Silicone emulsion composition

Abstract

The present invention is an addition reaction-curable silicone emulsion composition comprising a water-soluble silane coupling agent (I) and an organopolysiloxane (II) having at least two alkenyl groups in one molecule, characterized in that the water-soluble silane coupling agent (I) has at least one of a succinic anhydride group, a quaternary ammonium group, and a urea group, and the addition reaction-curable silicone emulsion composition contains 1 mass part or more of the water-soluble silane coupling agent (I) relative to 100 mass parts of the organopolysiloxane (II). Thus, an organopolysiloxane emulsion composition that provides a cured coating film that is well-adhered to a plastic film substrate regardless of the type of the plastic film substrate and has moderate peelability to an adhesive, and a release film formed by forming a cured coating film of the organopolysiloxane emulsion composition are provided.

Description

Technical Field

[0001] The present invention relates to an addition reaction curing type silicone emulsion composition and a release film obtained using the silicone emulsion composition, wherein the silicone emulsion composition is well adhered to a plastic film substrate. Background Technology

[0002] In the past, various silicone compositions have been known as release paper compositions for substrates such as paper and plastics. Among them, solvent-based silicones have been widely used due to their release properties and applicability to a wide range of substrates.

[0003] However, in recent years, considering environmental pollution, safety, and hygiene, measures such as reducing solvent usage or recycling solvents instead of releasing them into the environment have become necessary. Among these methods, using solvent-free organosilicon is effective in reducing solvent usage, but achieving a concentration of 0.1–1.0 g / m³ requires further research. 2 Achieving uniform coating thickness for these solvent-free silicones onto paper, laminated paper, and plastic film substrates requires expensive coating equipment and technology. Furthermore, switching from solvent-based to solvent-free silicones is generally not an easy process. (The last sentence appears to be incomplete and possibly refers to a specific coating thickness.) 2 The production cost will increase if the coating is carried out under the above conditions, so it is not the preferred method.

[0004] As another effective method to reduce solvent usage, the use of emulsion-type silicones can be cited. Such silicones have been used in the past, including: emulsion-type silicones obtained by mixing an emulsion composed of organovinyl polysiloxane, a platinum compound, an emulsifier, and water with an emulsion composed of organohydrosiloxane, an emulsifier, and water (Patent Document 1); emulsion-type silicones manufactured by emulsion polymerization (Patent Document 2); and emulsion-type silicones obtained by emulsifying organovinyl siloxane and organohydrosiloxane with a specific emulsifier and then mixing them with an emulsion of a platinum compound (Patent Document 3), etc.

[0005] These silicones can be diluted with water in any way, thus having the following advantages: unlike solvent-free types, they do not require expensive coating equipment or technology for film coating, and their ease of use is close to that of solvent-based types.

[0006] However, due to the drawbacks caused by the water-based dispersion medium, emulsion-type silicones have not yet achieved widespread adoption. One drawback is that water has a high latent heat of vaporization, requiring high-temperature curing and resulting in poor curing properties compared to solvent-based or solvent-free silicones. Another drawback is the high surface tension of water, leading to poor wettability and adhesion to the substrate. These drawbacks are particularly significant for plastic film substrates, and can be considered the reason why they have been largely unused.

[0007] To address these issues, numerous improvements have been proposed, such as the use of organopolysiloxanes with alkenyl groups at the molecular ends (Patent Document 4) and the incorporation of emulsions composed of non-organosilicon polymers (Patent Document 5). However, most of these improvements target paper substrates, and when coated onto plastic film substrates, sufficient adhesion cannot be achieved.

[0008] Furthermore, as a method to improve adhesion, a method has been reported to make the base polymer contain RSiO 3 / 2 A method for branching the unit (Patent Document 6). Although the material obtained by this method can adhere well to various plastic substrates, the organopolysiloxane containing a large number of trifunctional siloxane units and alkenes, which is the adhesive component, needs to account for more than 50% by mass. If you want to further improve the adhesion, it is difficult to peel it off from the adhesive sufficiently and easily (make it easy to peel off).

[0009] As a method for improving adhesion using silane coupling agents, there is a method using epoxypropoxysilane (Patent Document 7), but it is mainly applied to in-line coating. Furthermore, a method for improving adhesion using a base coat formed with a coating liquid containing a silane coupling agent has been reported; however, stretching is required after the base coat is formed, thus increasing the number of steps. Further, methods using silanes containing epoxycyclohexyl groups have been reported (Patent Document 9), or methods using the reaction product of a liquid polyorganosiloxane and a hydrolyzable silane as an additive, wherein the liquid polyorganosiloxane contains at least one alkenyl group and at least one silanol group, and the hydrolyzable silane contains at least one epoxy group (Patent Document 10), but silane coupling agents are mostly limited to silane coupling agents containing epoxy groups.

[0010] As mentioned above, almost no silicone emulsion solution has been found that can achieve satisfactory adhesion when coated on a plastic film substrate, and there is essentially no silicone emulsion available for practical use.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent Publication No. 57-53143

[0014] Patent Document 2: Japanese Patent Application Publication No. 54-52160

[0015] Patent Document 3: Japanese Patent Application Publication No. 63-314275

[0016] Patent Document 4: Japanese Patent Application Publication No. 6-57144

[0017] Patent Document 5: Japanese Patent Application Publication No. 11-222557

[0018] Patent Document 6: Japanese Patent No. 3824072

[0019] Patent Document 7: Japanese Patent Publication No. 7-57862

[0020] Patent Document 8: Japanese Patent No. 6130230

[0021] Patent Document 9: Japanese Patent No. 5074682

[0022] Patent Document 10: Japanese Patent Publication No. 2017-504674 Summary of the Invention

[0023] The technical problem to be solved by the present invention

[0024] The present invention was made to solve the above-mentioned problems, and its object is to provide a silicone emulsion composition and a release film formed by forming a cured coating of the silicone emulsion composition, wherein the silicone emulsion composition provides a cured coating that adheres well to the plastic film substrate regardless of the type of plastic film substrate and has moderate peelability to the adhesive.

[0025] Technical means to solve technical problems

[0026] To address the aforementioned technical problems, the present invention provides an addition-reaction curable silicone emulsion composition comprising a water-soluble silane coupling agent (I) and an organopolysiloxane (II) having at least two alkenyl groups in one molecule. The addition-reaction curable silicone emulsion composition is characterized in that the water-soluble silane coupling agent (I) has at least one of succinic anhydride, quaternary ammonium, and urea groups, and that, relative to 100 parts by mass of the organopolysiloxane (II), the addition-reaction curable silicone emulsion composition comprises at least one part by mass of the water-soluble silane coupling agent (I).

