Silicone emulsion composition

Abstract

The present invention pertains to an addition reaction-curable silicone emulsion composition characterized by containing at least one urea-based compound (I) selected from among non-polymer organic compounds having at least one urea group in the molecule, an organopolysiloxane (II) having at least two alkenyl groups in one molecule, and water (VI), with respect to 100.0 parts by mass of the organopolysiloxane (II), the amount of the water (VI) being 10 parts by mass of the at least one urea-based compound (I) being 10 parts by mass or more of the at least one urea-based compound (I), and the amount of the water (VI) being 10 parts by mass or more of the at least one urea-based compound (II). The urea compound (I) is contained in an amount of 1.0 parts by mass or more, and the water (VI) is contained in an amount of 100.0 parts by mass or more. As a result, it is possible to provide: a silicone emulsion composition which has good coatability and adhesion to paper or plastic film base materials, regardless of the type of base material, and which is capable of providing a release film formed from a cured coating film of the silicone emulsion composition; on the other hand, a cured film having an appropriate release force and a high residual adhesion rate with respect to an adhesive can be provided.

Description

TECHNICAL FIELD

[0001] The present application relates to an addition reaction-curable silicone emulsion composition and a release film using the same, which has good adhesion to a paper or plastic film substrate. BACKGROUND

[0002] In the past, as a silicone composition for a release paper for a substrate such as paper or plastic, various compositions have been known, and among them, solvent-type silicones have been widely used because of their release properties and because they can be used for a wide variety of substrates.

[0003] However, in recent years, from the viewpoints of environmental pollution, safety, hygiene, and the like, countermeasures such as reducing the amount of solvent used or recovering the used solvent without discharging it to the outside are required. Among these, using a solventless silicone is effective as a method for reducing the amount of solvent used, but it is necessary to uniformly coat the solventless silicone to a paper, laminated paper, or plastic film substrate at a film thickness of 0.1 to 1.0 g / m 2 , which requires expensive coating devices and techniques, and in general, changing from a solvent type to a solventless type silicone is not an easy method to adopt. When coating is performed at a film thickness of 1.0 g / m 2 , the production cost increases, and thus is not preferable.

[0004] As another effective method for reducing the amount of solvent used, the use of an emulsion-type silicone can be cited. Such silicones have been used for a long time, and known examples include: a silicone obtained by mixing an emulsion composed of an organovinyl polysiloxane, a platinum compound, an emulsifier, and water, and an emulsion composed of an organohydrogen polysiloxane, an emulsifier, and water; a silicone produced by emulsion polymerization; a silicone obtained by emulsifying an organovinyl siloxane and an organohydrogen polysiloxane using a specific emulsifier, and then mixing an emulsion of a platinum compound; and the like.

[0005] Because such a silicone can be diluted with water as desired, expensive coating devices and techniques for thin film coating are not required as in the case of a solventless type, and the advantage of easy handling close to that of a solvent type is obtained.

[0006] However, emulsion-type silicones have disadvantages caused by the fact that the dispersion solvent is water, and thus have not been widely used to date. As one of the disadvantages, high-temperature curing is required because of the large latent heat of vaporization of water, and the curing properties are inferior to those of solvent types and solventless types. Another disadvantage is that the surface tension of water is large, and thus the wettability of the substrate is poor and the adhesion is poor. These disadvantages, particularly for plastic film substrates, can be a serious problem, and can be said to be a reason for not being able to use them in general.

[0007] To solve these technical problems, various improvements have been proposed, such as the use of an organopolysiloxane having an alkenyl group at the molecular terminal, as described in Patent Document 1. Although the use of an alkenyl group at the terminal improves the curability, it is directed to paper substrates, and sufficient adhesion cannot be obtained for plastic film substrates. Patent Document 2 describes a substance prepared by formulating an emulsion composed of a non-silicone polymer, and the like. It exhibits easy peeling for porous paper substrates and improves the curability. However, Patent Document 2 is also directed to paper substrates, and sufficient adhesion cannot be obtained when applied to plastic film substrates.

[0008] Further, as a method for improving adhesion, a composition having a branched structure with an RSiO 3 / 2 unit in the base polymer has been reported (Patent Document 3). Although this composition can be well adhered to various plastic substrates, it is necessary to include an organopolysiloxane having a 3-functional siloxane unit and an alkenyl group in an amount of 50 mass% or more, and even if the adhesion is further improved, the release force to the adhesive becomes heavy when a release film is formed, and it is difficult to adjust the release force to a practical level.

[0009] Patent Document 4 describes a method for improving adhesion using a silane coupling agent. In this method, by using an epoxypropane-based silane, a film having less movement after 7 days and high re-adhesion rate can be provided, but this method is mainly directed to in-line coating. Patent Document 5 describes a method for improving adhesion by using a primer layer formed using a coating liquid composed of a silane coupling agent containing a specific amount of a negative ion-based antistatic agent. The interaction between the substrate, the primer layer, and the release layer becomes strong by the interaction of the hydroxyl group generated by hydrolysis and the organic group possessed by the silane coupling agent. However, extension is performed after the primer layer is formed, and thus the number of steps increases. The following methods have been reported: Patent Document 6 is a method using a silane containing an epoxy cyclohexyl group; and Patent Document 7 is a method using a reaction product as an additive, which is a polyorganosiloxane containing at least one alkenyl group and at least one silanol group, and a hydrolyzable silane containing at least one epoxide group. By the anchoring effect of the epoxy group and the silanol group, the adhesion of the substrate to the release layer is improved, but industrially useful silane coupling agents are mostly limited to those containing an epoxy group. In addition, Patent Literature 8 reports a method using a silane coupling agent having a succinic anhydride group and a hydrolyzable silane oligomer having at least one urea group as an additive. By the effect of the interaction between the substrate and the release layer due to the succinic anhydride group and the urea group, the alkoxysilane-bonding alkoxyl group, the adhesion is improved, but for the oligomer containing the urea group, the residual tack and the adhesion, the coating property cannot reach a level where both are satisfied, and there is still room for improvement.

[0010] As above, the current situation is that an organosilicon emulsion which can obtain satisfactory adhesion and coating property, release property when coating a paper or plastic film substrate has not been substantially proposed. Prior Art Documents Patent Literature

[0011] Patent Literature 1: Japanese Patent Application Laid-Open No. 6-57144 Patent Literature 2: Japanese Patent Application Laid-Open No. 11-222557 Patent Literature 3: Japanese Patent No. 3824072 Patent Literature 4: Japanese Patent Application Laid-Open No. 7-57862 Patent Literature 5: Japanese Patent No. 6130230 Patent Literature 6: Japanese Patent No. 5074682 Patent Literature 7: Japanese Patent Application Laid-Open No. 2017-504674 Patent Literature 8: Japanese Patent Application Laid-Open No. 2020-070311 SUMMARY Problems to be Solved by the Invention

[0012] The present application is to solve the above problems, and aims to provide an organosilicon emulsion composition and a release film formed by a cured coating film of the organosilicon emulsion composition, which has good coating property and adhesion to a paper or plastic film substrate regardless of the type of the substrate, and on the other hand, can provide a cured coating film having appropriate release force and high residual tack to an adhesive. Means for Solving the Problems

[0013] To achieve the above technical problems, the present application provides an addition reaction-curable organosilicon emulsion composition characterized by containing at least one urea compound (I) selected from non-polymer organic compounds having at least one urea group in the molecule, an organopolysiloxane (II) having at least two alkenyl groups in one molecule, and water, containing 1.0 parts by mass or more of the above urea compound (I), 100.0 parts by mass or more of water (VI) with respect to 100.0 parts by mass of the above organopolysiloxane (II).

