition was applied to a PET film substrate. 2 The coating was heated in a hot air dryer at 110°C for 30 seconds, and the resulting cured film was aged at 25°C for 1 day. The cured film was rubbed with a finger 10 times, and the presence or absence of clouding and peeling was visually determined to determine adhesion. In the table below, the notation for the adhesion evaluation means the following. No fall-off even after 10 rubs: Yes It fell off after rubbing it 10 times: △ Falls off after 1 to 10 rubs: ×

[0087] [Peeling force] Immediately after preparation, the silicone emulsion composition was applied to a PET film substrate under the above-mentioned curing conditions and cured at 110°C for 30 seconds to obtain a release film. A 25mm wide adhesive tape (Tesa 7475 tape, product name manufactured by Tesa Tape, Inc.) was laminated to the cured coating surface of the release film and aged at room temperature for 1 day. The adhesive tape laminated to the release film was peeled at an angle of 180° at a speed of 0.3 m / min using a tensile tester, and the force required for peeling (N / 2.5 cm) was measured.

[0088] [Residual adhesion rate] Using the same method as in the above peel force measurement, a release film having a cured film of silicone emulsion composition was obtained.A polyester adhesive tape (NO. 31B, product name manufactured by Nitto Denko Corporation) was attached to the cured film surface of the release film, and a load of 1976 Pa was applied and heated at 70 ° C for 20 hours, after which the adhesive tape was peeled off and attached to a stainless steel plate.The adhesive tape was then peeled off at an angle of 180 ° and a speed of 0.3 m / min using a tensile tester, and the force (N / 2.5 cm) required to peel off from the stainless steel plate was measured.The percentage of this peel force relative to the force required to peel untreated adhesive tape (standard tape) from the stainless steel plate was calculated, and this was taken as the residual adhesion rate of the adhesive tape.

[0089] The organopolysiloxanes (I) used in the examples and comparative examples are as follows: Organopolysiloxane (Ia): (CH3)2(CH2=CH)SiO 1 / 2 50 mol % of dimethylvinylsiloxane units represented by the formula 3 / 2 A siloxane having a viscosity of 30 mPa·s at 25°C and a vinyl group content of 0.60 mol / 100 g, which is composed of 50 mol% of methylsiloxane units represented by the formula: In the above general formula (I-1), an organopolysiloxane in which p=15, q=0, r=15, and s=0 (included in the organopolysiloxane represented by the above average composition formula (I-2)) Organopolysiloxane (Ib): (CH3)2(CH2=CH)SiO 1 / 2 0.04 mol % of dimethylvinylsiloxane units represented by (C6H5)2SiO 2 / 2 1.80 mol % of diphenylsiloxane units represented by (CH3)(CH2=CH)SiO 2 / 2 and 4.97 mol % of methylvinylsiloxane units represented by (CH3)2SiO 2 / 2 A siloxane containing terminal and side chain vinyl groups, which is composed of 93.19 mol% of dimethylsiloxane units represented by the formula: Organopolysiloxane in which p=2, q=5000, r=0, and s=0 in the above general formula (I-1) Organopolysiloxane (Ic): (CH3)2(CH2=CH)SiO 1 / 2 1.4 mol% of dimethylvinylsiloxane units represented by (CH3)2SiO 2 / 2 A dimethylpolysiloxane containing vinyl groups at both ends, which is composed of 98.6 mol% of dimethylsiloxane units represented by the formula: Organopolysiloxane in which p=2, q=146, r=0, and s=0 in the above general formula (I-1) Organopolysiloxane (Id): (CH3)2(CH2=CH)SiO 1 / 2 0.03 mol % of dimethylvinylsiloxane units represented by (CH3)(CH2=CH)SiO 2 / 2 and 3.00 mol % of methylvinylsiloxane units represented by (CH3)2SiO 2 / 2 A siloxane containing terminal and side chain vinyl groups, which is composed of 96.97 mol% of dimethylsiloxane units represented by the formula: Organopolysiloxane in which p=2, q=8000, r=0, and s=0 in the above general formula (I-1) Organopolysiloxane (Ie): (CH3)2(CH2=CH)SiO 1 / 2 0.02 mol % of dimethylvinylsiloxane units represented by (C6H5)2SiO 2 / 2 1.50 mol % of diphenylsiloxane units represented by (CH3)(CH2=CH)SiO 2 / 2 and 0.15 mol % of methylvinylsiloxane units represented by (CH3)2SiO 2 / 2 A siloxane containing terminal and side chain vinyl groups, which is composed of 98.33 mol% of dimethylsiloxane units represented by the formula: Organopolysiloxane in which, in the above general formula (I-1), p=2, q=12000, r=0, and s=0

