OIL-IN-WATER SILICONE EMULSION COMPOSITION FOR RELEASE FILM, RELEASE FILM AND METHOD FOR PRODUCING RELEASE FILM, AND METHOD FOR ADJUSTING COATING PROPERTIES AND RELEASE PROPERTIES OF RELEASE FILM

Abstract

An oil-in-water silicone emulsion along with a method of making and modifying the same.

Claims

1-11. (canceled)

12. An oil-in-water silicone emulsion composition, comprising components (A) to (E): a component (A) has 20 to 60 parts by mass of an organopolysiloxane resin that has an average composition formula represented by a general formula 1, and contains 1 to 5% by mole of an alkenyl group bonded to a silicon atom, 10 to 90% by mole of an M unit represented by a general formula 2, 0 to 90% by mole of a T unit represented by a general formula 3, and 5 to 90% by mole of a Q unit represented by a general formula 4, and in which a molar ratio M/Q of the M unit to the Q unit is 0.1 to 4 and a molar ratio T/Q of the T unit to the Q unit is 0 to 1,000, wherein an amount in parts by mass is represented when the whole mass of the composition is 100 parts by mass, and hereinafter, the amount of each component is represented in the same manner;
R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2  [general formula 1] wherein R.sup.1 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated group, wherein R.sup.2 is an alkenyl group, wherein a is 0.999 to 2.999, wherein b is 0.001 to 2, and wherein a+b is 1 to 3; ##STR00005## wherein R.sup.3 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond; wherein R.sup.4 is independently a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms; wherein R.sup.5 is a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and c is an integer of 0 to 3; a component (B) has 5 to 30 parts by mass of an organohydrogenpolysiloxane that has an average composition formula represented by a general formula 5 and contains two or more hydrogen atoms bonded to silicon atoms;
R.sup.6.sub.dH.sub.eSiO.sub.(4-a-e)/2  [general formula 5] wherein R.sup.6 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated group, wherein d is 0.999 to 2.999, wherein e is 0.001 to 2, and wherein d+e is 1 to 3; a component (C) has 1 to 10 parts by mass of a nonionic surfactant; a component (D) has 1 to 500 ppm of a platinum-based catalyst relative to the amount of the component (A); a component (E) has 30 to 80 parts by mass of water; wherein the content of the methyl group in the solid content in this release agent composition is 5% by mass or more; and wherein the content of the methyl group is a calculated value based on the amount of used raw material of the composition.

13. The oil-in-water silicone emulsion of claim 12, wherein the composition is prepared by a kit in which at least two or more of the components (A) to (D) are dispersed in the component (E).

14. The oil-in-water silicone emulsion of claim 12, wherein the oil-in-water silicone emulsion is a release film that is applied to a surface of a plastic film.

15. The oil-in-water silicone emulsion of claim 12, wherein the oil-in-water silicone emulsion is a release film for a multilayer ceramic capacitor (MLCC), a semiconductor interlayer insulating film, a capacitor film or a thermal conduction film.

Description

DESCRIPTION OF EMBODIMENTS

[0062] <Embodiments of Oil-In-Water Silicone Emulsion Composition for Release Film and Release Film Obtained by Applying the Composition>

[0063] Hereinafter, details of an oil-in-water silicone emulsion composition for a release film according to the present invention will be described. The oil-in-water silicone emulsion composition for a release film according to the present invention contains the following components (A) to (E).

(Component (A))

[0064] The component (A) is an organopolysiloxane resin that forms a crosslinking structure under an addition reaction in the presence of the following components (B) and (C) when the oil-in-water silicone emulsion composition for a release film according to the present invention is applied to a film to produce a release film. Therefore, favorable coating properties can be imparted to a release surface of the release film by the component (A). Specifically, as a chemical structure, the component (A) has an average composition formula represented by the general formula (1), and contains 1 to 5% by mole of alkenyl group bonded to a silicon atom, 10 to 90% by mole of an M unit represented by the general formula (2), 0 to 90% by mole of a T unit represented by the general formula (3), and 5 to 90% by mole of a Q unit represented by the general formula (4). The molar ratio M/Q of the M unit to the Q unit is 0.1 to 4, and the molar ratio T/Q of the T unit to the Q unit is 0 to 1,000.

[Chemical formula 1]

R.sup.1.sub.aR.sup.2.sub.bSiO.sub.(4-a-b)/2  (1)

(wherein R.sup.1 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated group, R.sup.2 is an alkenyl group, a is 0.999 to 2.999, b is 0.001 to 2, and a+b is 1 to 3),

##STR00004##

(wherein R.sup.3 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and no aliphatic unsaturated bond, R.sup.4 is independently a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, R.sup.5 is a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and c is an integer of 0 to 3.)

[0065] Examples of the alkenyl group in the component (A) may include alkenyl groups having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a 1-butenyl group, and a 1-hexenyl group. These alkenyl groups react with the component (B), which will be described later, to form a network structure. The content of the component (A) is 20 to 60 parts by mass relative to 100 parts by mass of the total mass of the components (A) to (E). If the amount is more than 60 parts by mass, the viscosity of the composition may increase and the handling property may deteriorate. More preferably, the amount is 25 to 55 parts by mass.

[0066] The component (A) is to be referred to as the main ingredient of the oil-in-water silicone emulsion composition for a release film, and is a component responsible for the coating properties and the release properties after the release film is formed. Since the component (A) is a polymer having a siloxane skeleton, the easily rotatable main chain and the presence of a methyl group in the M unit can lower the surface free energy of the release surface, whereby the release film exerts the release properties. In addition, the presence of the Q unit or T unit having a high density of siloxane bond causes a coating material having a high polarity and a thin film thickness to exert the coating properties of the coating material.