[0014] As long as it is the addition reaction curing type silicone emulsion composition of the present application, it is able to have good coatability and adhesion to paper or plastic film substrates regardless of the type of the substrate, and on the other hand, it is able to provide a cured coating film having appropriate peel strength and high residual tack to an adhesive.

[0015] The above non-polymer organic compound is preferably one or two or more selected from the group consisting of silane coupling agent monomers, 1-methyl urea, ethyl urea, 1,1-dimethyl urea, 1,1-diethyl urea, acetyl urea, 2-hydroxyethyl urea, butyl urea, 2-chloroethyl urea, phenyl urea, cyclohexyl urea, p-tolyl urea, o-tolyl urea, benzyl urea.

[0016] Thus, a non-polymer organic compound suitable for the present application can be selected.

[0017] Preferably, the above silane coupling agent monomer has a structure represented by the following general formula (Ia-1) and / or (Ia-2). [Chemical Formula 1] (In the general formula, R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is 2 or 3, X is a monovalent hydrocarbon group having 1 to 4 carbon atoms or hydrogen, i, j, k are integers of 2 to 20.)

[0018] As long as it is such an addition reaction curing type silicone emulsion composition, it is able to form a cured coating film having further improved adhesion to paper or plastic film substrates.

[0019] The addition reaction curing type silicone emulsion composition preferably contains (I) to (VI) below. (I) 1 to 15 parts by mass of the above urea-based compound (II) 100 parts by mass of the above organopolysiloxane represented by the following general formula (II-1), the absolute viscosity of the above organopolysiloxane at 25°C being in the range of 10 mPa-s or more to 50,000 mPa-s in terms of 30% toluene dilution viscosity, [Chemical Formula 2] (R 2 3Si-O / 2 ) p (R 2 2Si-O 2 / 2 ) q (R 2 Si-O 3 / 2 ) r (Si-O 4 / 2 ) s (II-1) (R 2R is a group selected from the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with an aliphatic unsaturated bond, or an alkenyl group having 2 to 12 carbon atoms which can have an oxygen atom interposed 2 at least 2 of R are alkenyl groups, and satisfy the following ranges: 2 ≤ p, 10 ≤ q ≤ 30000, and 0 ≤ r, 0 ≤ s, 0 ≤ r + s ≤ 30 (III) 1 to 30 parts by mass of an organohydrogenpolysiloxane having at least 2 hydrogen atoms directly bonded to Si atoms in one molecule (IV) 0.1 to 20 parts by mass of a surfactant with respect to 100 parts by mass of the total of the organopolysiloxane (II) and the organohydrogenpolysiloxane (III) (V) a catalytic amount of a platinum group metal-based catalyst (VI) 100 to 10000 parts by mass of water

[0020] As long as the addition reaction-curable silicone emulsion composition is as such, it can be well-adhered to a paper or plastic film substrate, and can provide a cured coating film having appropriate peelability to an adhesive.

[0021] Further, the present application provides a release film formed by forming a cured coating film of the above-mentioned addition reaction-curable silicone emulsion composition on a paper or plastic film substrate.

[0022] As long as the release film is as such, it can be well-adhered to a paper or plastic film substrate, and on the other hand, a cured coating film having appropriate peelability to an adhesive can be formed, so it is highly practical. Effects of the Invention

[0023] As above, as long as the addition reaction-curable silicone emulsion composition of the present application is as such, a cured coating film which is well-adhered to a substrate regardless of the kind of the substrate of a paper or plastic film substrate can be made by curing it. Further, the cured coating film has appropriate peelability to an adhesive, so it can be used as a release film. Further, the release film obtained by applying and curing the above-mentioned silicone emulsion composition on a paper or plastic film substrate has good coatability and adhesion to the substrate regardless of the kind of the substrate, and on the other hand, a cured coating film which has appropriate peel force and high residual tack to an adhesive and can be well-adhered can be formed, so it is highly practical. DETAILED DESCRIPTION

[0024] As above, development of a silicone emulsion composition which has good coatability and adhesion to a paper or plastic film substrate regardless of the kind of the substrate, and on the other hand, can provide a cured coating film which has appropriate peel force and high residual tack to an adhesive is sought.

[0025] Accordingly, the inventors have made intensive studies to solve the above technical problems and have found that an addition reaction-curable silicone emulsion composition containing a urea compound in an alkenyl-containing organopolysiloxane provides good adhesion to paper or plastic film substrates, thereby completing the present application.

[0026] That is, the present application is an addition reaction-curable silicone emulsion composition characterized by containing at least one urea compound (I) selected from non-polymer organic compounds having at least one urea group in the molecule, an organopolysiloxane (II) having at least two alkenyl groups in one molecule, 1.0 parts by mass or more of the above urea compound (I) and 100.0 parts by mass or more of water (VI) per 100.0 parts by mass of the above organopolysiloxane (II).

[0027] Hereinafter, the present application will be described in detail, but the present application is not limited to the following description.

[0028] [Silicone emulsion composition] The silicone emulsion composition of the present application is cured by addition reaction (addition reaction-curable) and contains a urea compound (I), an organopolysiloxane (II) having at least two alkenyl groups in one molecule, and water (VI), and contains 1.0 parts by mass or more of the above urea compound (I) and 100.0 parts by mass or more of water (VI) per 100.0 parts by mass of the above organopolysiloxane (II).

[0029] The addition reaction-curable silicone emulsion composition of the present application is a composition containing the above urea compound (I), and thus can provide good adhesion even to paper or plastic film substrates that have not been able to provide sufficient adhesion with the use of a conventional silane coupling agent containing an epoxy group. Furthermore, the cured coating film obtained by curing the composition of the present application can be easily peeled off from an adhesive with a high residual adhesive strength while maintaining sufficient adhesion to paper or plastic film substrates.

[0030] The addition reaction-curable silicone emulsion composition of the present application can contain, in addition to the above urea compound (I) and organopolysiloxane (II) having at least two alkenyl groups in one molecule, an organohydrogenpolysiloxane (III) having at least two hydrogen atoms directly bonded to a Si atom in one molecule, a surfactant (IV), a platinum group metal-based catalyst (V) in a catalytic amount, and water (VI). Hereinafter, each component will be described in detail.

[0031] [Urea compound (I)] In the present application, the urea compound (I) is at least one compound selected from non-polymer organic compounds having at least one urea group in the molecule. The urea-based compound (I) described above has at least one urea group in the molecule, and preferably one or more than one and four or less.

[0032] The organic compound described above is preferably one or more than one selected from the group consisting of silane coupling agent monomers, 1-methyl urea, ethyl urea, 1,1-dimethyl urea, 1,1-diethyl urea, acetyl urea, 2-hydroxyethyl urea, butyl urea, 2-chloroethyl urea, phenyl urea, cyclohexyl urea, p-tolyl urea, o-tolyl urea, benzyl urea; and more preferably 1-methyl urea, ethyl urea, butyl urea.

[0033] The silane coupling agent monomer described above can be exemplified by one or more than one selected from the group consisting of silane coupling agent monomers having at least one urea group in the molecule.