[0027] If the addition reaction curing type silicone emulsion composition of the present invention is used, it can provide a cured coating that adheres well to the plastic film substrate regardless of the type of plastic film substrate and has moderate peelability to the adhesive.

[0028] In this case, the water-soluble silane coupling agent (I) is preferably represented by the following general formula (Ia).

[0029] [Chemical Formula 1]

[0030]

[0031] In the formula, R1 X is a monovalent hydrocarbon group with 1 to 10 carbon atoms, where n is 2 or 3. X is a monovalent hydrocarbon group with 1 to 4 carbon atoms. k is an integer from 2 to 20.

[0032] If it is such an addition-reaction cured silicone emulsion composition, the adhesion to the plastic film substrate is further improved.

[0033] Furthermore, the addition reaction curing type silicone emulsion composition of the present invention preferably contains the following (1) to (6):

[0034] (1) 1 to 20 parts by weight of the water-soluble silane coupling agent (I);

[0035] (2) 100 parts by weight of the organopolysiloxane (II), represented by the following general formula (II-1), and having an absolute viscosity at 25°C in the range of 10 mPa·s to 50,000 mPa·s, wherein the upper limit is the absolute viscosity measured as a viscosity diluted with 30% toluene.

[0036] [Chemical Formula 2]

[0037]

[0038] R 2 R is any group, either identical or different, selected from unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms that do not have aliphatic unsaturated bonds, or from alkenyl groups with 2 to 12 carbon atoms that optionally contain oxygen atoms. 2 At least two of them are alkenyl groups. p, q, r1, r2, s, and t are in the range of 10 ≤ p ≤ 30,000, 0 ≤ q, r1, r2 ≤ 500, and 0 ≤ s + t ≤ 20.

[0039] (3) 1 to 30 parts by mass of organohydrogen polysiloxane (III), which has at least two hydrogen atoms directly bonded to silicon atoms in one molecule;

[0040] (4) Surfactant (IV), which is 0.1 to 20 parts by mass relative to a total of 100 parts by mass of the organopolysiloxane (II) and the organohydropolysiloxane (III);

[0041] (5) Catalytic amount of platinum group metal catalyst (V); and

[0042] (6) 100 to 10,000 parts by mass of water (VI).

[0043] Such addition-reaction-cured silicone emulsion compositions can provide cured films that adhere better to plastic film substrates and have excellent peelability to adhesives.

[0044] Furthermore, the present invention provides a release film, which is formed by forming a cured coating of the above-mentioned addition reaction-cured silicone emulsion composition on a plastic film.

[0045] If it is this type of release film, it is highly practical because it forms a cured coating that adheres well to the plastic film substrate and has moderate peelability to the adhesive.

[0046] Invention Effects

[0047] As described above, the addition-reaction curable silicone emulsion composition of the present invention can be cured to produce a cured coating that adheres well to the plastic film substrate regardless of the type of plastic film substrate. Furthermore, this cured coating has moderate peelability to adhesives, and therefore can be used as a release film. Furthermore, the release film obtained by coating the above-mentioned silicone emulsion composition onto a plastic film and curing it forms a cured coating that adheres well to the plastic film substrate and has moderate peelability to adhesives, thus exhibiting high practicality. Detailed Implementation

[0048] As described above, there is a requirement to develop a silicone emulsion composition that provides a cured coating that adheres well to the plastic film substrate regardless of its type and has moderate peelability to the adhesive.

[0049] Therefore, the inventors of this application conducted dedicated research to solve the above-mentioned technical problems and discovered that an organosilicon emulsion composition obtained by adding a water-soluble silane coupling agent to an alkenyl-containing organopolysiloxane can be well bonded to a plastic film substrate, thus completing the present invention.

[0050] That is, the present invention is an addition reaction curable silicone emulsion composition comprising a water-soluble silane coupling agent (I) and an organopolysiloxane (II) having at least two alkenyl groups in one molecule. The addition reaction curable silicone emulsion composition is characterized in that the water-soluble silane coupling agent (I) has at least one of succinic anhydride, quaternary ammonium and urea groups, and the addition reaction curable silicone emulsion composition comprises more than 1 part by mass of the water-soluble silane coupling agent (I) relative to 100 parts by mass of the organopolysiloxane (II).

[0051] The present invention will now be described in detail, but it is not limited thereto.

[0052] [Organosilicon emulsion composition]

[0053] The silicone emulsion composition of the present invention is cured by an addition reaction (addition reaction curing type). The silicone emulsion composition comprises a water-soluble silane coupling agent (I) and an organopolysiloxane (II) having at least two alkenyl groups in one molecule. The water-soluble silane coupling agent (I) has at least one selected from succinic anhydride, quaternary ammonium and urea groups. The silicone emulsion composition contains more than 1 part by mass of the water-soluble silane coupling agent (I) relative to 100 parts by mass of the organopolysiloxane (II).

[0054] The addition-reaction curable silicone emulsion composition of the present invention, because it contains the aforementioned water-soluble silane coupling agent (I), can achieve good adhesion even to plastic film substrates for which sufficient adhesion could not be obtained when adding conventionally used epoxy-containing silane coupling agents. Furthermore, the cured film formed by curing the composition of the present invention maintains sufficient adhesion to the plastic substrate and can be easily peeled off from the adhesive (making it easy to peel off).

[0055] The addition-reaction curable silicone emulsion composition of the present invention, in addition to comprising the above-mentioned water-soluble silane coupling agent (I) and an organopolysiloxane (II) having at least two alkenyl groups in one molecule, may also comprise an organohydrogen polysiloxane (III), a surfactant (IV), a catalytic amount of a platinum group metal catalyst (V), and water (VI), wherein the organohydrogen polysiloxane (III) has at least two hydrogen atoms in one molecule that are directly bonded to silicon atoms. The above components will be described in detail below.

[0056] [Water-soluble silane coupling agent (I)]

[0057] The water-soluble silane coupling agent (I) of the present invention is not particularly limited as long as it has at least one of succinic anhydride group, quaternary ammonium group, and urea group. Other than the groups mentioned above, it may include hydroxyl group, carboxylic acid group, amino group, etc. For example, water-soluble silane coupling agents represented by the following general formula can be listed.