[0090] The organohydrogenpolysiloxanes (II) used in the following examples and comparative examples are as follows: Organohydrogenpolysiloxane (IIa): (CH3)3SiO 1 / 2 2 mol % of trimethylsiloxane units represented by (CH3)2SiO2 / 2 28 mol% of dimethylsiloxane units represented by (CH3)HSiO 2 / 2 A methylhydrogenpolysiloxane having a viscosity of 117.3 mPa·s at 25°C and a SiH group content of 1.08 mol / 100 g, which is composed of 70 mol% of methylhydrogensiloxane units represented by the formula: Organohydrogenpolysiloxane represented by the above general formula (II), wherein a=2, c=28, and d=70. Organohydrogenpolysiloxane (IIb): (CH3)3SiO 1 / 2 5 mol % of trimethylsiloxane units represented by (CH3)HSiO 2 / 2 A methylhydrogenpolysiloxane having a viscosity of 20.13 mPa·s at 25°C and an SiH group content of 1.6 mol / 100 g, which is composed of 95 mol% of methylhydrogensiloxane units represented by the formula: Organohydrogenpolysiloxane represented by the above general formula (II), wherein a=2 and d=38

[0091] The polyvinyl alcohol (IV) used in the following examples and comparative examples is as follows: 18% aqueous solution of polyvinyl alcohol (1) with a degree of polymerization of 1800 and a degree of saponification of 88.0 15% aqueous solution of polyvinyl alcohol (2) with a degree of polymerization of 1500 and a degree of saponification of 87.0 18% aqueous solution of polyvinyl alcohol (2) with a degree of polymerization of 1500 and a degree of saponification of 87.0 18% aqueous solution of polyvinyl alcohol (3) with a degree of polymerization of 1800 and a degree of saponification of 88.1 15% aqueous solution of polyvinyl alcohol (4) with a degree of polymerization of 1500 and a degree of saponification of 87.0 18% aqueous solution of polyvinyl alcohol (4) with a degree of polymerization of 1500 and a degree of saponification of 87.0 18% aqueous solution of polyvinyl alcohol (5) with a degree of polymerization of 1500 and a degree of saponification of 87.0

[0092] The amount of sodium acetate contained in each of the above polyvinyl alcohols is as follows: Sodium acetate content in polyvinyl alcohol (1): 0.098% Sodium acetate content in polyvinyl alcohol (2): 0.297% Sodium acetate content in polyvinyl alcohol (3): 0.698% Amount of sodium acetate in polyvinyl alcohol (4): 1.112% Sodium acetate content in polyvinyl alcohol (5): 1.128%

[0093] In the following, the sodium acetate contained in the silicone emulsions 1 to 4 and the platinum catalyst emulsion is derived from the raw material polyvinyl alcohol. The amount of sodium acetate contained in each of the polyvinyl alcohols (1) to (5) was determined by dissolution titration in accordance with JIS K 6726-1994. Specifically, 5 g of polyvinyl alcohol was added to 150 mL of water and heated to about 90°C to dissolve. The cooled polyvinyl alcohol solution was added to the methyl orange solution, and titration was performed with 0.1 mol / mL hydrochloric acid at room temperature. The titration volume was determined as the endpoint when the solution color changed from orange-yellow to red. The titration volume of the blank test was subtracted from the titration volume to determine the amount of sodium acetate in the polyvinyl alcohol. The amounts of sodium acetate shown in Tables 1 to 3 described below are calculated as ppm by mass of sodium acetate relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) based on the amounts of sodium acetate in each of the polyvinyl alcohols (1) to (5).