[0034] The silane coupling agent monomer described above is preferably a structure represented by the following general formula (Ia-1) or (Ia-2). [Chemical Formula 3]

[0035] In the above (Ia-1) and (Ia-2), R 1 is a monovalent hydrocarbon group having 1 to 10, preferably 1 to 6 carbon atoms, and can be exemplified by alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, octyl, and the like; cycloalkyl groups such as cyclohexyl, and the like; alkenyl groups such as vinyl, allyl, propenyl, and the like; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and the like; aralkyl groups such as benzyl, phenethyl, phenpropyl, and the like; and the like; and among these, methyl, ethyl, and phenyl are preferred. Furthermore, n is 2 or 3, and preferably 3. As long as the silane coupling agent is one in which n is 2 or 3, a sufficient amount of silanol is generated by hydrolysis to make the silane coupling agent highly water-soluble, the stability of the aqueous solution is sufficient, and the reaction efficiency with inorganic materials is also high, and thus it is preferred.

[0036] X is a monovalent hydrocarbon group having 1 to 4 carbon atoms or hydrogen, and with respect to the hydrocarbon group, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, and the like can be exemplified, and among these, methyl and ethyl are preferred.

[0037] In the above (Ia-1) and (Ia-2), i, j, k are integers of 2 to 20, and preferably 2 to 10, and from an industrial viewpoint, i, j = 3 and k = 2 are more preferred.

[0038] As a specific example of the urea group-containing silane coupling agent monomer, the compound shown below can be exemplified 1-[3-(trimethoxysilyl)propyl]urea [Chemical Formula 4]

[0039] 1-[3-(Triethoxysilyl)propyl]urea [Chemical Formula 5]

[0040] 1-[3-(Methyldimethoxysilyl)propyl]urea [Chemical Formula 6]

[0041] 1-[3-(Methyldiethoxysilyl)propyl]urea [Chemical Formula 7]

[0042] N-(2-ureidoethyl)-3-ureidopropyltrimethoxysilane [Chemical Formula 8] Preferred are 1-[3-(trimethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]urea, and N-(2-ureidoethyl)-3-ureidopropyltrimethoxysilane, and the best is N-(2-ureidoethyl)-3-ureidopropyltrimethoxysilane, but are not limited to the compounds exemplified here (wherein Me represents a methyl group and Et represents an ethyl group).

[0043] Furthermore, the silane coupling agent monomer is presumed to partially convert into a hydrolyzed structure or a condensed structure in water, but these components are also believed to be effective in improving the adhesion to the substrate. [Chemical Formula 9] (As in (Ia-1) and (Ia-2) above, i, j, and k are integers of 2 to 20, preferably 2 to 10, and more preferably i, j = 3 and k = 2 from an industrial point of view. In the formula, X is a monovalent hydrocarbon group having 1 to 4 carbon atoms or hydrogen. t and u are integers of 1 to 50. R 3 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms or an -OX group.

[0044] The reason why the addition reaction-curable silicone emulsion composition of the present invention can provide a cured film that adheres well to paper or plastic film substrates, regardless of the type of substrate, is still unclear, but it is believed that the urea group exhibits affinity for the substrate surface, and the silicon group in the silane coupling agent monomer therein bonds with the silicone layer, thereby improving adhesion.

[0045] In particular, it is considered that, by the addition of the above silane coupling agent monomer (Ia-1) or (Ia-2), the urea group will exhibit strong affinity on the surface of the film and the alkoxysilyl group will bond with the silicone layer, so the adhesion to the substrate will be improved.

[0046] The addition reaction-curable silicone emulsion composition of the present application contains 1 mass part or more of the urea-based compound (I) relative to 100 mass parts of the organopolysiloxane (II). If less than 1 mass part, a cured coating film having sufficient adhesion to a paper or plastic film substrate cannot be obtained. On the other hand, the upper limit of the amount of the urea-based compound (I) to be added is not particularly limited as long as it is set in accordance with the substrate, and is preferably 15 mass parts or less, more preferably 10 mass parts or less.

[0047] [Alkenyl-containing organopolysiloxane (II)] The main component of the silicone emulsion composition of the present application, i.e., the alkenyl-containing organopolysiloxane, has at least 2, preferably 3 or more and 300 or less alkenyl groups in one molecule. As long as it is emulsified to obtain an emulsion and has at least 2 alkenyl groups in one molecule, it is not particularly limited. If the number of alkenyl groups is less than 2, sometimes the curability will be reduced, and if it is 300 or less, the release properties of the cured coating film will be good.

[0048] In order to impart more desirable functions to the release film obtained from the silicone emulsion composition of the present application, it is preferable to use an organopolysiloxane represented by the following general formula (II-1). [Chemical Formula 10] (R 2 3Si-O 1 / 2 ) p (R 2 2Si-O 2 / 2 ) q (R 2 Si-O 3 / 2 ) r (Si-O 4 / 2) s (II-1) (R 2 is a group selected from monovalent hydrocarbon groups having a carbon number of 1 to 20 which are unsubstituted or substituted and do not have an aliphatic unsaturated bond, or alkenyl groups having a carbon number of 2 to 12 which can have an oxygen atom interposed, R 2 of which at least 2 are alkenyl groups, and satisfy the following ranges: 2 ≤ p, 0 ≤ q ≤ 30000, and 0 ≤ r, 0 ≤ s, 0 ≤ r + s ≤ 30.

[0049] In the above general formula (II-1), R 2R is a group selected from the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have an aliphatic unsaturated bond, or an alkenyl group having 2 to 12 carbon atoms which can have an oxygen atom interposed, and 2 at least 2 of R are alkenyl groups.

[0050] As the monovalent hydrocarbon group having 1 to 20 carbon atoms which does not have an aliphatic unsaturated bond, specifically, there can be mentioned: an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, and the like; a cycloalkyl group having 5 to 8 carbon atoms such as cyclohexyl, and the like; an aryl group having 6 to 10 carbon atoms such as phenyl, tolyl, and the like; an aralkyl group having 7 to 10 carbon atoms such as benzyl, and the like; or, a substituted hydrocarbon group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a hydroxyl group, an alkoxy group, a polyether group, an alkoxyalkyl group, an epoxy group, a halogen atom, and the like (for example, a hydroxypropyl group, a chloropropyl group, a 3,3,3-trifluoropropyl group, and the like), and, from the viewpoint of release properties, an alkyl group, an aryl group, a methyl group, an ethyl group, a propyl group, a phenyl group are preferred, and a methyl group, an ethyl group, a propyl group, a phenyl group are more preferred.

[0051] As the alkenyl group having 2 to 12 carbon atoms which can have an oxygen atom interposed, preferably, there is mentioned a group represented by - (CH2) x - CH = CH2 (x is 0 or an integer of 1 to 10), and, specifically, there can be mentioned: a vinyl group, an allyl group, a butenyl group, a hexenyl group, an octenyl group, a decenyl group. Furthermore, an ether bond can be present in the alkenyl chain, and the position of the oxygen atom interposed (the position of the ether bond) is not particularly limited, and, for example, - (CH2) 2 - O - CH2 - CH = CH2, - (CH2) 3 - O - CH2 - CH = CH2, and the like can be mentioned. Among these, a vinyl group is preferred. x

[0052] Furthermore, the viscosity of the organopolysiloxane (II-1) is preferably in the range of 10 mPa s or more to 50,000 mPa s in terms of 30% toluene dilution viscosity at an absolute viscosity of 25°C, and more preferably in the range of 50 mPa s or more to 30,000 mPa s in terms of 30% toluene dilution viscosity. As long as the absolute viscosity is 10 mPa s or more, the storage stability of the silicone emulsion composition becomes high, and as long as the absolute viscosity is 50,000 mPa s or less in terms of 30% toluene dilution viscosity, emulsification becomes easy. In the present application, the viscosity of the (II) component is a value measured by a BM-type viscometer (for example, manufactured by Tokyo Keiki Inc.). Furthermore, the rotor, the rotation speed, and the rotation time can be appropriately selected in accordance with the viscosity and based on a general method. The 30% toluene dilution viscosity is a value measured by the above-mentioned viscosity measurement after 30 g of the organopolysiloxane is added to 70 g of toluene, and mixed and stirred until the organopolysiloxane is dissolved.