[0058] [Chemical Formula 3]

[0059]

[0060] In the formula, B is a monovalent hydrocarbon group with 1 to 10 carbon atoms, either substituted or unsubstituted, and m is 2 or 3. A is a monovalent hydrocarbon group with 1 to 4 carbon atoms, either substituted or unsubstituted. l is an integer from 2 to 20. Z is a succinic anhydride group, a quaternary ammonium group, or a urea group.

[0061] Furthermore, the aforementioned water-soluble silane coupling agent (I) can be a hydrolyzed water-soluble silane coupling agent or a condensed water-soluble silane coupling agent, for example: the co-hydrolysis product of epoxypropoxyalkyltrialkoxysilane and a tetraalkylammonium salt obtained by substituting trialkoxysilane, or the co-hydrolysis product of aminoalkyltrialkoxysilane and ureoalkyltrialkoxysilane.

[0062] The water-soluble silane coupling agent (I) is preferably represented by the following general formula (Ia).

[0063] [Chemical Formula 4]

[0064]

[0065] In the above formula (Ia), R 1 The silane coupling agent is a monovalent hydrocarbon group with 1 to 10 carbon atoms, preferably a monovalent hydrocarbon group with 1 to 6 carbon atoms. Specifically, examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and octyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl, and butenyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl, phenethyl, and phenylpropyl. Among these, methyl, ethyl, and phenyl are preferred. Furthermore, n is 2 or 3. If the silane coupling agent has n of 2 or 3, the amount of silanol produced by hydrolysis is sufficient, resulting in high water solubility, sufficient stability of the aqueous solution, and high reaction efficiency with inorganic materials, thus making it preferred.

[0066] X is a monovalent hydrocarbon group with 1 to 4 carbon atoms. Specifically, examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl, with methyl and ethyl being preferred.

[0067] In the above formula (Ia), k is an integer from 2 to 20, preferably from 2 to 10, and from an industrial perspective, k = 3 is more preferred.

[0068] Specific examples of silane coupling agents containing succinic anhydride groups include: trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, methyldimethoxysilylpropylsuccinic anhydride, methyldiethoxysilylpropylsuccinic anhydride, etc., but are not limited to the silane coupling agents containing succinic anhydride groups exemplified herein.

[0069] In addition, water-soluble silane coupling agents (Ia) also include water-soluble silane coupling agents with hydrolyzed structures or water-soluble silane coupling agents with condensed structures.

[0070] The reason why the addition reaction curing type silicone emulsion composition of the present invention provides a cured coating that adheres well to the plastic film substrate regardless of the type of plastic film substrate is not fully explained, but it is believed that the reason is as follows: by having the water-soluble silane coupling agent (I) have at least one of succinic anhydride group, quaternary ammonium group and urea group, these groups show affinity to the film surface and the silicon side is bonded to the silicone layer, thus the adhesion is improved.

[0071] It is believed that, in particular, by adding the aforementioned water-soluble silane coupling agent (Ia), the succinic anhydride group exhibits a strong affinity for the membrane surface, and the alkoxysilane group bonds with the organosilicon layer, thus improving the membrane adhesion.

[0072] Relative to 100 parts by weight of organopolysiloxane (II), the addition reaction curing type organosilicon emulsion composition of the present invention contains 1 part by weight or more of water-soluble silane coupling agent (I). If it is less than 1 part by weight, a cured coating with sufficient adhesion to the plastic film substrate cannot be obtained. On the other hand, the upper limit of the amount of water-soluble silane coupling agent (I) can be set according to the substrate and is not particularly limited, but it is preferably 30 parts by weight or less, more preferably 20 parts by weight or less.

[0073] [Alkenyl-containing organopolysiloxanes (II)]

[0074] There are no particular limitations on the alkenyl-containing organopolysiloxanes that are the main components of the organosilicon emulsion compositions of the present invention, provided that they have at least two alkenyl groups in a molecule and do not impede emulsification and the stability of the resulting emulsion. If there are fewer than two alkenyl groups, curing is not possible.

[0075] To impart more desirable properties to the release film obtained from the silicone emulsion composition of the present invention, it is preferable to use an organopolysiloxane represented by the following general formula (II-1).

[0076] [Chemical Formula 5]

[0077]

[0078] In (II-1) above, R 2 R is any group, either identical or different, selected from unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms that do not have aliphatic unsaturated bonds, or from alkenyl groups with 2 to 12 carbon atoms that optionally contain oxygen atoms. 2 At least two of them are alkenyl groups.

[0079] As for the aforementioned unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms that do not have aliphatic unsaturated bonds, specifically, examples include: alkyl groups such as methyl, ethyl, propyl, and butyl with 1 to 6 carbon atoms; cycloalkyl groups such as cyclohexyl with 5 to 8 carbon atoms; aryl groups such as phenyl and tolyl with 6 to 10 carbon atoms; aralkyl groups such as benzyl with 7 to 10 carbon atoms; or substituted hydrocarbon groups (e.g., hydroxypropyl, chloropropyl, 3,3,3-trifluoropropyl, etc.) where some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced by hydroxyl, alkoxy, polyether, alkoxyalkyl, epoxy, halogen atoms, etc. From the perspective of exfoliation, alkyl and aryl are preferred, and methyl, ethyl, propyl, and phenyl are more preferred.

[0080] The alkenyl group, which has 2 to 12 carbon atoms and optionally contains oxygen atoms, is preferably -(CH2). x The group represented by -CH=CH2 (x is 0 or an integer from 1 to 10) can include, specifically, vinyl, propenyl, butenyl, hexenyl, octenyl, and decenyl groups. Furthermore, ether bonds may be present in its methylene chain, and the position of the oxygen atom (the position of the ether bond) is not particularly limited; examples include -(CH2)2-O-CH2-CH=CH2 and -(CH2)3-O-CH2-CH=CH2.

[0081] Vinyl is preferred.

[0082] Furthermore, regarding the viscosity of the organopolysiloxane (II-1), the absolute viscosity at 25°C is preferably in the range of 10 mPa·s to 50,000 mPa·s, more preferably in the range of 50 mPa·s to 30,000 mPa·s, with the upper limit being the absolute viscosity calculated based on 30% toluene dilution. If the absolute viscosity is 10 mPa·s or higher, the storage stability of the organosilicone emulsion composition becomes higher; if the absolute viscosity is 50,000 mPa·s or lower based on 30% toluene dilution, it becomes easier to emulsify.