[0094] [Preparation of emulsion composition] [Preparation Example 1] Silicone emulsion 1 A 5-liter composite emulsifier (TK Combimix M type, product name of PRIMIX Corporation) having an anchor-type agitator capable of agitating the entire container and a rotatable disk with small tooth-shaped protrusions alternately provided on the periphery, was charged with 44.96 parts by mass of the organopolysiloxane (Ia), 15.32 parts by mass of the organopolysiloxane (Ib), 36.52 parts by mass of the organopolysiloxane (Ic), and 20.28 parts by mass of the organohydrogenpolysiloxane (IIa). Amount parts, 15.81 parts by mass of the organohydrogenpolysiloxane (IIb), 1.30 parts by mass of polyoxyethylene styrenated phenyl ether (HLB 13.0) as surfactant (IIIa), 15.47 parts by mass of an 18% aqueous solution of polyvinyl alcohol (1) with a degree of polymerization of 1800 and a degree of saponification of 88.0, 0.82 parts by mass of ethynylcyclohexanol as a catalyst activity inhibitor, and 16.3 parts by mass of water as phase inversion water were charged and mixed uniformly at 25 ° C. 159.19 parts by mass of water was added as dilution water to the obtained mixture and stirred to obtain an O / W type emulsion 1 with a silicone content of 41% and an average particle size of 763 nm.

[0095] [Preparation Example 2] Silicone Emulsion 2 The steps of Preparation Example 1 were repeated, except that 36.22 parts by mass of an 18% aqueous solution of polyvinyl alcohol (1) having a degree of polymerization of 1800 and a degree of saponification of 88.0 and 138.43 parts by mass of water were added as dilution water, to obtain O / W type emulsion 2 having a silicone content of 41% and an average particle size of 810 nm.

[0096] [Preparation Example 3] Silicone Emulsion 3 The steps of Preparation Example 1 were repeated, except that 36.22 parts by mass of an 18% aqueous solution of polyvinyl alcohol (2) having a degree of polymerization of 1500 and a degree of saponification of 87.0 and 138.43 parts by mass of water were added as dilution water, to obtain O / W type emulsion 3 having a silicone content of 41% and an average particle size of 796 nm.

[0097] [Preparation Example 4] Silicone Emulsion 4 The formulation in Preparation Example 1 above was 21.04 parts by mass of the organopolysiloxane (Ia), 5.71 parts by mass of the organopolysiloxane (Id), 18.25 parts by mass of the organopolysiloxane (Ie), 52.10 parts by mass of the organopolysiloxane (Ic), 15.15 parts by mass of the organohydrogenpolysiloxane (IIa), and polyoxyethylene styrenated phenyl ether (HLB 10. The process of Preparation Example 1 was repeated, except that the ingredients were changed to 0.59 parts by mass of 6), 0.59 parts by mass of polyoxyethylene styrenated phenyl ether (HLB 17.5) as surfactant (IIId), 68.05 parts by mass of a 15% aqueous solution of polyvinyl alcohol (2) having a degree of polymerization of 1500 and a degree of saponification of 87.0, 0.36 parts by mass of ethynylcyclohexanol as a catalyst activity inhibitor, and 2.96 parts by mass of water as phase inversion water. The above components were uniformly stirred and mixed at 25 ° C. 109.97 parts by mass of water was added to the resulting mixture as dilution water and stirred to obtain O / W type emulsion 4 having a silicone content of 38% and an average particle size of 796 nm.

[0098] [Preparation Example 5] Silicone Emulsion 5 The steps of Preparation Example 1 were repeated, except that 36.22 parts by mass of an 18% aqueous solution of polyvinyl alcohol (3) having a degree of polymerization of 1800 and a degree of saponification of 88.1 and 138.43 parts by mass of water were added as dilution water, to obtain O / W type emulsion 5 having a silicone content of 41% and an average particle size of 821 nm.