[0053] ​p is 2 ≤ p, preferably 2 ≤ p ≤ 20, q is 0 ≤ q ≤ 30,000, preferably 100 ≤ q ≤ 10,000, r, s are 0 ≤ r, 0 ≤ s, 0 ≤ r + s ≤ 30, preferably 1 ≤ r, 0 ≤ s, 1 ≤ r + s ≤ 20, as long as the organic polysiloxane (II-1) falls within the above-mentioned viscosity range. As long as the organic polysiloxane (II-1) is one in which r + s is 30 or less, it can be obtained without gelling at the time of synthesis.

[0054] The organic polysiloxane (II) of the present application can be obtained by using a publicly known method for producing an organic polysiloxane. For example, trialkoxymethylsilane is co-hydrolyzed with dienyltetramethyldisiloxane and hexamethyldisiloxane in an alcohol solvent using an acid catalyst. As the acid catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, activated clay, ferric chloride, boric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like can be exemplified. After neutralizing the reaction product, removing the by-product ethanol, and performing water washing, the target organic polysiloxane can be obtained by removing the unreacted product. In addition, the catalyst can be an alkali catalyst. As the alkali catalyst, KOH, CsOH, NaOH, (CH3)4NOH, (n-C4H9)4POH, and metal silicates of potassium and phosphorus, and the like can be exemplified.

[0055] The organic polysiloxane (II) has a great influence on the release force in the silicone emulsion composition of the present application, and by varying the structure and substituent of the organic polysiloxane (II), the release properties of the cured film of the silicone emulsion composition can be changed.

[0056] The organic polysiloxane (II) need not be a single composition, and for example, when it is an organic polysiloxane (II-1), as long as the average of the plurality of components satisfies the requirements of the above general formula, it can also be a mixture of several different compositions of organic polysiloxanes. As specific examples of the organic polysiloxane (II), the following components can be exemplified, but are not limited to these components. Furthermore, Me, Vi, Ph in the following formulae each represent a methyl group, a vinyl group, and a phenyl group, respectively.

[0057] [Chemical Formula 11] (50 ≤ q1≤ 2500)

[0058] [Chemical Formula 12] (50 ≤ q1≤ 10,000)

[0059] [Chemical Formula 13] (50 ≤ q1≤ 19,000, 2 ≤ q2≤ 500)

[0060] [Chemical Formula 14] (50≤q1≤19000, 1≤q2≤500)

[0061] [Chemical Formula 15] (50≤q1≤19000, 1≤q2≤500, 1≤q3≤500)

[0062] [Chemical Formula 16] (50≤q1≤10000, 0≤q4≤500, 1≤r≤20)

[0063] [Chemical Formula 17] (50≤q1≤5000, 1≤q3≤500, 0≤q4≤500, 1≤r≤20)

[0064] [Chemical Formula 18] (50≤q1≤5000, 1≤q2≤500, 0≤q4≤500, 1≤r≤20)

[0065] [Chemical Formula 19] (50≤q1≤10000, 0≤q4≤500, 0≤q5≤500, 0≤q6≤500, 1≤r and / or s, 1≤r+s≤20)

[0066] [Chemical Formula 20] (200≤q1≤10000, 1≤q3≤500, 0≤q4≤500, 0≤q5≤500, 0≤q6≤500, 1≤r and / or s, 1≤r+s≤20)

[0067] [Chemical Formula 21] (1≤r≤20, Y is a group selected from methyl, methoxy, vinyl, or a group that can be given a cyclic structure by an oxygen atom)

[0068] [Organohydrogenpolysiloxane (III)] The addition reaction-curable silicone emulsion composition of the present application can contain an organohydrogenpolysiloxane (III). The organohydrogenpolysiloxane (III) has at least 2 or more hydrogen atoms (SiH group) directly bonded to a Si atom in one molecule. The SiH group undergoes an addition reaction with the alkenyl group possessed by the organopolysiloxane (II) and functions as a crosslinking agent to form a cured coating film. The configuration of the siloxane unit having 2 or more SiH groups in one molecule is represented by the following general formula. R 4 a H b SiO (4-a-b) / 2 (III)

[0069] In the above general formula (III), R 4 is an unsubstituted or substituted monovalent hydrocarbon group, and specifically, examples include: an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, a butyl group, and the like; a cycloalkyl group having 5 to 8 carbon atoms, preferably a cyclohexyl group, and the like; a halogen-substituted alkyl group, such as a 3,3,3-trifluoropropyl group; an aryl group having 6 to 10 carbon atoms, preferably a phenyl group, a tolyl group, and the like; an aralkyl group having 7 to 10 carbon atoms, preferably a benzyl group, and the like; or, a part or all of the hydrogen atoms bonded to the carbon atom of these groups are substituted with a hydroxyl group, a cyano group, a halogen atom, and the like to form a hydroxypropyl group, a cyanoethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, and the like. Among these, an alkyl group and an aryl group are preferred, and from the viewpoint of improving the addition reaction speed, a methyl group is further preferred. a and b are integers satisfying the following conditions: 0 ≤ a ≤ 3, 0 ≤ b ≤ 3, a + b ≤ 3, and preferably a = 1 or 2 and b = 1.

[0070] The content of the SiH group is preferably at least 2, more preferably 3 to 300, further preferably 4 to 200, and further more preferably 5 to 100, in one molecule of the organohydrogenpolysiloxane (III). As long as it is 2 or more, curability is obtained, as long as it is 3 or more, good curability is obtained, and as long as it is 300 or less, an appropriate release force can be obtained.

[0071] The viscosity of the organohydrogenpolysiloxane (III) at 25°C is preferably 1 Pa·s or less, and more preferably 0.005 to 1 Pa·s. As long as it is 1 Pa·s or less, the emulsion composition is easily obtained.

[0072] The blending amount of the organohydrogenpolysiloxane (III) is an amount adjusted by the amount of the alkenyl groups contained in the organopolysiloxane (II), and is preferably an SiH group to alkenyl group molar ratio (H / Vi ratio) in the range of 0.40 to 11.0. Further, it is preferably in the range of 1.0 to 5.0. In consideration of the formation of the cured coating film and its release properties, the blending amount of the organohydrogenpolysiloxane (III) can be in the range of 1 to 30 parts by mass with respect to the organopolysiloxane (II). As long as it is 1 part by mass or more, the curability is improved, and as long as it is 30 parts by mass or less, the release force does not exceed the limit of practicality. It can be in the range of 2 to 15 parts by mass.