[0083] For viscosities where s and t are in the range of 0 ≤ s + t ≤ 20, and p, q, r1, r2 are 10 ≤ p ≤ 30,000 and 0 ≤ q, r1, r2 ≤ 500, the organopolysiloxane (II-1) can be selected as long as it falls within the above viscosity range. If the organopolysiloxane (II-1) has s + t below 20, it can be obtained in the synthesis without gelation.

[0084] The organopolysiloxane (II) of the present invention can be obtained by known methods for manufacturing organopolysiloxanes. For example, using an acid catalyst, trialkoxymethylsilane is co-hydrolyzed with dienetetramethyldisiloxane or hexamethyldisiloxane in an alcohol solvent. Examples of acid catalysts include sulfuric acid, hydrochloric acid, phosphoric acid, activated clay, ferric chloride, boric acid, trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. After neutralizing the reactants, the alcohol byproduct is removed, and the mixture is washed with water. Then, by removing unreacted substances, the target organopolysiloxane can be obtained. Alternatively, the catalyst can be a base catalyst. Examples of base catalysts include KOH, CsOH, NaOH, (CH3)4NOH, (n-C4H9)4POH, and metal silicates such as potassium or phosphorus.

[0085] Organopolysiloxane (II) is the component in the organosilicone emulsion composition of the present invention that has a great influence on peel strength. The peel characteristics of the cured coating of the organosilicone emulsion composition can be changed by making various changes to the structure or substituents of organopolysiloxane (II).

[0086] Organopolysiloxane (II) need not be a single component. For example, in the case of organopolysiloxane (II-1), it can be a mixture of several organopolysiloxanes with different compositions, provided that the average of the multiple components satisfies the requirements of the above general formula. Specific examples of organopolysiloxane (II) include the following organopolysiloxanes, but are not limited thereto. Furthermore, in the following formulas, Me, Vi, and Ph represent methyl, vinyl, and phenyl, respectively.

[0087] [Chemical Formula 6]

[0088]

[0089] 150≤p1≤2,500

[0090] [Chemical Formula 7]

[0091]

[0092] 150≤p1≤10,000

[0093] [Chemical Formula 8]

[0094]

[0095] 150≤p1≤19,000,2≤p2≤500

[0096] [Chemical Formula 9]

[0097]

[0098] 150≤p1≤19,000,1≤p2≤500

[0099] [Chemical Formula 10]

[0100]

[0101] 150≤p1≤19,000, 1≤p2≤500, 1≤p3≤500

[0102] [Chemical Formula 11]

[0103]

[0104] 150≤p1≤5,000, 1≤p2≤5000, 0≤q≤500, 1≤s≤20

[0105] [Chemical Formula 12]

[0106]

[0107] 150≤p1≤5,000, 1≤p2≤500, 0≤q≤500, 1≤s≤20

[0108] [Chemical Formula 13]

[0109]

[0110] 150≤p1≤5,000, 1≤p2≤500, 0≤q≤500, 1≤s≤20

[0111] [Chemical Formula 14]

[0112]

[0113] 150≤p1≤5,000, 0≤p2≤5,000, 0≤q≤500, 0≤r1≤500, 0≤r2≤500, 1≤s+t≤20

[0114] [Chemical Formula 15]

[0115]

[0116] 150≤p1≤5,000, 1≤p2≤500, 150≤p3≤5,000, 0≤q≤500, 0≤r1≤500, 0≤r2≤500, 1≤s+t≤20

[0117] [Organohydrogen polysiloxane (III)]

[0118] The addition-reaction curable silicone emulsion composition of the present invention can contain organohydrogen polysiloxane (III). The organohydrogen polysiloxane (III) has at least two hydrogen atoms (SiH groups) directly bonded to silicon atoms in one molecule. These SiH groups undergo an addition reaction with the alkenyl groups present in the organohydrogen polysiloxane (II), acting as a crosslinking agent for forming a cured coating. When there are two or more of these groups in one molecule, the structure of the siloxane unit having these groups is represented by the following formula.

[0119] R 3 a H b SiO (4-a-b) / 2 (III)

[0120] In equation (III) above, R 3 It is an unsubstituted or substituted monovalent hydrocarbon group. Specifically, examples include: alkyl groups such as methyl, ethyl, propyl, and butyl, preferably with 1 to 6 carbon atoms; cycloalkyl groups such as cyclohexyl, preferably with 5 to 8 carbon atoms; halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl; aryl groups such as phenyl and tolyl, preferably with 6 to 10 carbon atoms; aralkyl groups such as benzyl, preferably with 7 to 10 carbon atoms; or hydroxypropyl, cyanoethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, etc., in which some or all of the hydrogen atoms bonded to the carbon atom of these groups are replaced by hydroxyl, cyano, or halogen atoms. Among these, alkyl and aryl groups are preferred, and methyl is further preferred from the perspective of increasing the addition reaction rate. a and b are positive numbers that satisfy a + b ≤ 3.

[0121] The amount of organohydrogen polysiloxane (III) incorporated is adjusted according to the amount of alkenyl groups contained in organohydrogen polysiloxane (II), and the molar ratio of SiH groups to alkenyl groups (H / Vi ratio) is preferably in the range of 0.40 to 11.0. Considering the formation of the cured coating and its peel characteristics, it is sufficient to set the amount of organohydrogen polysiloxane (III) in the range of 1 to 30 parts by mass relative to 100 parts by mass of organohydrogen polysiloxane (II). If it is more than 1 part by mass, the curability is improved; if it is less than 30 parts by mass, the peel strength will not exceed the limit of practicality. It is more preferably set in the range of 1 to 15 parts by mass.

[0122] [Surfactant (IV)]

[0123] The addition-reaction curable silicone emulsion composition of the present invention can contain a surfactant (IV). Examples of surfactants (IV) include nonionic surfactants, such as alkyl ether surfactants like polyoxyethylene lauryl ether, polyoxyethylene styrene phenyl ether, and polyoxyethylene tridecyl ether; and alkyl ester surfactants like polyoxyethylene oleate and polyoxyethylene lauryl ester, preferably polyoxyethylene lauryl ether and polyoxyethylene styrene phenyl ether. These 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 value of these individual nonionic emulsifiers or the HLB value of their mixture be 10 to 15.