[0099] [Preparation Example 6] Silicone Emulsion 6 The steps of Preparation Example 1 were repeated, except that 36.22 parts by mass of an 18% aqueous solution of polyvinyl alcohol (4) having a degree of polymerization of 1500 and a degree of saponification of 87.0 and 138.43 parts by mass of water were added as dilution water, to obtain O / W type emulsion 6 having a silicone content of 41% and an average particle size of 854 nm.

[0100] [Preparation Example 7] Silicone Emulsion 7 The steps of Preparation Example 1 were repeated, except that 36.22 parts by mass of an 18% aqueous solution of polyvinyl alcohol (5) having a degree of polymerization of 1500 and a degree of saponification of 87.0 and 138.43 parts by mass of water were added as dilution water, to obtain O / W type emulsion 7 having a silicone content of 41% and an average particle size of 860 nm.

[0101] [Preparation Example 8] Silicone Emulsion 8 The steps of Preparation Example 4 were repeated, except that 68.05 parts by mass of a 15% aqueous solution of polyvinyl alcohol (4) with a degree of polymerization of 1500 and a degree of saponification of 87.0 was added, to obtain O / W type emulsion 8 with a silicone content of 38% and an average particle size of 834 nm.

[0102] [Preparation Example 9] Platinum Catalyst Emulsion 9 A 5-liter composite emulsifier (TK Combimix M model, product name of PRIMIX Corporation) equipped with an anchor-type agitator capable of stirring the entire vessel and a rotatable disk with small teeth-shaped protrusions alternately provided on the periphery was charged with 3.20 parts by mass of (Ic) in which 0.07 parts of a platinum vinylsiloxane complex (Va) containing approximately 25% platinum was dispersed, 0.03 parts by mass of polyoxyethylene lauryl ether (HLB 13.6) as surfactant (IIIb), and 1.07 parts by mass of a 15% aqueous solution of polyvinyl alcohol (2) with a degree of polymerization of 1500 and a degree of saponification of 87.0 as polyvinyl alcohol (IV), and mixed uniformly at 25 ° C. 12.87 parts by mass of water was added to the resulting mixture as dilution water and stirred to obtain O / W platinum catalyst emulsion 9.

[0103] Example 1 Silicone emulsion 1 obtained in Preparation Example 1 above was diluted with water to the composition shown in Table 1 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was added in an amount such that the amount of platinum metal relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) shown in Table 1 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the method described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 4.

[0104] Example 2 Silicone emulsion 2 obtained in Preparation Example 2 above was diluted with water to the composition shown in Table 1 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was added to the organopolysiloxane (I) and organohydrogensiloxane (II) in an amount such that the amount of platinum metal relative to the total mass was the amount (ppm) shown in Table 1 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 4.

[0105] Example 2 Silicone emulsion 3 obtained in Preparation Example 3 above was diluted with water to the composition shown in Table 1 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was added in an amount such that the amount of platinum metal relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) shown in Table 1 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 4.

[0106] Examples 4, 5, 6, and 8 The corresponding amount of sodium acetate shown in Table 1 below was added to Silicone Emulsion 3 obtained in Preparation Example 3 above, diluted with water, and then Platinum Catalyst Emulsion 9 obtained in Preparation Example 9 above was added in an amount such that the amount of platinum metal relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) shown in Table 1 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 4.

[0107] Example 7 Silicone emulsion 4 obtained in Preparation Example 4 above was diluted with water to the composition shown in Table 2 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was added to the organopolysiloxane (I) and organohydrogensiloxane (II) in an amount (ppm) of platinum metal relative to the total mass shown in Table 2 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 5.

[0108] Example 9 Silicone emulsion 5 obtained in Preparation Example 5 above was diluted with water to the composition shown in Table 2 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was added in an amount such that the amount of platinum metal relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) shown in Table 2 below, and the mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the method described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 5.