[0067] The content of the M unit in the component (A) is preferably within a range of 10 to 90% by mole. When the content is less than 10% by mole, sufficient release properties cannot be exerted. When the content is more than 90% by mole, the introduction proportion of the Q unit or the T unit is not increased and the length of a polymer chain is decreased in terms of design of the component (A). In this case, the release film does not have sufficient strength or an unreacted chain is produced, so that some defects may be caused.

[0068] The content of the Q unit in the component (A) is preferably within a range of 5 to 90% by mole. When the content is less than 5% by mole, sufficient coating properties cannot be exerted. When the content is more than 90% by mole, the introduction proportion of the M unit is not increased in terms of design of the component (A). In this case, the crosslink density of the whole release film becomes too high, so that flexibility is deteriorated.

[0069] The component (A) may contain the T unit as an optional component. The presence of the T unit can increase the density of siloxane bond in the release film like the Q unit. The density of siloxane bond per unit of the T unit is lower than that of the Q unit. The content of the T unit in the component (A) is preferably within a range of 0 to 90% by mole. When the content is more than 90% by mole, the introduction proportion of the M unit is not increased in terms of design of the component (A). In this case, the crosslink density of the whole release film becomes too high, so that flexibility is deteriorated.

[0070] The molar ratio M/Q of the content of the M unit to the content of the Q unit in the component (A) is a factor of mostly affecting the coating properties in the composition. The content of the Q unit that increases the density of siloxane bond directly affects the coating properties. However, in introduction of the Q unit into the organopolysiloxane component, the Q unit is generally introduced in a form in which a terminal thereof is capped with the M unit. Therefore, it is reasonable that the content of the Q unit is substantially adjusted by the molar ratio M/Q. The molar ratio M/Q is preferably within a range of 0.1 to 4. When the molar ratio is less than 0.1, the content of methyl group in the composition is low. Therefore, sufficient release properties are not exerted. When the molar ratio is more than 4, the crosslink density of the whole release film becomes too high, and flexibility is deteriorated. The molar ratio M/Q is more preferably within a range of 0.2 to 2.5, and further preferably within a range of 0.5 to 1.5.

[0071] Even when the molar ratio M/Q is less than 0.01 or more than 4, the content of the methyl group in the release film that affects the releasability can also be adjusted by adjusting the content of the Q unit or introducing a methyl group using a different component into the release film. However, it is difficult to simultaneously achieve both favorable coating properties and favorable release properties. Therefore, it is preferable that the molar ratio M/Q fall within the aforementioned range.

[0072] When the T unit is introduced, the density of siloxane bond in the component (A) is increased. However, the increase by introduction of the T unit is less effective than that by introduction of the Q unit. Therefore, the molar ratio T/Q of the T unit to the Q unit has a certain proper range. The molar ratio T/Q is preferably within a range of 0 to 1,000. When the molar ratio is more than 1,000, the content of the Q unit becomes too low. Therefore, the effect of increasing the density of siloxane bond is insufficient, and sufficient coating properties are not obtained. The molar ratio T/Q is more preferably within a range of 0 to 500.

[0073] The component (A) may be a single component or a mixture of two or more types of components that satisfy conditions described above.

(Component (B))

[0074] The component (B) is an organohydrogenpolysiloxane having an average composition formula represented by the general formula (5) and containing two or more hydrogen atoms bonded to silicon atoms in one molecule, and is a cross-linking component for the component (A).

(Chemical formula 5)

R.sup.6.sub.dH.sub.eSiO.sub.(4-d-e)/2  (5)

In the formula (5), R.sup.5 is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated group, d is 0.999 to 2.999, e is 0.001 to 2, and d+e is 1 to 3. R.sup.5 used is a hydrocarbon group exemplified as examples of R.sup.1, and is preferably an alkyl group, more preferably a methyl group. The number of hydrogen atoms bonded to the silicon atom of the component (B) is preferably 3 or more in one molecule. The viscosity of this component (B) at 25° C. is usually 1 to 3,000 mPa-s, and preferably 5 to 500 mPa-s.

[0075] The content of the component (B) is 5 to 30 parts by mass relative to 100 parts by mass of the total mass of the components (A) to (E). If the content is less than 5 parts by mass, the curing of the component (A) is insufficient and the strength of the release film is insufficient. If the content is more than 30 parts by mass, the viscosity of the composition is increased and the handling property may deteriorate as well as the SiH group becomes excessive. Thus, there is a possibility that unreacted crosslinking agent bleeds out after the formation of the release film, so that some trouble may occur. The content is more preferably 10 to 20 parts by mass.

[0076] The amount of the component (B) to be mixed in the oil-in-water silicone emulsion composition for a release film according to the present invention is adjusted according to the number of the alkenyl group of the component (A). The amount of the component (B) to be mixed is adjusted so that the ratio (NE/NA) of the number (NE) of the hydrogen atoms bonded to a silicon atom of the component (B) to the number (NA) of the alkenyl group bonded to a silicon atom of the component (A) is 1.0 or more and 6.0 or less (1.0≤(NE/NA)≤6.0), and preferably 1.5 or more and 4.0 or less (1.5≤(NE/NA)≤4.0). When NE/NA is less than 1, curing of the composition is not sufficiently promoted, and an unreacted alkenyl group remains in a release agent layer. In this case, the release properties are likely to be changed over time. When NE/NA is more than 6, the release properties are enhanced due to the organohydrogenpolysiloxane despite the intension of the present invention. Those skilled in the art can produce the component (B) by a publicly known method.