[0124] Furthermore, anionic or cationic surfactants can also be used, and their simultaneous use with nonionic surfactants is desirable, considering factors such as the stability of the silicone emulsion or its wettability to the substrate. Examples of anionic surfactants include: higher alcohol sulfates, alkylphenyl ether sulfates, alkylbenzene sulfonates, higher alcohol phosphates, ethoxylated higher alcohol sulfates, and ethoxylated higher alcohol phosphates. Examples of cationic surfactants include: alkyltrimethylammonium chloride, alkylamine hydrochloride, alkylamine acetate, and alkylphenyl dimethylammonium chloride.

[0125] It is desirable to set the amount of surfactant incorporated to the minimum amount necessary to achieve sufficient stability and wettability of the silicone emulsion to the substrate. Specifically, the amount is 0.1 to 20 parts by mass relative to a total of 100 parts by mass of organopolysiloxane (II) and organohydropolysiloxane (III), preferably 0.5 to 15 parts by mass. If it is 0.1 parts by mass or more, it becomes easier to emulsify; if it is 20 parts by mass or less, the curability of the silicone emulsion is improved.

[0126] To aid emulsification and improve stability, both surfactants and water-soluble resins can be used simultaneously. Examples of water-soluble resins include polyvinyl alcohol, cellulose derivatives, and carbopol, with polyvinyl alcohol being more preferred. This water-soluble resin can also function as a thickener. It is preferable to select a water-soluble resin that minimizes catalyst poisoning of platinum group metal catalysts (V). Similar to surfactants, it is desirable to set the blending amount to the minimum required to achieve sufficient stability of the silicone emulsion and wettability to the substrate. Specifically, it is preferably set to 1 to 10 parts by mass relative to a total of 100 parts by mass of organopolysiloxane (II) and organohydropolysiloxane (III).

[0127] [Platinum group metal catalysts (V)]

[0128] The addition-reaction curable silicone emulsion composition of the present invention can contain a platinum group metal catalyst (V). A platinum group metal catalyst (V) is a catalyst used to promote addition reactions, and known platinum group metal catalysts can be used as addition reaction catalysts. Examples of such platinum group metal catalysts include platinum, palladium, rhodium, and ruthenium catalysts, among which platinum catalysts are particularly preferred. Examples of such platinum catalysts include chloroplatinic acid, alcoholic or aldehyde solutions of chloroplatinic acid, and chelates of chloroplatinic acid with various olefins or vinylsiloxanes.

[0129] The amount of these platinum group metal catalysts added is the catalyst amount, which, from the perspective of obtaining a good cured coating and from an economic point of view, is preferably set to a range of 1 to 1000 ppm relative to the total mass of organopolysiloxane (II) and organohydropolysiloxane (III) in terms of platinum group metal content.

[0130] [Water (VI)]

[0131] The addition-reaction curable silicone emulsion composition of the present invention can contain water (VI). The amount of water (VI) is adjusted to meet the viscosity suitable for practical use of the coating apparatus and the amount of silicone coating on the target substrate, and is not particularly limited, but is preferably 100 to 10,000 parts by weight relative to 100 parts by weight of organopolysiloxane (II). If it is 100 parts by weight or more, an oil-in-water (O / W) emulsion can be easily obtained; if it is 10,000 parts by weight or less, the stability of the emulsion can be maintained.

[0132] As for usable water, as long as the impurity concentration is the same as that of tap water, it is sufficient. Water that does not contain strong acids, strong alkalis, large amounts of alcohol, salts, etc., can maintain the stability of the emulsion, so it is preferred.

[0133] [Other ingredients]

[0134] The addition-reaction curable silicone emulsion composition of the present invention can contain any components other than those listed above. As other arbitrary components, for example, for the purpose of inhibiting the catalytic activity of platinum group metal catalysts, catalytic activity inhibitors (control agents) selected from various organonitrogen compounds, organophosphorus compounds, alkyne compounds, oxime compounds, organochlorine compounds, etc., can be listed. Examples include: alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, phenylbutynol, etc.; alkyne compounds such as 3-methyl-3-1-penten-1-yne, 3,5-dimethyl-1-hexyn-3-yne, etc.; reaction products of these alkyne compounds with alkoxysilanes, siloxanes, or hydrosilanes; vinylsiloxanes such as tetramethylvinylsiloxane cyclic compounds; organonitrogen compounds such as benzotriazole; and other organophosphorus compounds, oxime compounds, organochromium compounds, etc.

[0135] Furthermore, for the purpose of controlling peelability, leveling agents such as silicone resins, silica, or organopolysiloxanes without hydrogen atoms or alkenyl groups bonded to silicon atoms, fluorinated surfactants, etc., can be added as needed; water-soluble polymers, such as methylcellulose, polyvinyl alcohol, etc., can also be added as thickeners. In addition, the amount of any component added can be set as needed.

[0136] [Preparation method of organosilicon emulsion composition]

[0137] When preparing the addition-reaction curable silicone emulsion composition of the present invention, known methods can be used. When the composition contains the above-described components (I) to (VI), a high-shear stirring device such as a planetary stirrer, a combined stirrer, or a high-pressure homogenizer can be used to mix a specified amount of the above-described components (I) to (VI) and a portion of water (VI), and emulsify by phase inversion. Then, the remaining water (VI) is added to dilute the emulsion. Each component can be used alone or in combination with two or more components.

[0138] The above-mentioned water-soluble silane coupling agent (I) can be added in various ways, such as: adding it to an emulsion solution containing the above-mentioned components (II) to (IV); adding it to an emulsion solution containing the above-mentioned components (II) to (VI); adding water first to prepare an aqueous solution before adding it; self-emulsifying formulation; or incorporating it as a raw material when manufacturing an emulsion solution containing the above-mentioned components (II) to (IV).

[0139] It is desirable to avoid emulsifying the platinum group metal catalyst (V) simultaneously with other components, and instead prepare an emulsion of components (I) to (IV) and add it just before using the emulsion. It is preferable that the platinum group metal catalyst is water-dispersible before addition; for example, methods such as preparing an emulsion by pre-mixing it with the surfactant (IV) are effective.

[0140] [Release film]

[0141] Thus, the prepared silicone emulsion composition can be coated onto a plastic film and thermo-cured to produce a release film for use.