[0109] Examples 10 and 11 To the silicone emulsion 3 obtained in Preparation Example 3 above, the corresponding amount of sodium acetate listed in Table 2 below was added, diluted with water to the composition listed in Table 2 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was added in an amount such that the amount of platinum metal relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) listed in Table 2 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured according to the methods described above. The results are shown in Table 5.

[0110] Comparative Examples 1, 2, and 3 To the silicone emulsion 3 obtained in Preparation Example 3 above, the corresponding amount of sodium acetate listed in Table 2 or 3 below was added, and the mixture was diluted with water to obtain the composition listed in Table 2 or 3 below. The platinum catalyst emulsion 9 obtained in Preparation Example 9 above was then blended in such an amount that the amount of platinum metal relative to the total mass of the organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) listed in Table 2 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 5.

[0111] Comparative Example 4 Silicone Emulsion 6 obtained in Preparation Example 6 above was diluted with water to the composition shown in Table 3 below, and Platinum Catalyst Emulsion 9 obtained in Preparation Example 9 above was then blended in such an amount that the amount of platinum metal relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) shown in Table 3 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and its adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 6.

[0112] Comparative Example 5 Silicone Emulsion 7 obtained in Preparation Example 7 above was diluted with water to the composition shown in Table 3 below, and Platinum Catalyst Emulsion 9 obtained in Preparation Example 9 above was then blended with organopolysiloxane (I) and organohydrogensiloxane (II) in an amount (ppm) of platinum metal relative to the total mass shown in Table 3 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and its adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 6.

[0113] Comparative Example 6 To the silicone emulsion 3 obtained in Preparation Example 3 above, the corresponding amount of sodium acetate listed in Table 3 below was added, and the mixture was diluted with water to obtain the composition listed in Table 3 below. The platinum catalyst emulsion 9 obtained in Preparation Example 9 above was then blended in such an amount that the amount of platinum metal relative to the total mass of the organopolysiloxane (I) and organohydrogensiloxane (II) was the amount (ppm) listed in Table 3 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and the adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 6.

[0114] Comparative Example 7 Silicone emulsion 8 obtained in Preparation Example 8 above was diluted with water to the composition shown in Table 3 below, and platinum catalyst emulsion 9 obtained in Preparation Example 9 above was then blended with organopolysiloxane (I) and organohydrogensiloxane (II) in an amount (ppm) of platinum metal relative to the total mass shown in Table 3 below. The mixture was thoroughly mixed at 25°C to obtain a silicone emulsion composition. The silicone emulsion composition was heat-cured according to the methods described above, and its adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 6.

[0115] In the following Tables 4 to 6, PET stands for polyester film substrate.

[0116] [Table 1] Note 1: The values ​​in the table are the amount of platinum metal (ppm) relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II). Note 2: The values ​​in the table are the amount of sodium acetate (ppm) relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II).

[0117] [Table 2] Note 1: The values ​​in the table are the amount of platinum metal (ppm) relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II). Note 2: The values ​​in the table are the amount of sodium acetate (ppm) relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II).

[0118] [Table 3] Note 1: The values ​​in the table are the amount of platinum metal (ppm) relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II). Note 2: The values ​​in the table are the amount of sodium acetate (ppm) relative to the total mass of organopolysiloxane (I) and organohydrogensiloxane (II).

[0119] [Table 4]

[0120] [Table 5]

[0121] [Table 6]

[0122] As shown in Examples 1 to 11, cured films obtained by curing the addition reaction curable silicone emulsion composition of the present invention at low temperatures and in a short time exhibit good adhesion to film substrates. That is, comparing Examples 1 to 11 with Comparative Examples 1 to 7, cured films obtained from compositions containing 450 ppm or less of sodium acetate relative to the total of organopolysiloxane (I) and organohydrogenpolysiloxane (II) exhibit good adhesion to substrates. Furthermore, as shown in Examples 1 to 11, the lower the amount of sodium acetate relative to organopolysiloxane (I), the better the adhesion of the resulting cured film to the substrate. In contrast, as shown in Comparative Examples 1 to 7, the higher the amount of sodium acetate relative to organopolysiloxane (I), the poorer the adhesion of the resulting cured film to the substrate.