(Component (C))

[0077] The component (C) is a nonionic surfactant and plays a role of dispersing the components (A) and (B) and the component (D) described later in water, so that the oil-in-water silicone emulsion composition for a release film according to the present invention can be provided. The component (C) is preferably a nonionic surfactant having an HLB value of 8.0 to 19.0, preferably 10.0 to 18.0, and particularly preferably 10.0 to 16.0. Note that an HLB value represents the balance between hydrophilicity and lipophilicity. The component (C) is not particularly limited as long as the component (C) is a nonionic surfactant having an HLB value falling within the aforementioned range. If the HLB value of the surfactant used is not appropriate, even when emulsification is achieved, storage stability and dilution stability are poor and sufficient performance cannot be exerted. As another emulsifying aid, a surfactant having a low HLB value may be used in combination.

[0078] Examples of such nonionic surfactants may include a sorbitan fatty acid ester, a glycerin fatty acid ester, a decaglycerin fatty acid ester, a polyglycerin fatty acid ester, a propylene glycol pentaerythritol fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene solibit fatty acid ester, a polyethylene glycerin fatty acid ester, a polyethyleneglycol fatty acid ester, a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene caster oil, hydrogenated caster oil, a polyoxyethylene alkyl amine fatty acid amide, and a polyalkyl glicoside. These nonionic surfactants are preferable in terms of safety, stability, and price, and can be used solely or as a mixture of two or more types thereof. In particular, from the viewpoint of emulsion stability, a polyoxyethylene alkyl ether is preferable. The content of the component (C) is 1 to 10 parts by mass relative to 100 parts by mass of the total mass of the components (A) to (E). If the content is less than 1 part by mass, dispersion is difficult to occur, and if it is more than 10 parts by mass, the viscosity of the resulting composition becomes high and the handling property becomes poor. It is more preferably 3 to 6 parts by mass.

(Component (D))

[0079] The component (D) is a platinum-based catalyst. The component (D) is a hydrosilylation catalyst that catalyzes an addition reaction in which the crosslinking structure of the component (A) through the component (B) is formed. The component (D) is contained in an amount of 1 to 500 ppm, preferably 5 to 200 ppm, and more preferably 20 to 100 ppm, relative to the weight of the component (A). When the content of the component (D) is less than 1 ppm, it takes a long time to cure the composition, and the production efficiency of the release film in which the oil-in-water silicone emulsion composition for a release film according to the present invention has been applied may be deteriorated. When the content is more than 500 ppm, the time required for processing the composition is short. Therefore, workability when the composition is applied to a film substrate may be deteriorated.

[0080] The component (D) is composed of a metal or a compound containing the metal. Examples of the metal and compounds thereof may include platinum, rhodium, palladium, ruthenium, and iridium. Preferred examples used may be platinum and a compound containing platinum. Among these, platinum-based catalysts are particularly suitable because of their high reactivity. The metal may be fixed on a particulate carrier material, such as activated carbon, aluminum oxide, or silicon oxide. Examples of the platinum compounds may include platinum halides (for example, reaction products of cyclohexane and PtCl.sub.4, H.sub.2PtCl.sub.4.6H.sub.2O, Na.sub.2PtCl.sub.4.4H.sub.2O or H.sub.2PtCl.sub.4.6H.sub.2O), a platinum-olefin complex, a platinum-alcohol complex, a platinum-alcoholate complex, a platinum-ether complex, a platinum-aldehyde complex, a platinum-ketone complex, a platinum-vinylsiloxane complex (for example, a platinum-1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex, bis-(γ-picoline)-platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, and cyclopentadiene-platinum dichloride), a bis(alkynyl)bis(triphenylphosphine) platinum complex, and a bis(alkynyl) (cyclooctadiene) platinum complex. The hydrosilylation catalyst can also be used in a microencapsulated form. The particulate solid which contains the catalyst in this case and is insoluble in an organopolysiloxane is, for example, a thermoplastic resin such as a polyester resin or silicone resin. It is also possible to use the platinum-based catalyst in the form of a inclusion compound, for example in cyclodextrins.

(Component (E))

[0081] The component (E) is water that is a dispersion medium during emulsification of the components (A) to (D). Water is not particularly limited, and ion exchange water is preferably used. The pH of the water is preferably 2 to 12, and particularly preferably 4 to 10. Use of mineral water is not recommended. However, when mineral water is used, it is preferable that mineral water be used in combination with a metal deactivator, or the like. When the total mass of components dispersed is 100 parts by mass, the component (E) is added in an amount corresponding to 30 to 80 parts by mass, and preferably 35 to 70 parts by mass.