[0142] Here, examples of plastic films include: biaxially oriented polypropylene films, polyethylene films, ethylene-propylene copolymer films, and other polyolefin films; or polyester films such as polyethylene terephthalate. There are no limitations on the thickness of these film substrates; typically, film substrates of approximately 5–100 μm can be used.

[0143] To coat the composition of the present invention onto a substrate, gravure coating machines, air knife coating machines, roller coating machines, Mayer rods, etc., can be used. There are no particular limitations on the coating amount; typically, it only needs to be 0.1 to 2.0 g / m³ based on the solid content of the organosilicon. 2 The concentration should be around 0.1-1.0 g / m³, with 0.1-1.0 g / m³ being more preferred. 2 .

[0144] After coating the composition of the present invention, a cured silicone film can be formed on the substrate by heating it at 80°C to 160°C for about 3 minutes to 5 seconds using, for example, a hot air circulating dryer, and this process imparts peelability. The film can be cured by irradiation with infrared or ultraviolet light, or the curing efficiency can be improved by using these methods simultaneously.

[0145] Thus, if the addition reaction curable silicone emulsion composition of the present invention is used, a cured coating with excellent curing properties can be produced, which can adhere well to the film substrate regardless of the type of plastic film substrate. Furthermore, since this cured coating has moderate peelability to adhesives, it can be used as a release film. Furthermore, the release film obtained by coating the above-mentioned silicone emulsion composition onto a plastic film and curing it has a cured coating that adheres well to the plastic film substrate and has moderate peelability to adhesives, thus it is highly practical. Moreover, after coating the composition of the present invention, a silicone cured coating can be formed on the substrate by heating the coated substrate at 80°C to 160°C for about 3 minutes to 5 seconds, thus a release film with peelability can be easily manufactured without using expensive equipment and without going through complicated processes.

[0146] Example

[0147] The present invention will now be specifically described using examples and comparative examples, but the present invention is not limited to these examples.

[0148] Next, embodiments and comparative examples of the present invention are given, where parts in the examples refer to parts by mass, and the physical property values ​​in the examples and tables represent measured values ​​obtained by the following test methods. Furthermore, unless otherwise specified, viscosity refers to absolute viscosity.

[0149] [Curing properties]

[0150] Regarding curability, the silicone emulsion composition, immediately after preparation, becomes 0.25 g / m³. 2The method involves coating a siloxane composition onto a PET film (DIAFOIL 38μm, trade name manufactured by Mitsubishi Chemical Corporation) substrate and heating it in a hot air dryer at 150°C for a specified time to form a cured film. The cured film is then scratched several times with a finger, and the presence of turbidity and peeling is visually assessed and evaluated. The curing time (in seconds) required for curing is used to express the curing performance.

[0151] [Seamlessness]

[0152] After preparing the organosilicon emulsion composition, it was immediately prepared at a concentration of 0.25 g / m³. 2 The method involves coating a siloxane composition onto various film substrates and heating it in a hot air dryer at 150°C for a specified time to form a cured film. The cured film is then scratched several times with a finger, and any turbidity or peeling is visually assessed to determine its adhesion.

[0153] [Peeling force]

[0154] After preparing the silicone emulsion composition, it was immediately cured at 150°C for 30 seconds using the same method as the curability test. A 25 mm wide adhesive tape (Tesa 7475 tape, trade name manufactured by Tesa Tape. Inc.) was then applied and aged at room temperature for 1 day. The adhesive tape was then peeled off from the sample at a 180° angle and a speed of 0.3 m / min using a tensile testing machine, and the force required for peeling (N / 2.5 cm) was measured.

[0155] [Residual Adhesion Rate]

[0156] In the same manner as for peel force, a cured film of the silicone emulsion composition was formed, and polyester adhesive tape (Nitto 31B, trade name manufactured by NITTO DENKO CORPORATION) was adhered to its surface. A load of 1976 Pa was applied, and the film was heat-treated at 70°C for 20 hours. The tape was then peeled off and adhered to a stainless steel plate. The treated tape was then peeled off, and the force required to peel it off from the stainless steel plate (N / 2.5 cm) was measured. The percentage of the force required to peel off the untreated standard tape was defined as the residual adhesion rate.

[0157] [Preparation of Emulsion Compositions]

[0158] Organosilicon emulsion 1

[0159] To a 5-liter composite emulsifying unit (TK COMBI MIX Model M, PRIMIX Corporation) equipped with an anchor-type stirrer capable of stirring the entire container and a rotating circular plate with small toothed protrusions alternately arranged on the upper and lower edges, the following is added: 100 parts by weight of siloxane (IIa) with a viscosity of 252 mPa·s and a vinyl content of 0.027 mol / 100 g, comprising 1.9 mol% of (CH3)2(CH2=CH)SiO 1 / 2 The dimethylvinylsiloxane unit represented is 97.5 mol% of (CH3)2SiO 2 / 2 The dimethylsiloxane unit represented is 0.6 mol% of CH3SiO 3 / 2 The composition is methylsiloxane; 3.58 parts by mass of methylhydropolysiloxane (IIIa) with a viscosity of 122.2 mPa·s and an H-group content of 1.080 mol / 100 g, which is an organohydropolysiloxane (III), consists of 2 mol% of (CH3)3SiO 1 / 2 The trimethylsiloxane unit is represented by 28 mol% of (CH3)2SiO 2 / 2 The dimethylsiloxane unit represented is 70 mol% of (CH3)HSiO 2 / 2 The emulsion consists of methylhydrosiloxane units; 0.78 parts by mass of polyoxyethylene lauryl ether (HLB 13.6) as surfactant (IV); 51.95 parts by mass of a 10% aqueous solution of polyvinyl alcohol as a water-soluble resin (thickener); and 0.39 parts by mass of ethynylcyclohexanol as a catalytic activity inhibitor. The mixture is stirred and mixed uniformly to induce a phase inversion, followed by stirring for 15 minutes. Then, 103.04 parts by mass of water (VI) as dilution water is added and stirred to obtain an O / W emulsion 1 with a silicone component of 40%.