[0073] As a specific structure of the organohydrogenpolysiloxane (III), a structure represented by the following formula, for example, can be given. [Chemical Formula 22] (3 ≤ c1 ≤ 300)

[0074] [Chemical Formula 23] (1 ≤ c2 ≤ 298)

[0075] [Chemical Formula 24] (3 ≤ c3 ≤ 300, 1 ≤ d1 ≤ 500)

[0076] [Chemical Formula 25] (1 ≤ c3 ≤ 298, 1 ≤ d1 ≤ 500)

[0077] [Chemical Formula 26] (0 ≤ c3 ≤ 100, 0 ≤ c2 ≤ 100, 1 ≤ e1 ≤ 50)

[0078] [Chemical Formula 27] (0 ≤ c3 ≤ 100, 0 ≤ c2 ≤ 100, 0 ≤ c3 ≤ 100, 0 ≤ c4 ≤ 100, 1 ≤ e2 ≤ 50, 1 ≤ f ≤ 50)

[0079] [Surfactant (IV)] The addition reaction type silicone emulsion composition of the present invention may contain a surfactant (IV). Examples of the surfactant (IV) of the present invention include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene styrenated phenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid ester amides, polyoxyethylene modified organopolysiloxanes, and polyoxyethylene polyoxypropylene modified organopolysiloxanes. Polyoxyethylene alkyl ethers and polyoxyethylene styrenated phenyl ethers are preferred. These nonionic emulsifiers may be used alone or in combination of two or more. In order to obtain a stable silicone emulsion composition, the HLB of these nonionic emulsifiers alone or in combination is preferably 10 to 15.

[0080] In addition, anionic surfactants and cationic surfactants can also be used, but from the perspective of the stability of the silicone emulsion and the wettability to the substrate, it is preferably used in combination with a nonionic surfactant. Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfonates, alkyldiphenyl ether disulfonates, alkane sulfonates, N-acyltaurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acylamino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, and polyoxyethylene alkyl ether phosphate salts. Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylene alkyldimethylammonium salts, dimeroxyethylene alkylmethylammonium salts, trimeroxyethylene alkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamideamine salts.

[0081] The surfactant is preferably added in the minimum amount that provides sufficient stability of the silicone emulsion and wettability to the substrate. Specifically, it is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of the combined organopolysiloxane (II) and organohydrogenpolysiloxane (III). Emulsification is facilitated when the surfactant is 0.1 parts by mass or greater, while curability of the silicone emulsion is improved when the surfactant is 20 parts by mass or less.

[0082] As a compound that can exhibit the same action as the surfactant, a water-soluble resin can also be used or used in combination. As the water-soluble resin, polyvinyl alcohol, cellulose derivatives, carboxyvinyl polymers, and the like can be listed, and polyvinyl alcohol is more preferable. The water-soluble resin can also function as a thickening agent. It is preferable to select a water-soluble resin that is less likely to cause poisoning of the catalyst with respect to the platinum group metal-based catalyst (V). The amount is the same as that of the surfactant, and is preferably set to the minimum amount at which the stability of the silicone emulsion and the wettability with respect to the substrate can be sufficiently obtained. Specifically, 1 to 10 parts by mass, more preferably 3 to 8 parts by mass, with respect to 100 parts by mass of the total of the organopolysiloxane (II) and the organohydrogenpolysiloxane (III) is preferable.

[0083] [Platinum group metal-based catalyst (V)] The addition reaction type silicone emulsion composition of the present application can contain a platinum group metal-based catalyst (V). The platinum group metal-based catalyst (V) is a catalyst for promoting the addition reaction, and a publicly known catalyst for the addition reaction catalyst can be used. As such a platinum group metal-based catalyst, a catalyst such as a platinum-based, palladium-based, rhodium-based, ruthenium-based catalyst, and the like can be listed, and among these, the use of a platinum-based catalyst is particularly preferable. As the platinum-based catalyst, a chloroplatinic acid, an alcohol solution or an aldehyde solution of chloroplatinic acid, a complex of platinum with various olefins or alkenylsiloxanes, and the like can be listed.

[0084] The addition amount of these platinum group metal-based catalysts is the catalyst amount, and from the viewpoint of obtaining a good cured coating film while also being economical, it is preferable to set to a range of 1 to 1000 ppm in terms of the amount of platinum group metal with respect to the total mass of the organopolysiloxane (II) and the organohydrogenpolysiloxane (III). As long as it is 1 ppm or more, good curability can be obtained. As long as it is 1000 ppm or less, the service life of the treatment bath can be kept longer. Further preferably, it is in a range of 5 to 500 ppm.

[0085] [Water (VI)] The addition reaction type silicone emulsion composition of the present application can contain water (VI). The amount of water (VI) is an amount adjusted in a manner that satisfies the viscosity suitable for the coating device actually used, and the amount of silicone coating with respect to the substrate set as the target. It is 100.0 parts by mass or more with respect to 100.0 parts by mass of the organopolysiloxane (II), and preferably 100.0 to 10000 parts by mass with respect to 100.0 parts by mass of the organopolysiloxane (II). As long as it is 100.0 parts by mass or more, an O / W type emulsion can be easily obtained, and as long as it is 10000 parts by mass or less, the stability of the emulsion can be maintained. More preferably, it is 1000 to 5000 parts by mass.

[0086] As water which can be used, it is sufficient if the impurity concentration is tap water level, but in order to be able to maintain the stability of the emulsion, water which does not contain strong acid, strong base, a large amount of alcohol, salt, etc. is preferred.

[0087] [Other components] The addition reaction type silicone emulsion composition of the present application can contain any component other than the above respective components. As other arbitrary components, for example, in order to suppress the catalyst activity of platinum group metal catalysts, catalyst activity suppressors (control agents) selected from various organic nitrogen compounds, organic phosphorus compounds, acetylene-based compounds, oxime compounds, etc. can be listed. Acetylene-based alcohols such as 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-pentyne-3-ol, 2-phenyl-3-butyne-2-ol, etc. can be listed; acetylene-based compounds such as 3-methyl-3-pentene-1-yne, 3,5-dimethyl-1-hexene-1-yne, etc., reaction products of these acetylene-based compounds with alkoxysilane or siloxane or hydrosilane; vinylsiloxanes such as tetramethylvinylsiloxane cyclics, etc., organic nitrogen compounds such as benzotriazole, etc., and other organic phosphorus compounds, oxime compounds, compounds having multiple unsaturated groups such as maleic acid diallyl ester, etc.

[0088] Furthermore, in order to control the release properties, a leveling agent such as a silicone resin, silica, or an organopolysiloxane having no hydrogen atom and alkenyl group bonded to a silicon atom, a fluorine-based surfactant, etc. can be added as needed. Furthermore, the addition amount of the arbitrary components can be set as needed.

[0089] [Method for producing the silicone emulsion composition] In the production of the addition reaction type silicone emulsion composition of the present application, a publicly known method can be used. For example, a method in which a planetary mixer, a mixing stirrer, a high-pressure homogenizer, etc. capable of high shear can be used to mix the above-described (I) to (IV) components with part of the water (VI), or the above-described (IV) and (V) components with part of the water (VI) in a prescribed amount, emulsification is performed by a phase inversion method, and the remaining amount of water (VI) is added to dilute it can be used. The respective components can be used individually or in combination with two or more.

[0090] The above-described urea composition can be added by various methods such as a method in which the emulsion solution containing the above-described (II) to (VI) is added, a method in which water is added to make an aqueous solution and then added, a self-emulsification formulation, a method in which the emulsion solution containing the above-described (II) to (VI) is prepared as a raw material and formulated, etc. The self-emulsification formulation is a formulation in which a urea-based compound and a surfactant are mixed in advance, the mixed solution is added to the emulsion solution, and thereby the compound is dispersed in the emulsion solution without being separated.

[0091] The platinum group metal-based catalyst (V) is not emulsified simultaneously with other components, so it is preferable to add the platinum group metal-based catalyst (V) after the emulsions of (I) to (IV) are prepared and just before the emulsions are used. The platinum group metal-based catalyst is preferably one that can be dispersed in water in advance before addition, and for example, a pre-emulsified formulation in which the platinum group metal-based catalyst is mixed with the surfactant (IV) in advance, a method in which the emulsion is prepared in advance using the above method, and the like are effective.