[0082] It is preferable that the oil-in-water silicone emulsion composition for a release film according to the present invention be not produced by dispersing all the components (A) to (D) once in the component (E) but be produced by preparing a kit in which among the components (A) to (D), at least two or more types of components are dispersed in the component (E) and finally mixing the kit as an oil-in-water silicone emulsion composition. When all the components (A) to (D) are dispersed once in the component (E), an addition reaction of the components (A), (B), and (D) advances in production of the composition. As a result, the release agent layer cannot be formed on the film substrate. Examples of producing methods may include a method including preparing a kit in which the components (A), (C), and (D) are dispersed in the component (E), preparing another kit in which the components (B) and (D) are dispersed in the component (E), and mixing these kits. Even when some types of kits are prepared, the amounts of the components (A) and (B) are adjusted so that in a final oil-in-water silicone emulsion composition, the ratio (NE/NA) of the number (NE) of the hydrogen atoms bonded to a silicon atom of the component (B) to the number (NA) of the alkenyl group bonded to a silicon atom of the component (A) is 1.0 or more and 6.0 or less (1.0≤(NE/NA)≤6.0), and preferably 1.5 or more and 4.0 or less (1.5≤(NE/NA)≤4.0), and the amount of the component (C) is necessarily adjusted to 1 to 500 ppm, preferably 5 to 200 ppm, and more preferably 20 to 100 ppm, relative to the weight of the component (A). Even when some of the components (A) to (D) are dispersed in the component (E) to form kits, the oil-in-water silicone emulsion composition for a release film according to the present invention is finally made as an emulsion composition in which influence on the environment and the human body is considered, unlike a solvent-containing composition. This is because the component (E) as the dispersion medium is water.

[0083] As a method for dispersing the components (A) to (D) in the component (E), a publicly known method can be employed. For example, a method for mixing and emulsifying the components with a homogenizer, a colloid mill, a homomixer, a high-speed stator rotor stirrer, or the like can be employed. In dispersing the components (A) to (D) in the component (E), specifically, a part of the component (E) is added to the components (A) to (D), and the mixture is stirred to form a water-in-oil emulsion. The rest of water is further added to form an oil-in-water emulsion. In this manner, dispersion of the components (A) to (D) is facilitated, and the stability of the emulsion is improved.

[0084] For example, the oil-in-water silicone emulsion composition for a release film according to the present invention may contain a component other than silicone, such as an organic polymer. When desired conditions are satisfied, target coating properties and release properties are achieved. In order to achieve more sufficient coating properties and release properties, it is preferable that the composition contain silicone as a main component.

[0085] When the oil-in-water silicone emulsion composition for a release film according to the present invention contains an organopolysiloxane having a polar modifying group, the coating properties can be enhanced more. In particular, a polyether-modified silicone is the most preferable.

[0086] The content of the silicone in the silicone composition is preferably 1 to 50 parts by mass. When the content is less than 1 part by mass, an effect of improving the coating properties is insufficient. When the content is more than 50 parts by mass, the release properties are deteriorated. The content is particularly preferably within a range of 2 to 30 parts by mass.

[0087] The oil-in-water silicone emulsion composition for a release film according to the present invention may contain an adhesion-enhancing agent to enhance the adhesion to the film substrate, a migration component to adjust the release properties, or a preservative to prevent corrosion without impairing the object of the present invention. Examples of such an adhesion-enhancing agent may include a general silane coupling agent, examples of such a migration component may include an oil-in-water silicone emulsion, and examples of such a preservative may include sorbic acid, sorbate, acetic acid, lactic acid, and formalin.

[0088] The release film obtained by applying the oil-in-water silicone emulsion composition for a release film according to the present invention is in accordance with the following embodiment.

[0089] Examples of the substrate of the release film according to the present invention may include vinyl-based resins such as a polyvinyl chloride resin, a polyvinylidene chloride resin, and a polyvinyl alcohol resin; polyester-based resins such as a polybutylene terephthalate resin, a polyethylene terephthalate resin, and a polyethylene naphthalate resin; polyolefin resins such as a polyethylene resin, a polypropylene resin, a polymethylpentene resin, and an ethylene-vinyl acetate copolymer; plastics such as a polycarbonate, a polystyrene, an ionomer, a polyacrylic acid ester, nylon, a polyamide, a polyether sulfone, a polyphenyl sulfide, a polyimide, a polyurethane, a polyether imide, a modified polyphenylene ether, a polyether-ether ketone, a polyacrylonitrile, norbornene, cycloolefin, cellophane, and films made of cellulose acetate, vinylon, and regenerated cellulose.

Plastics is particularly preferable.

[0090] A method for applying the oil-in-water silicone emulsion composition for a release film according to the present invention is not particularly limited, and examples thereof may include a gravure coating method, a bar coating method, a spray coating method, a spin coating method, an air-knife coating method, a roll coating method, a blade coating method, a gate roll coating method, a die coating method, a doctor coating method, and a brush coating method. The application of the oil-in-water silicone emulsion composition for a release film according to the present invention may be off-line coating of a plastic film after stretching or in-line coating in a stretching process during production of plastics. When the amount of the component (B) is small, in-line coating is preferable. In the present invention, the thickness of the release agent layer after drying is 0.01 to 3 μm, preferably 0.01 to 0.5 μm, and more preferably 0.01 to 0.3 μm.

[0091] The method for curing the oil-in-water silicone emulsion composition for a release film according to the present invention is not particularly limited. For example, an ordinary method for curing the oil-in-water silicone emulsion composition for a release film with a heating drum or a hot air drying furnace may be employed. A curing condition is not particularly limited. When the oil-in-water silicone emulsion composition is processed at 50 to 250° C. for 5 seconds to 10 minutes, the release agent layer is formed.

[0092] A method for applying a coating material to a release surface is not particularly limited. The same method as the method employed when the oil-in-water silicone emulsion composition for a release film according to the present invention is applied to the film substrate may be employed. The coating material can be applied in a thin thickness of 0.01 to 0.3 μm.

[0093] As described above, favorable coating properties are obtained by the oil-in-water silicone emulsion composition for a release film according to the present invention and the release film obtained by applying the composition, regardless of a variety of coating material, that is, the presence or absence of polarity, and the film thickness of the coating material. Even when a high polar coating material is thinly applied, the release properties inherent in silicone can be kept, and favorable coating properties can be achieved. In the present invention, even when the polarity of the coating material is high or the film thickness is thin, favorable coating properties can be imparted. In particular, even when the polarity of the coating material is high and the film thickness is thin, that is, even in the most difficult case, favorable release properties can be kept, and favorable coating properties can be imparted.