[0160] Organosilicon emulsion 2

[0161] Using the same method as described above for organosilicon emulsion 1, add 46.45 parts by mass of siloxane (IIb) with a viscosity of 30 mPa·s and a vinyl content of 0.60 mol / 100 g, which is composed of 50 mol% of (CH3)2(CH2=CH)SiO 1 / 2 The dimethylvinylsiloxane unit represented by 50 mol% is composed of CH3SiO 3 / 2The composition is methylsiloxane; 15.83 parts by weight of a 30% toluene-diluted siloxane (IIc) with a viscosity of 5000 mPa·s and a vinyl content of 0.070 mol / 100 g, containing vinyl groups at the ends and on the side chains, which is composed of 0.03 mol% of (CH3)2(CH2=CH)SiO 1 / 2 The dimethylvinylsiloxane unit represented is 93.2 mol% of (CH3)2SiO 2 / 2 The dimethylsiloxane unit represented is 1.80 mol% of (C6H5)2SiO 2 / 2 The diphenylsiloxane unit represented is 4.97 mol% of (CH3)(CH2=CH)SiO 2 / 2 The indicated composition is methyl vinyl siloxane units; 37.72 parts by mass of dimethyl polysiloxane (IId) with vinyl groups at both ends, having a viscosity of 400 mPa·s and a vinyl content of 0.02 mol / 100 g, consisting of 1.4 mol% of (CH3)2(CH2=CH)SiO 1 / 2 The dimethylvinylsiloxane unit represented is 98.6 mol% of (CH3)2SiO 2 / 2 The composition is dimethylsiloxane; 20.95 parts by mass of methylhydropolysiloxane (IIIa) with a viscosity of 122.2 mPa·s and an H-group content of 1.08 mol / 100 g, which is an organohydropolysiloxane (III), consists of 2 mol% of (CH3)3SiO 2 / 2 The trimethylsiloxane unit is represented by 28 mol% of (CH3)2SiO 2 / 2 The dimethylsiloxane unit represented is 70 mol% of (CH3)HSiO 2 / 2 The indicated composition is methylhydrosiloxane units; 16.34 parts by mass of a siloxane (IIIb) with a viscosity of 20.13 mPa·s and an H-group content of 1.6 mol / 100 g, which consists of 5 mol% of (CH3)3SiO 2 / 2 The trimethylsiloxane unit is represented by 95 mol% of (CH3)HSiO 2 / 2 The mixture consists of methylhydrosiloxane units; 1.34 parts by mass of polyoxyethylene lauryl ether (HLB 13.6) as a surfactant (IV); 67.4 parts by mass of a 10% aqueous solution of polyvinyl alcohol as a water-soluble resin (thickener); and 0.84 parts by mass of ethynylcyclohexanol as a catalytic activity inhibitor. The mixture is stirred and mixed uniformly. 190.56 parts by mass of water is added as dilution water to the mixture, and the mixture is stirred to obtain an O / W type emulsion 2 with an organosilicon component of 41%.

[0162] Platinum catalyst emulsion 3

[0163] Using the same method as described above for silicone emulsion 1, the vinylsiloxane chelate of chloroplatinic acid was emulsified to obtain O / W type emulsion 3 with a platinum mass relative to the silicone component of 150 ppm.

[0164] Synthesis of water-soluble silane coupling agents

[0165] Additionally, in the following text, viscosity is the measured value at 25°C using an Ostwald viscometer, and non-volatile components are the measured values ​​based on the heating residue method after drying on an aluminum dish at 105°C for 3 hours.

[0166] [Synthesis example 1] Synthesis of water-soluble silane coupling agents (Ic)

[0167] A 50% by mass methanol solution of 200 g water, 1.0 g acetic acid, 28.5 g 3-epoxypropoxypropyltrimethoxysilane, and 50.0 g n-octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to a 300 mL separable flask equipped with a stirrer, reflux condenser, ester adapter, and thermometer. The solution was heated to 120 °C. 95 g of the methanol and water mixture produced by hydrolysis was removed by distillation under normal pressure to obtain a water-soluble silane coupling agent (Ic).

[0168] The obtained reaction product has a viscosity equivalent to 17.4 mm. 2 / s, a water-soluble silane coupling agent with 31% by mass of non-volatile components and containing quaternary ammonium groups and hydroxyl groups.

[0169] [Synthesis example 2] Synthesis of water-soluble silane coupling agent (Id)

[0170] A 500 mL separable flask equipped with a stirrer, reflux condenser, ester receiving tube, and thermometer was filled with 300 g of water, 55.3 g of 3-aminopropyltriethoxysilane, and 132 g of a 50% by mass methanol solution of 3-ureopropyltriethoxysilane. The solution was heated to 120 °C. 230 g of the mixture of methanol, ethanol, and water produced by hydrolysis was removed by distillation under normal pressure to obtain a water-soluble silane coupling agent (Id).

[0171] The obtained reaction product has a viscosity equivalent to 15.7 mm. 2 / s, a water-soluble silane coupling agent with 29% by mass of non-volatile components and containing urea and amino groups.

[0172] <Example 1>

[0173] The silicone emulsion 1 was diluted with water and mixed with 1.0 part of platinum catalyst emulsion 3 (platinum weight relative to silicone component was 150 ppm) and a water-soluble silane coupling agent (Ib) manufactured by Shin-Etsu Chemical Co., Ltd., represented by the following formula. After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 3.

[0174] [Chemical Formula 16]

[0175]

[0176] <Example 2>

[0177] The silicone emulsion 1 was diluted with water and mixed with 5.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Ib). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 3.

[0178] <Example 3>

[0179] The silicone emulsion 1 was diluted with water and mixed with 12.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Ib). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 3.

[0180] <Example 4>

[0181] The silicone emulsion 1 was diluted with water and mixed with 20.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Ib). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 3.

[0182] <Example 5>

[0183] The silicone emulsion 1 was diluted with water and mixed with 5.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Ic). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 3.

[0184] <Example 6>

[0185] The silicone emulsion 1 was diluted with water and mixed with 12.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Ic). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 3.

[0186] <Example 7>

[0187] The silicone emulsion 1 was diluted with water and mixed with 5.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Id). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel force and residual adhesion were measured. The results are shown in Table 4.

[0188] <Example 8>

[0189] The silicone emulsion 1 was diluted with water and mixed with 12.0 parts of platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm) and silane coupling agent (Id). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 4.

[0190] <Comparative Example 1>

[0191] Silicone emulsion 1 was diluted with water and mixed with platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm). After uniform mixing, it was used as a silicone emulsion composition, and its curing properties, adhesion, peel strength, and residual adhesion were measured. The results are shown in Table 4.