[0123] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. 1. An addition reaction curable silicone emulsion composition comprising an organopolysiloxane (I) having at least two alkenyl groups per molecule, an organohydrogenpolysiloxane (II) having at least two hydrogen atoms directly bonded to Si atoms per molecule, and polyvinyl alcohol (IV), wherein the amount of sodium acetate contained in the composition is 450 ppm or less, based on the total mass of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II).

2. 2. The addition reaction curable silicone emulsion composition according to claim 1, wherein the organopolysiloxane (I) is an organopolysiloxane represented by the following general formula (I-1): 【Chemistry 1】 (In formula (I-1), R １ are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 12 carbon atoms, which may be interrupted by an oxygen atom, and which do not contain an aliphatic unsaturated bond, and R １ At least two of R are alkenyl groups; ２ are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bonds, alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, hydroxyl groups, and alkoxy groups, and p, q, r, and s are numbers which satisfy 2≦p≦100, 0≦q≦30,000, 0≦r, 0≦s, and 0≦r+s≦200.

3. 2. The addition reaction curable silicone emulsion composition according to claim 1, wherein the amount of the polyvinyl alcohol is 1 to 30 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II).

4. Of 100 parts by mass of the organopolysiloxane (I), 15 parts by mass or more is represented by the following average composition formula (I-2): 【Chemistry 2】 (In formula (I-2), R ３ are each independently an alkenyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R ４ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, and R ５ are each independently a hydrogen atom or an alkyl group, t is a positive number of 2 or greater, m is a positive number, and n is 0 or a positive number, satisfying (m+n) / t=0.6 to 1.5 and 0≦n / (m+n)≦0.05, and t, m, and n are numbers such that the viscosity of the organopolysiloxane at 25°C is 5 to 200 mPa s.

3. The addition reaction curable silicone emulsion composition according to claim 2, wherein the organopolysiloxane is represented by the formula:

5. The addition reaction curable silicone emulsion composition according to claim 1, which contains the following components (I) to (VI): (I) 100 parts by mass of an organopolysiloxane represented by the following general formula (I-1): 【Transformation 3】 (In formula (I-1), R １ are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 12 carbon atoms, which may be interrupted by an oxygen atom, and which do not contain an aliphatic unsaturated bond, and R １ At least two of R are alkenyl groups; ２ are each independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bonds, alkenyl groups having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, hydroxyl groups, and alkoxy groups, and p, q, r, and s are numbers which satisfy the following: 2≦p≦100, 0≦q≦30,000, 0≦r, 0≦s, and 0≦r+s≦200). (II) organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to Si atoms per molecule: 1 to 60 parts by mass, (III) surfactant: 0.1 to 20 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II); (IV) polyvinyl alcohol: 1 to 30 parts by mass per 100 parts by mass of the total of the organopolysiloxane (I) and the organohydrogenpolysiloxane (II); (V) a catalytic amount of a platinum group metal catalyst, and (VI) Water: 100 to 10,000 parts by mass.

6. Of 100 parts by mass of the organopolysiloxane (I), 15 parts by mass or more is represented by the following average composition formula (I-2): 【Chemistry 4】 (In formula (I-2), R ３ are each independently an alkenyl group having 2 to 12 carbon atoms which may be interrupted by an oxygen atom, and R ４ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, and R ５ are each independently a hydrogen atom or an alkyl group, t is a positive number of 2 or greater, m is a positive number, and n is 0 or a positive number, satisfying (m+n) / t=0.6 to 1.5 and 0≦n / (m+n)≦0.05, and t, m, and n are numbers such that the viscosity of the organopolysiloxane at 25°C is 5 to 200 mPa s.

6. The addition reaction curable silicone emulsion composition according to claim 5, wherein the organopolysiloxane is represented by the formula:

7. A release film comprising a plastic film and a cured coating of the addition reaction curable silicone emulsion composition according to any one of claims 1 to 6.

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