[0094] When the release properties are deteriorated by decreasing the film thickness, it is conventionally difficult to balance the coating properties and the release properties. However, the present invention solves this problem.

[0095] Specifically, a case where the high polar coating material is thinly applied means a case where a coating material (e.g., a ceramic material typified by a ceramic slurry, such as barium titanate) having such a high polarity that repelling or a pinhole after drying occurs during application is applied in a film thickness within a range of 0.01 to 0.3 μm to a release film obtained by applying a variety of silicone release agent disclosed in the conventional techniques. In this case, the occurrence of repelling or a pinhole is caused by the release properties inherent in silicone.

[0096] Even in such a case, favorable coating properties can be imparted to the release surface of the release film by applying the composition according to the present invention to the film substrate. Therefore, even when such a high polar coating material that repelling or a pinhole occurs in a conventional release film having a silicone release agent layer is applied in the aforementioned film thickness, the occurrence of repelling and a pinhole can be prevented.

[0097] The coating properties in a case where a coating material is applied on a film depend on the wetting properties of an interface between the film and the coating material. This mainly depends on a relationship between the surface free energy of the film and that of the coating material, that is, a problem mainly about the interface.

[0098] In the present invention, the coating properties are increased not by solving the problem about the interface but by an interaction between the whole film and the whole coating material, that is, an action corresponding to so-called electrostatic attraction. In order to increase the coating properties of the high polar coating material such as a ceramic slurry, it is necessary that the electrostatic attraction be applied between the coating material and the release film. Therefore, it is preferable that the release film have a structure in which the polarity is higher. In order to most efficiently and reasonably form the structure, introduction of a structure having high siloxane density into the release film is preferable. To speak plainly, the density of the Q unit is mainly increased, and the polarity on a side of the film is also increased. Thus, it is estimated that electric polarization between both the materials is increased and the attraction is enhanced. Accordingly, the problem such as occurrence of repelling and a pinhole can be solved. Further, the present invention contributes to stabilization not only at the early stage of the problem but also over time.

[0099] The release properties inherent in silicone are not lost. Therefore, even when the high polar coating material is thinly applied as describe above, the coating material can be released from the release surface without poor release.

[0100] Conventionally, the coating properties are adjusted by the surface free energy of the release surface. Therefore, the adhesion of the coating material to the release surface may be deteriorated over time by migration of a silicone component and the like over time after applying the coating material to the release surface, production of any decomposed substance, physical or chemical change of the interface, or the like. The present invention can suppress such temporal deterioration.

[0101] The present invention is effective for not only a case where the high polar coating material is applied but also a case where a low polar coating material is applied. When the low polar coating material is applied, the coating properties may be adjusted by the surface free energy of the release surface. However, when the adjustment is insufficient, the coating properties can be adjusted by the electrostatic attraction as described above.

[0102] Accordingly, both the coating properties and the release properties can be simultaneously achieved without deterioration.

[0103] Even when the high polar coating material is thinly applied, favorable coating properties can be imparted to the release surface without losing the release properties by the composition according to the present invention and the release film obtained by applying the composition. This is because by the density of a crosslinking structure derived from the M unit and the Q unit that is obtained by an addition reaction that advances between the components (A), (B), and (C) during formation of the release agent layer from the composition on the film substrate, the coating properties with respect to the release surface can be adjusted, and by exposure of the methyl group contained in the composition to the release surface of the release film, the release properties inherent in silicone can be adjusted. With reference to an example of the oil-in-water silicone emulsion composition for a release film according to the present invention, when each methyl group derived from the components (A) and (B) (when the nonionic surfactant is an organosiloxane, the methyl group derived from the component (D) is also added) satisfies the constituent unit defined above, the methyl group in an amount sufficient to impart the release properties inherent in silicone is exposed to the release surface of the release film. Therefore, the release properties from the release surface are obtained.

[0104] In a mechanism in which the coating properties with respect to the release surface are adjusted by the density of the crosslinking structure derived from the M unit and the Q unit of the component (A) and the release properties from the release surface are adjusted by the methyl group exposed to the release surface, the coating properties with respect to the release surface and the release properties from the release surface can be independently adjusted by factors that are different from each other, such as the density of the crosslinking structure derived from the M unit and the Q unit of the component (A) that is formed on a surface of the release film and the methyl group exposed to the release surface of the release film. Therefore, even when the high polar coating material is thinly applied, the release properties inherent in silicone can be kept, and favorable coating properties can be reliably achieved.

<Embodiment of Method for Adjusting Coating Properties and Release Properties>

[0105] According to a method for adjusting the coating properties and the release properties of the present invention, a method for independently adjusting and optimizing the coating properties with respect to the release surface of the release film and the release properties from the release surface of the release film can be obtained.

[0106] In the conventional techniques, the coating properties and the release properties are balanced for optimization of the properties while the properties are deteriorated each other. This is because the coating properties and the release properties are controlled mainly by the surface free energy of the release film. In the present invention, the coating properties are adjusted by the density of siloxane bond in the release agent composition, and the release properties are adjusted by the methyl group in the composition. From a relationship in which the coating properties and the release properties are balanced while the properties are deteriorated each other, a relationship of the properties is changed, and both the properties can be simultaneously achieved under a preferable condition. In this term, the idea of the present invention is different from that of the conventional techniques.