[0192] <Comparative Example 2>

[0193] The silicone emulsion 1 was diluted with water, and a platinum catalyst emulsion 3 (platinum mass relative to silicone component of 150 ppm) and an aqueous solution of silane coupling agent (e) / 1.0 mol / L acetic acid aqueous solution = 2 / 0.16 (mass ratio) were mixed uniformly with 5.0 parts of silane coupling agent (e) as shown in the following formula. This mixture was then used as a silicone emulsion composition, and its curing properties, adhesion, peel strength, and residual adhesion were measured. The results are shown in Table 4.

[0194] [Chemical Formula 17]

[0195]

[0196] Comparative Example 3 (Refer to Patent Document 6)

[0197] The silicone emulsion 2 was diluted with water and mixed with platinum catalyst emulsion 3 (platinum mass relative to silicone component was 150 ppm). After uniform mixing, it was used as a silicone emulsion composition, and the curing properties, adhesion, peel strength and residual adhesion were measured. The results are shown in Table 4.

[0198] The composition of the embodiments and comparative examples is shown in Tables 1 and 2.

[0199] [Table 1]

[0200]

[0201] Note 1: Parts of (II) + (III) relative to 100 parts by mass

[0202] Note 2: ppm relative to the mass of (II) + (III)

[0203] [Table 2]

[0204]

[0205] Note 1: Parts of (II) + (III) relative to 100 parts by mass

[0206] Note 2: ppm relative to the mass of (II) + (III)

[0207] Note 3: Prepare an aqueous solution of (e) / 1.0 mol / L acetic acid aqueous solution = 2 / 0.16 (mass ratio) for addition.

[0208] [Table 3]

[0209]

[0210] Note 1: PET = Polyester film

[0211] Note 2: In the marking of tightness, ○ indicates no detachment and × indicates detachment.

[0212] [Table 4]

[0213]

[0214] Note 1: PET = Polyester film

[0215] Note 2: In the marking of tightness, ○ indicates no detachment and × indicates detachment.

[0216] As can be seen from Examples 1-8, the cured film formed by curing the addition reaction curing type silicone emulsion composition of the present invention adheres well to the film substrate. That is, as can be seen from Examples 1-8 and Comparative Example 1, better adhesion can be obtained by adding silane coupling agents (Ib), (Ic), and (Id); as can be seen from Examples 1-8 and Comparative Example 2, sufficient adhesion cannot be obtained if an epoxy-containing silane coupling agent is added. Furthermore, as can be seen from Examples 1-8 and Comparative Example 3 (refer to Patent Document 6), in the conventional art, organopolysiloxanes containing a large number of trifunctional siloxane units or alkenes as the adhesive development component are difficult to peel off from the adhesive sufficiently and easily if further improvement of adhesion is desired (making them easy to peel off). However, the cured film formed by curing the addition reaction curing type organosilicon emulsion composition of the present invention with added silane coupling agents (Ib), (Ic), and (Id) maintains sufficient adhesion to the plastic substrate and can be peeled off from the adhesive sufficiently and easily.

[0217] As described above, the addition-reaction curable silicone emulsion composition of the present invention can produce a cured coating with excellent curability, which adheres well to the plastic film substrate regardless of its type. Furthermore, since this cured coating has moderate peelability to adhesives, it can be used in release films. Furthermore, the release film obtained by coating the above-mentioned silicone emulsion composition onto a plastic film and curing it forms a cured coating that adheres well to the plastic film substrate and has moderate peelability to adhesives, thus offering high practicality. Moreover, after coating the composition of the present invention, a silicone cured coating can be formed on the substrate by heating it under relatively gentle conditions, thus enabling the easy manufacture of release films with peelability without using expensive equipment or undergoing complex processes.

[0218] Furthermore, this invention is not limited to the above-described embodiments. The above embodiments are merely illustrative, and any technical solution having a substantially identical structure and achieving the same effect as the technical concept described in the claims of this invention is included within the protection scope of this invention.

Claims

1. An addition-reaction-curable silicone emulsion composition comprising a water-soluble silane coupling agent (I), an organopolysiloxane having two or more alkenyl groups in one molecule (II), and an organohydrogen polysiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule (III), wherein the addition-reaction-curable silicone emulsion composition is characterized in that: The water-soluble silane coupling agent (I) contains quaternary ammonium groups and hydroxyl groups. Furthermore, relative to 100 parts by mass of the organopolysiloxane (II), the addition reaction curing type silicone emulsion composition contains more than 1 part by mass of the water-soluble silane coupling agent (I), and relative to a total of 100 parts by mass of the organopolysiloxane (II) and the organohydrogen polysiloxane (III), the addition reaction curing type silicone emulsion composition further contains 1 to 10 parts by mass of polyvinyl alcohol.

2. The addition-reaction curable silicone emulsion composition according to claim 1, characterized in that, It contains: (1) 1 to 20 parts by weight of the water-soluble silane coupling agent (I); (2) 100 parts by weight of the organopolysiloxane (II), which is represented by the following general formula (II-1), and has an absolute viscosity at 25°C in the range of 10 mPa·s to 50,000 mPa·s, wherein the upper limit is the absolute viscosity measured by 30% toluene dilution. ， R 2 R is any group, either identical or different, selected from unsubstituted or substituted monovalent hydrocarbon groups with 1 to 20 carbon atoms that do not have aliphatic unsaturated bonds, or from alkenyl groups with 2 to 12 carbon atoms that optionally contain oxygen atoms. 2 Two or more of them are alkenyl groups; p, q, r1, r2, s, and t are in the range of 10 ≤ p ≤ 30,000, 0 ≤ q, r1, r2 ≤ 500, and 0 ≤ s + t ≤ 20; (3) 1 to 30 parts by mass of organohydrogen polysiloxane (III), which has more than two hydrogen atoms directly bonded to silicon atoms in one molecule; (4) Surfactant (IV), which is 0.1 to 20 parts by mass relative to a total of 100 parts by mass of the organopolysiloxane (II) and the organohydropolysiloxane (III); (5) Catalytic amount of platinum group metal catalyst (V); (6) 1 to 10 parts by mass of polyvinyl alcohol relative to 100 parts by mass of the total of the organopolysiloxane (II) and the organohydropolysiloxane (III); and (7) 100 to 10,000 parts by mass of water (VI).

3. A peeling film, characterized in that, It is formed by curing a film on a plastic film by forming an addition reaction curing type silicone emulsion composition as described in claim 1 or 2.

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