[0092] [Release paper or release film] By so operating, the adjusted silicone emulsion composition can be used by being coated on a paper or plastic film substrate and heat-cured, i.e., can be used by being made into a release film.

[0093] Here, as the paper substrate, Grajex paper, polyethylene laminated paper, fine paper, kraft paper, clay-coated paper, mirror-coated paper, and the like can be exemplified, and as the plastic film, polyolefin films such as biaxially stretched polypropylene film, polyethylene film, ethylene-propylene copolymer film, and polyester films such as polyethylene terephthalate can be exemplified. The thickness of these paper and film substrates is not limited, but a thickness of about 5 to 300 μm can be generally used.

[0094] In order to coat the composition of the present application on a substrate, a gravure coater, an air-knife coater, a roll coater, a wire-wound rod coater, and the like can be used. The coating amount is not particularly limited, and as the solid content of silicone, generally 0.05 to 2.0 g / m 2 2.0 g / m 2 2 can be used, and more preferably 0.1 to 1.0 g / m

[0095] After the composition of the present application is coated, the coated substrate is heat-cured at 80 to 160°C, for example, using a hot air circulation type dryer or the like, but is heat-cured at 80°C for 3 minutes and the higher the temperature, the shorter the time, and at 160°C, the heat is applied for about 5 seconds, whereby a cured coating film of silicone is formed on the substrate and release properties can be imparted. The curing of the coating film can be performed by irradiation of infrared rays or ultraviolet rays, and by using these methods in combination, the time for lowering the temperature during heat curing can be shortened and the curing efficiency can be improved.

[0096] As long as the addition-cured silicone emulsion composition of the present application is thus, a cured coating film that can be well adhered to a substrate regardless of the kind of the paper or plastic film substrate can be formed. Further, the cured coating film has appropriate release force with respect to an adhesive, so it can be used as a release film. Furthermore, after the composition of the present application is coated, the coated substrate is heated at 80 to 160°C for 3 minutes to about 5 seconds, whereby a cured coating film of silicone is formed on the substrate, so a release film imparted with release properties can be easily manufactured without using an expensive device and without going through a complicated procedure. [Examples]

[0097] Hereinafter, the present application will be specifically described using examples and comparative examples, but the present application is not limited to these examples.

[0098] Next, examples of the present application, comparative examples are cited, and in the examples, the physical property values in the table represent measured values produced by the following test methods. In addition, unless otherwise specified, viscosity means absolute viscosity.

[0099] [Coatability] Immediately after the silicone emulsion composition was prepared, the prepared silicone emulsion composition was coated on a 38 μm PET film substrate at 0.25 g / m 2 of solid content, and at this time, whether the emulsion composition could be uniformly coated on the substrate was visually judged, and then it was set as coatability.

[0100] [Adhesion] Immediately after the silicone emulsion composition was prepared, the prepared silicone emulsion composition was coated on a 38 μm PET film substrate at 0.25 g / m 2 of solid content, and heated in a hot air dryer at 150°C for 30 seconds to form a cured coating film, and the cured coating film was rubbed with a finger 10 times, and whether there was fogging and peeling was visually judged, and then it was set as adhesion.

[0101] [Peeling force] Immediately after the silicone emulsion composition was prepared, curing was performed under the same conditions as the coatability and adhesion measurement at 150°C x 30 seconds, and then it was left to stand at 25°C for 24 hours. An adhesive tape (Tesa 7475 tape, manufactured by Tesa Tape Inc.) having a width of 25 mm was applied under a load of 70 g / cm 2 at 25°C for 20 hours, and then using a tensile testing machine, the adhesive tape adhered to the test sample was peeled off at an angle of 180° and a speed of 0.3 m / minute, and the force (N) required to peel it off was measured at a width of 25 mm.

[0102] [Residual tack] Curing of the silicone emulsion composition was performed in the same manner as the peeling force, and a polyester adhesive tape (No. 31B, manufactured by Nitto Electric Industrial Co., Ltd.) was adhered to the surface thereof, and a load of 20 g / cm 2After heat treatment with a load of 100 μm for 20 hours, the tape was attached to a stainless steel plate. The treated tape was then removed and the force A (N) required to peel the tape from the stainless steel plate was measured at a width of 25 mm. A separate untreated polyester adhesive tape was used as a standard tape and the force B (N) required to peel the tape from the stainless steel plate was similarly measured. The percentage of force A to force B was then defined as the residual adhesion rate.

[0103] [Preparation of emulsion composition] Silicone emulsion 1 The following components were poured into a 5-liter composite emulsifier (TK Mixer M model, manufactured by PRIMIX Corp.) equipped with an anchor-type stirring device capable of stirring the entire container and a rotating circular plate having small tooth-shaped protrusions provided alternately in an up-and-down manner on its circumference, and uniformly stirred and mixed to achieve phase inversion, and then stirred for 15 minutes: 100 parts by mass of siloxane (IIa) as the organopolysiloxane (II), which was 1.9 mol% of (CH3)2(CH2=CH)SiO 1 / 2 dimethylvinylsiloxane units, 97.5 mol% of (CH3)2SiO 2 / 2 dimethylsiloxane units, 0.6 mol% of CH3SiO 3 / 2 The organic hydrogen polysiloxane (III) is composed of 2 mol% of (CH3)3SiO 1 / 2 The trimethylsiloxane units represented by 28 mol% are (CH3)2SiO 2 / 2 dimethylsiloxane units, 70 mol% of (CH3)HSiO 2 / 2 The following preparations were prepared: a methylhydrogensiloxane emulsion (VI) composed of methylhydrogensiloxane units, having a viscosity of 122.2 mPa·s and a Si-H group content of 1.080 mol / 100 g; 0.78 parts by mass of polyoxyethylene lauryl ether (IVa, HLB 13.6) as a surfactant (IV); 51.95 parts by mass of a 10% aqueous solution of polyvinyl alcohol (IVa-1) as a water-soluble resin (thickener); and 0.39 parts by mass of ethynylcyclohexanol as a catalyst activity inhibitor. Subsequently, 103.04 parts of water (VI) was added as dilution water and stirred to obtain an O / W emulsion 1 containing 40% silicone.

[0104] Silicone Emulsion 2 In a 5 liter compound emulsifier (TK Mix-Emulsor M type, manufactured by PRIMIX Corp.) having an anchor type stirring device capable of stirring the entire container and a rotatable circular plate provided with small tooth type projections on the circumference in an up-and-down and alternate manner, 100 parts by mass of the siloxane (IIa) as the organopolysiloxane (II) consisting of 1.3 mole% of dimethylvinylsiloxane units represented by the formula: (CH3)2(CH2=CH)SiO1 / 2, 98.7 mole% of dimethylsiloxane units represented by the formula: (CH3)2SiO1 / 2, and 0.1 mole% of methylhydrogenosiloxane units represented by the formula: (CH3)HSiO1 / 2, having a viscosity of 386 mPa-s and a vinyl group content of 0.018 mole / 100 g; 2.26 parts by mass of the methylhydrogenopolysiloxane (IIIa) as the organohydrogenopolysiloxane (III) consisting of 2 mole% of trimethylsiloxane units represented by the formula: (CH3)3SiO1 / 2, 28 mole% of dimethylsiloxane units represented by the formula: (CH3)2SiO1 / 2, and 70 mole% of methylhydrogensiloxane units represented by the formula: (CH3)HSiO1 / 2, having a viscosity of 122.2 mPa-s and a Si-H group content of 1.080 mole / 100 g; 0.78 parts by mass of the polyoxyethylene lauryl ether (IVa, HLB = 13.6) as the surfactant (IV); 51.95 parts by mass of a 10% aqueous solution of polyvinyl alcohol (IVa-1) as the water-soluble resin (thickening agent); and 0.21 parts by mass of the acetylenic cyclohexanol as the catalyst activity inhibitor were uniformly stirred and mixed to effect phase inversion, and then stirred for 15 minutes to obtain an organic silicon component 40% O / W emulsion 2. 1 / 2 2 / 2 1 / 2 2 / 2 2 / 2