[0107] In the present invention, the coating properties are adjusted by a mechanism in which a structure factor such as the density of siloxane bond in the release film acts on not only the release surface but also the whole film and the whole coating material while the surface free energy is kept to a sufficiently low value of less than 25 mJ/m.sup.2 that is a value of surface free energy of the release film with a general silicone release agent, which is considered to exert sufficient release properties. That is, the coating properties and the release properties can be each independently adjusted.

[0108] In the present invention, the coating properties and the release properties can also be each independently adjusted in a release film having a large surface free energy of more than 30 mJ/m.sup.2.

[0109] The density of siloxane bond in the release agent composition is generally increased in an order of structural units of siloxane of an M unit, a D unit, a T unit, and a Q unit. As the content of the Q unit in the release agent composition is increased, the coating properties are simply improved.

[0110] On the other hand, as the content of the methyl group on the surface of the release film formed from the release agent composition is larger, the surface free energy is lowered, and the release properties are improved. The concentration of the methyl group on the surface of the release film is substantially effective. However, as the content of the methyl group in the release agent composition is larger, the concentration of the methyl group on the film surface is generally higher. In this case, the methyl group may be a methyl group derived from an organopolysiloxane or another compound, for example, an organic polymer. The methyl group may be a methyl group derived from a low-molecular-weight compound or a polymer.

[0111] Setting of an amount of the Q unit and setting of an amount of the methyl group are independent factors. Therefore, the coating properties and the release properties can be each independently adjusted, unlike the conventional techniques. Further, both the coating properties and the release properties can be simultaneously achieved as preferable properties.

[0112] When the main component of the release agent composition is silicone generally having excellent releasability, the content of the Q unit and the content of the methyl group can be substantially independently adjusted. However, they cannot be completely independently adjusted. In the silicone, the methyl group is present as the M unit. Therefore, a change in amount of the Q unit and a change in amount of the methyl group are slightly affected on each other.

[0113] In a resin including the Q unit, a terminal thereof is capped with the M unit, or the like. Therefore, in the silicone, a resin in which a pure Q unit is present is generally rare.

[0114] When the release agent contains the silicone as a main component, it is preferable that the molar ratio M/Q be used as the content of the Q unit that is the most exactly and reasonably represented. In the present invention, the molar ratio M/Q is set as the proportion of the Q unit present in the release agent composition.

[0115] In order to make the crosslink density in the release agent layer appropriate for favorable coating properties, it is preferable that the release agent composition contain a component in which the molar ratio M/Q of the M unit to the Q unit is 0.001 to 4. This is due to the same reason as that in the description of the component (A).

[0116] The content of the methyl group in the release agent composition is defined as that in % by mass in the solid content of the whole composition. In order to impart sufficient release properties to the release surface, the content of the methyl group in the solid content is preferably 5% by mass or more. When the content is less than 5% by mass, a sufficient amount of methyl group does not exist on the release surface, the surface free energy is not decreased, and the release properties are not sufficiently exerted.

[0117] The content of the methyl group is a calculated value based on the amount of used raw material of the composition.

[0118] The release agent composition containing the silicone as a main component contains the M unit and the D unit as essential components, but may contain the T unit. The T unit is not an essential component. A proper amount of the T unit can be introduced according to a purpose. When the T unit is introduced, the density of siloxane bond can be increased less than that when the Q unit is introduced. A structure that is soluble and has high heat resistance, such as a silsesquioxane structure, may be introduced. When the molar ratio M/Q satisfies the preferable range and the molar ratio T/Q satisfies the preferable range, both the coating properties and the release properties are simultaneously achieved by the present invention.

[0119] The purpose herein means physical properties required for a film, such as strength and toughness, in various types of uses of MLCC, a semiconductor interlayer insulating film, a capacitor film, a thermal conduction film, and the like.

[0120] When completely independent adjustment of the coating properties by the density of siloxane bond in the release film and the release properties by the methyl group is prioritized, it is necessary to design a system of a composition capable of completely independently changing adjustment of the content of a portion where the density of siloxane bond is high, such as the Q unit, and adjustment of the content of the methyl group.

[0121] Therefore, a hybrid composition containing an organic material containing the Q unit, silicone, and another material, or the like is effective.

[0122] As an example of the foregoing material, the organic material containing the Q unit will be described.

[0123] The type of the organic material is not limited. However, it is necessary that the organic material have a methyl group. Examples of such an organic material may include polyethylene, polypropylene, polyisobutylene, polyurethane, and polyacrylonitrile. The polymer is configured to have a reaction group on a part thereof, so that therefore the Q unit can be introduced. For example, an alkenyl group is introduced into the polymer, an alkoxysilyl group is introduced by a hydrosilylation reaction, and cohydrolysis is carried out with an alkoxysilane that is a Q unit source.

[0124] In this case, the content of the methyl group in the release agent composition is also defined as that in % by mass in the solid content of the whole composition. In order to impart sufficient release properties to the release surface, the content of the methyl group in the solid content is preferably 5% by mass or more. When the content is less than 5% by mass, a sufficient amount of methyl group does not exist on the release surface, the surface free energy is not decreased, and the release properties are not sufficiently exerted. The content of the methyl group is a calculated value based on the amount of used raw material of the composition.

[0125] The amount of the Q unit in the release agent composition is preferably 5% by mass or more. When the amount is less than 5% by mass, sufficient coating properties cannot be exerted. The amount is more preferably 10% by mass or more. The content of the Q unit is a calculated value based on the amount of used raw material of the composition.