[0105] Platinum catalyst emulsion 3 The following components were uniformly stirred and mixed to effect phase inversion, and then stirred for 20 minutes: 20.0 parts by mass of the vinyl siloxane complex (V) of platinum having addition reaction activity dispersed in a substance containing a vinyl group-containing organopolysiloxane; 0.2 parts by mass of the surfactant (IV); and 1.0 part by mass of the water-soluble resin. Then, 67.9 parts by mass of water (VI) were added as dilution water and stirred to obtain a platinum concentration of 1000 ppm of the O / W platinum catalyst emulsion 3.

[0106] [Synthesis Example 1] Synthesis of silane coupling agent (Ib) ​​​​​In a 300 mL separable flask equipped with a stirrer, a reflux cooler, and a thermometer, 148.3 g (0.83 mol) of 3-aminopropyltrimethoxysilane and 51.7 g (0.86 mol) of urea were charged, and heated to 120°C. The ammonia gas generated by the reaction was distilled off under reduced pressure, and a silane coupling agent (Ib) was obtained. [Chemical Formula 28]

[0107] [Synthesis Example 2] Synthesis of Silane Coupling Agent (Ic) In a 300 mL separable flask equipped with a stirrer, a reflux cooler, and a thermometer, 128.9 g (0.58 mol) of 3-(2-aminoethylamino)propyltrimethoxysilane and 71.1 g (1.2 mol) of urea were charged, and heated to 130°C. The ammonia gas generated by the reaction was distilled off under reduced pressure, and 180 g of methanol was added, and a 50% methanol solution of a silane coupling agent (Ic) was obtained. [Chemical Formula 29]

[0108] [Synthesis Example 3] Synthesis of Silane Coupling Agent (f) In a 500 mL separable flask equipped with a stirrer, a reflux cooler, an esterification reactor, and a thermometer, 300 g of water, 55.3 g of 3-aminopropyltriethoxysilane, and 132 g of a 50% by mass methanol solution of 3-ureidopropyltriethoxysilane were charged, and heated to 120°C. A mixture of methanol, ethanol, and water generated by hydrolysis was distilled off under reduced pressure, and a silane coupling agent oligomer (f) containing ureido and amino groups was obtained.

[0109] [Synthesis Example 4] Synthesis of Silane Coupling Agent (g) In a 500 mL separable flask equipped with a stirrer, a reflux cooler, an esterification reactor, and a thermometer, 1.83 g of water, 82 g of methanol, 155 g of 3-glycidoxypropyltrimethoxysilane, and 145 g of 3-ureidopropyltrimethoxysilane were charged, and heated to 120°C. A mixture of methanol and water generated by hydrolysis was distilled off under reduced pressure, and a silane coupling agent oligomer (g) containing ureido and glycidoxy groups was obtained.

[0110] <Example 1> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. The composition in which 5.0 parts by mass of silane coupling agent (Ib) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results thereof are shown in Table 3.

[0111] <Example 2> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. The composition in which 10.0 parts by mass of silane coupling agent (Ib) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results thereof are shown in Table 3.

[0112] <Example 3> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. The composition in which 15.0 parts by mass of silane coupling agent (Ib) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results thereof are shown in Table 3.

[0113] <Example 4> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. The composition in which 5.0 parts by mass of silane coupling agent (Ic) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results thereof are shown in Table 3.

[0114] <Example 5> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner such that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. A composition in which 10.0 parts by mass of silane coupling agent (Ic) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results are shown in Table 3.

[0115] <Example 6> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner such that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. A composition in which 5.0 parts by mass of the following 1-methyl urea (Id) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results are shown in Table 3. [Chemical Formula 30]

[0116] <Example 7> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner such that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. A composition in which 10.0 parts by mass of urea compound (Id) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results are shown in Table 3.

[0117] <Example 8> The 259 parts by mass of silicone emulsion 1 (total amount of silicone oxane: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added in a manner such that the platinum group mass relative to the total amount of silicone component in silicone emulsion 1 became 150 ppm. A composition in which 5.0 parts by mass of the following butyl urea (Ie) was formulated and mixed well was used as a silicone emulsion composition, and the coating property, adhesion, peeling strength, and residual tack were measured, and the results are shown in Table 4. [Chemical Formula 31]

[0118] <Example 9> 256 parts by mass of silicone emulsion 2 (total organosiloxane content: 100 parts by mass) was diluted with 1023 parts by mass of water (VI), and platinum catalyst emulsion 3 was added so that the mass of the platinum group component relative to the total amount of silicone in silicone emulsion 1 was 150 ppm. 1.9 parts by mass of silane coupling agent (Ib) was prepared and mixed well to form a silicone emulsion composition. The coating properties, adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 4.

[0119] <Comparative Example 1> 259 parts by mass of silicone emulsion 1 (total organosiloxane content: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added so that the mass of the platinum group component relative to the total amount of silicone in silicone emulsion 1 was 150 ppm. The well-mixed composition was used as a silicone emulsion composition, and coating properties, adhesion, peel strength, and residual adhesion were measured. The results are shown in Table 4.

[0120] <Comparative Example 2> 259 parts by mass of silicone emulsion 1 (total organosiloxane content: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added so that the mass of the platinum group component relative to the total amount of silicone in silicone emulsion 1 was 150 ppm. 5.0 parts by mass of silane coupling agent (f) was prepared and mixed well to form a silicone emulsion composition. The coating properties, adhesion, peel strength, and residual adhesion rate were measured. The results are shown in Table 4.

[0121] <Comparative Example 3> 259 parts by mass of silicone emulsion 1 (total organosiloxane content: 100 parts by mass) was diluted with 1813 parts by mass of water (VI), and platinum catalyst emulsion 3 was added so that the mass of the platinum group component relative to the total amount of silicone in silicone emulsion 1 was 150 ppm. 5.0 parts by mass of a silane coupling agent (g) was prepared and mixed well, and the resulting composition was used as a silicone emulsion composition. Coating properties, adhesion, peel strength, and residual adhesion were measured. The results are shown in Table 4.