[0126] A procedure for forming such a material on a substrate is not limited, and a procedure for obtaining a uniform coating film through an emulsion is preferable.

[0127] In the present invention, all the contents of the M unit, the T unit, the Q unit, and the methyl group, the molar ratio M/Q, and the molar ratio T/Q in the components or the whole composition can be determined by calculation from the ratio of used raw material. In a sampling test, the composition after crosslinking was collected, and analyzed by a .sup.29Si-NMR method. The analyzed value was coincident with the value calculated from the used ratio.

[0128] In the present invention, bleeding of a silicone component through the release surface from the inside of the release film or migration of the silicone component to a coating layer can be prevented or suppressed. When the composition contains the silicone as a main component and a component at a portion between the components is cured, production of low-molecular-weight compound or unreacted compound of the silicone can be prevented or suppressed. When the composition has a hybrid structure of the silicone and the other material and is reactive, production of low-molecular-weight compound or unreacted compound of the silicone can be prevented or suppressed.

[0129] According to a purpose, the silicone component may be forced to be migrated. For example, the purpose includes supporting the release properties or another purpose. This purpose is achieved by a method in which a low-molecular-weight or unreacted silicone component is added. When migration over time should be controlled, the purpose can be achieved by selecting the structure or molecular weight of the migration component.

[0130] Even when unintended migration of the silicone component occurs, the present invention is effective.

[0131] Even when the silicone component is positively migrated or the silicone component is migrated as an unintended result, the coating properties can be adjusted to achieve desired coating properties without being affected by the migration of silicone. This is because in the present invention, the coating properties are not adjusted by the surface free energy of the release surface.

EXAMPLES

[0132] Specifically, the present invention will be described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

<Method for Producing Release Film>

[0133] A release agent composition prepared in each of Examples and Comparative Examples was diluted with purified water so that the solid content concentration was 2%, to prepare a coating liquid.

[0134] The coating liquid prepared by the aforementioned method was applied to Teijin Tetoron Film G2 (thickness: 38 μm) manufactured by Teijin DuPont Films Japan Limited with a Mayer bar coater No. 3, dried at normal temperature for 2 minutes, and then heat-cured in an oven at 200° C. for 1 minute, to prepare a release film.

<Method for Measuring Release Force and Evaluation Method>

[0135] To a coating surface of the release film prepared as described above, TESA7475 was attached, and pressure-bonded with a roller. The release film was stored for 2 hours with a 20-g/cm.sup.2 weight disposed on the release film. After that, the release force of the tape at a release angle of 1800 and a release rate of 0.3 m/minute was measured.

[0136] For release properties, a case where the release force was 7 N/inch or less was evaluated as pass.

<Test of Paintability (Coating Properties) and Evaluation Method>

[0137] For a method for evaluating the coating properties of a high polar coating material with respect to a surface of the release film prepared by the aforementioned method, a test of paintability of an ink was performed.

[0138] As the ink, “FELT MARKER” manufactured by Teranishi Chemical Industry Co., Ltd., was used. With black, blue, and red felt markers, a lower-case alphabetic character “a” was written on a surface of a release surface.

[0139] The paintability was evaluated in accordance with five stages.

[0140] 5: With the three felt markers, the letter was well written without repelling and defects.

[0141] 4: With the three felt markers, the letter was written without repelling and defects, but ununiform color tone was partially found.

[0142] 3: On the letter written with one of the felt markers, a partial defect was found, but the letter was sufficiently read. With the rest thereof, the letter was well written without repelling and defects.

[0143] 2: On the letter written with two or three of the felt markers, a partial defect was found. Alternatively, on the letter written with one of the felt markers, repelling occurred.

[0144] 1: On the letter written with two or three of the felt markers, repelling occurred.

[0145] A case where the stage was 3 or more was evaluated as pass.

[0146] As a wetting reagent, a mixed solution No. 22.6 for determination of wetting tension having a surface tension of 22.6 mN/m, manufactured by Wako Pure Chemical Industries, Ltd., was added dropwise on a surface of each of the release film samples. Whether the sample was wet with the wetting agent was determined.

Example 1

[0147] Thirty four parts by mass of an organopolysiloxane having an M unit and a Q unit as the component (A), 6.0 parts by mass of an organopolysiloxane having an M unit and a D unit as the component (A), 7.4 parts by mass of an organopolysiloxane having an SiH group as the component (B), 3.4 parts by mass of a nonionic surfactant as the component (C), 0.0025 parts by mass of a platinum catalyst as the component (D), 11 parts by mass of an organic solvent as an optional component, and a balance of purified water as the component (E) were used to prepare 100 parts by mass of an emulsion.

[0148] The components (A) and (D) were mechanically emulsified with the component (C), to prepare an emulsion. Separately, the component (B) was mechanically emulsified with the component (C), to prepare an emulsion. After that, the emulsions were mixed and an addition reaction was caused to take place, thereby obtaining an emulsion in which a silicone cured product obtained by curing the component (A) and the component (B) was dispersed.

[0149] In the component (A), the content of the M unit was 39% by mole, and the content of the Q unit was 45% by mole. The content of the methyl group in the solid content of the whole composition was 15% by mass.

[0150] In the component (A), the molar ratio M/Q was 0.88, and the molar ratio T/Q was 0.

[0151] The ratio B/A of the number by mole of the SiH group in the component (B) to the number by mole of the alkenyl group in the component (A) was 2.9.

[0152] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 4.2 N/inch. The paintability was evaluated to be 4. The wetting reagent was added dropwise on a film surface. The wetting agent was repelled.