[0122] [Table 1] Note 1: Parts by mass relative to 100 parts by mass of (II) + (III) Note 2: Concentration (ppm) in terms of platinum mass relative to the mass of (II) + (III)

[0123] [Table 2] Note 1: Parts by mass relative to 100 parts by mass of (II) + (III) Note 2: Concentration (ppm) in terms of platinum mass relative to the mass of (II) + (III)

[0124] [Table 3] Note 1: The number that can be evenly coated on the substrate is indicated by 0, and the number that cannot be evenly coated is indicated by ×. Note 2: The tightness is indicated by 0 if the seal does not fall off after 10 times of friction, △ if the seal falls off after 10 times of friction, and × if the seal falls off after a few times of friction. Note 3: PET = Polyester film

[0125] [Table 4] Note 1: The number that can be evenly coated on the substrate is indicated by 0, and the number that cannot be evenly coated is indicated by ×. Note 2: The tightness is indicated by 0 if the seal does not fall off after 10 times of friction, △ if the seal falls off after 10 times of friction, and × if the seal falls off after a few times of friction. Note 3: PET = Polyester film

[0126] The cured films formed by curing the addition reaction-curable silicone emulsion composition of the present invention through Examples 1 to 9 can achieve good adhesion to the film substrate. That is, based on Examples 1 to 9 and Comparative Example 1, it can be seen that good adhesion can be achieved by adding urea compounds (Ib), (Ic), (Id), and (Ie). In particular, it can be seen that the urea compound (Ic) not only has good adhesion, but also achieves easy peeling and high residual adhesion compared to (Ib), (Id), and (Ie). Based on Examples 1 to 9 and Comparative Example 2, it can be seen that the urea-containing oligomer and the urea-containing monomer can achieve good adhesion and residual adhesion. Based on Comparative Examples 2 and 3, it can be seen that if the amino group is changed to an epoxy group in order to improve the adhesion and residual adhesion, the dispersibility in the emulsion solution will be reduced, resulting in deterioration of the coating property.

[0127] As described above, the addition reaction-curable silicone emulsion composition of the present invention has excellent curing properties and can also be made into a cured film that can be well adhered to the substrate, regardless of the type of paper or plastic film substrate. Furthermore, the cured film has appropriate peeling force for the adhesive, so it can be used as a peeling film. Furthermore, the peeling film obtained by applying and curing the above-mentioned silicone emulsion composition on a paper or plastic film substrate can be well adhered to the substrate, and on the other hand, a cured film with appropriate peeling force for the adhesive can be formed, so it is highly practical. In addition, after applying the composition of the present invention, as long as the coated substrate is heated under relatively stable conditions, a cured silicone film can be formed on the substrate. Therefore, a peeling film with peeling properties can be easily produced without using expensive equipment or going through complicated steps.

[0128] This manual contains the following methods. [1] An addition reaction curable silicone emulsion composition comprising at least one urea compound (I) selected from non-polymeric organic compounds having at least one urea group in the molecule, an organopolysiloxane (II) having at least two alkenyl groups in one molecule, and water (VI); The urea compound (I) is contained in an amount of 1.0 part by mass or more and water (VI) is contained in an amount of 100.0 parts by mass or more relative to 100.0 parts by mass of the organopolysiloxane (II). [2] The addition reaction curable silicone emulsion composition as described in [1] above, wherein the non-polymer organic compound is selected from one or more of the following compounds: a silane coupling agent monomer, 1-methylurea, ethylurea, 1,1-dimethylurea, 1,1-diethylurea, acetylurea, 2-hydroxyethylurea, butylurea, 2-chloroethylurea, phenylurea, cyclohexylurea, p-tolylurea, o-tolylurea, and benzylurea. [3] The addition reaction curable silicone emulsion composition according to [2] above, wherein the silane coupling agent monomer has a structure represented by the following general formula (Ia-1) and / or (Ia-2): [Chemical Formula 32] (In the general formula, R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is 2 or 3, X is a monovalent hydrocarbon group having 1 to 4 carbon atoms or hydrogen, and i, j, and k are integers of 2 to 20). [4] The addition reaction-curable silicone emulsion composition according to any one of [1] to [3] above, comprising: (I) 1 to 15 parts by mass of the above-mentioned urea-based compound; (II) 100 parts by mass of the organopolysiloxane 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 in terms of 30% toluene dilution viscosity, [Chemical Formula 33] (R 2 3Si-O 1 / 2 ) p (R 2 2Si-O 2 / 2 ) q (R 2 Si-O 3 / / 2 ) r (Si-O 4 / 2 ) s (II-1) (R 2 is a group selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bond, or alkenyl groups having 2 to 12 carbon atoms which may contain oxygen atoms, and R 2 At least two of them are alkenyl groups and satisfy the following ranges: 2≤p, 0≤q≤30000 and 0≤r, 0≤s, 0≤r+s≤30); (III) 1 to 30 parts by mass of an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to Si atoms in one molecule; (IV) a surfactant in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the total of the organopolysiloxane (II) and the organohydrogenpolysiloxane (III); (V) a catalytic amount of a platinum group metal catalyst; (VI) 100 to 10,000 parts by mass of water. [5] A release film comprising a cured film of the addition reaction-curable silicone emulsion composition according to any one of [1] to [4] formed on a paper or plastic film substrate.

[0129] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are exemplary, and any other embodiments having substantially the same structure and exhibiting the same effects as those described in the claims of the present invention are within the technical scope of the present invention.

Claims

1. An addition reaction curable silicone emulsion composition, characterized in that: comprising at least one urea compound (I) selected from non-polymeric organic compounds having at least one urea group in the molecule, an organopolysiloxane (II) having at least two alkenyl groups in one molecule, and water (VI), The urea compound (I) is contained in an amount of 1.0 part by mass or more and water (VI) is contained in an amount of 100.0 parts by mass or more relative to 100.0 parts by mass of the organopolysiloxane (II).

2. The addition reaction curable silicone emulsion composition according to claim 1, characterized in that: The non-polymer organic compound is selected from one or more of the following compounds: silane coupling agent monomer, 1-methylurea, ethylurea, 1,1-dimethylurea, 1,1-diethylurea, acetylurea, 2-hydroxyethylurea, butylurea, 2-chloroethylurea, phenylurea, cyclohexylurea, p-tolylurea, o-tolylurea, and benzylurea.

3. The addition reaction curable silicone emulsion composition according to claim 2, characterized in that: The silane coupling agent monomer has a structure represented by the following general formula (Ia-1) and / or (Ia-2); [Chemical Formula 1] In the general formula, R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is 2 or 3, X is a monovalent hydrocarbon group having 1 to 4 carbon atoms or hydrogen, and i, j, and k are integers of 2 to 20.

4. The addition reaction curable silicone emulsion composition according to claim 1, characterized in that: contain: (I) 1 to 15 parts by mass of the urea compound; (II) 100 parts by mass of the organopolysiloxane, wherein the organopolysiloxane is represented by the following general formula (II-1), and the organopolysiloxane has an absolute viscosity at 25° C. in the range of 10 mPa·s to 50,000 mPa·s as a 30% toluene dilution viscosity, [Chemical Formula 2] (R 2 3Si-O 1 / 2 ) p (R 2 2Si-O 2 / 2 ) q (R 2 Si-O 3 / 2 ) r (Si-O 4 / 2 ) s (II-1) Among them, R 2 is a group selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms and no aliphatic unsaturated bond, or alkenyl groups having 2 to 12 carbon atoms which may contain oxygen atoms, and R 2 At least two of them are alkenyl groups and satisfy the following ranges: 2≤p; 0≤q≤30000 and 0≤r; 0≤s; 0≤r+s≤30; (III) 1 to 30 parts by mass of an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to Si atoms in one molecule; (IV) a surfactant, wherein the amount of the surfactant is 0.1 to 20 parts by mass relative to 100 parts by mass of the total of the organopolysiloxane (II) and the organohydrogenpolysiloxane (III); (V) a catalytic amount of a platinum group metal catalyst; and (VI) 100 to 10,000 parts by mass of water.

5. A peeling film, characterized in that The release film is formed by forming a cured film of the addition reaction-curable silicone emulsion composition according to any one of claims 1 to 4 on a paper or plastic film substrate.

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