[0153] The indication about the formulation of the composition and the test results of the composition are shown in Table 1. (Hereinafter the same is applied to Examples and Comparative Examples)

Example 2

[0154] Twenty nine parts by mass of an organopolysiloxane having an M unit and a Q unit as the component (A), 12 parts by mass of an organopolysiloxane having an M unit and a D unit as the component (A), 6.7 parts by mass of an organopolysiloxane having an SiH group as the component (B), 3.7 parts by mass of a nonionic surfactant as the component (C), 0.0025 parts by mass of a platinum catalyst as the component (D), 9.1 parts by mass of an organic solvent as an optional component, and a balance of purified water as the component (E) were used to prepare 100 parts by mass of an emulsion in the same method as that in Example 1.

[0155] In the component (A), the content of the M unit was 30% by mole, and the content of the Q unit was 34% by mole. The content of the methyl group in the solid content of the whole composition was 16% by mass.

[0156] In the component (A), the molar ratio M/Q was 0.88, and the molar ratio T/Q was 0.

[0157] The ratio B/A of the number by mole of the SiH group in the component (B) to the number by mole of the alkenyl group in the component (A) was 2.9.

[0158] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 1.9 N/inch. The paintability was evaluated to be 4. The wetting reagent was added dropwise on a film surface. The wetting agent was repelled.

Example 3

[0159] Cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container using vinyltrimethoxysilane, tetraethoxysilane, trimethylethoxysilane, and vinylmethyldimethoxysilane. The obtained solid substance was taken out, and water, methanol, and ethanol were sufficiently removed to obtain a solid content. This solid content was used as the component (A).

[0160] The aforementioned solid content was weighed so that 40 parts by mass of the total amount of respective silanes as the raw material of the component (A) was used. The weighed solid content, 7.4 parts by mass of an organopolysiloxane having an SiH group as the component (B), 3.4 parts by mass of a nonionic surfactant as the component (C), 0.0025 parts by mass of a platinum catalyst as the component (D), 11 parts by mass of an organic solvent as an optional component, and a balance of purified water as the component (E) were used to prepare 100 parts by mass of an emulsion in the same method as that in Example 1.

[0161] In the component (A), the content of the M unit was 74% by mole, and the content of the Q unit was 24% by mole. The content of the methyl group in the solid content of the whole composition was 24% by mass.

[0162] In the component (A), the molar ratio M/Q was 3.1, and the molar ratio T/Q was 0.

[0163] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 1.0 N/inch. The paintability was evaluated to be 3.

Example 4

[0164] Cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container using tetraethoxysilane, trimethylethoxysilane, and vinylmethyldimethoxysilane. The obtained solid substance was taken out, and water, methanol, and ethanol were sufficiently removed to obtain a solid content. This solid content was used as the component (A).

[0165] The aforementioned solid content was weighed so that 26 parts by mass of the total amount of respective silanes as the raw material of the component (A) was used. The weighed solid content was used together with the components (B) to (E) to prepare an emulsion in the same method as that in Example 3 except that 17 parts by mass of an organopolysiloxane having an SiH group was used as the component (B).

[0166] In the component (A), the content of the M unit was 31% by mole, and the content of the Q unit was 64% by mole. The content of the methyl group in the solid content of the whole composition was 11% by mass.

[0167] In the component (A), the molar ratio M/Q was 0.48, and the molar ratio T/Q was 0.

[0168] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 5.3 N/inch. The paintability was evaluated to be 3.

Example 5

[0169] Thirty four parts by mass of an organopolysiloxane having an M unit and a Q unit as the component (A), 5.9 parts by mass of an organopolysiloxane having an M unit and a D unit as the component (A), 7.3 parts by mass of an organopolysiloxane having an SiH group as the component (B), 1.1 parts by mass of a polyether modified silicone oil as an optional component, 3.4 parts by mass of a nonionic surfactant as the component (C), 0.0025 parts by mass of a platinum catalyst as the component (D), 11 parts by mass of an organic solvent as an optional component, and a balance of purified water as the component (E) were used to prepare 100 parts by mass of an emulsion.

[0170] The components (A) and (D) were mechanically emulsified with the component (C), to prepare an emulsion. Separately, the component (B) was mechanically emulsified with the component (C), to prepare an emulsion. After that, the emulsions were mixed and an addition reaction was caused to take place, thereby obtaining an emulsion in which a silicone cured product obtained by curing the component (A) and the component (B) was dispersed.

[0171] In the component (A), the content of the M unit was 39% by mole, and the content of the Q unit was 45% by mole. The content of the methyl group in the solid content of the whole composition was 15% by mass.

[0172] In the component (A), the molar ratio M/Q was 0.88, and the molar ratio T/Q was 0.

[0173] The ratio B/A of the number by mole of the SiH group in the component (B) to the number by mole of the alkenyl group in the component (A) was 2.9.

[0174] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 4.5 N/inch. The paintability was evaluated to be 5.

Example 6

[0175] Cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container using vinyltrimethoxysilane, tetraethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, and vinylmethyldimethoxysilane. The obtained solid substance was taken out, and water, methanol, and ethanol were sufficiently removed to obtain a solid content. This solid content was used as the component (A).

[0176] The aforementioned solid content was weighed so that 27 parts by mass of the total amount of respective silanes as the raw material of the component (A) was used. The weighed solid content was used together with the components (B) to (E) to prepare an emulsion in the same method as that in Example 3 except that 26 parts by mass of an organopolysiloxane having an SiH group was used as the component (B).

[0177] In the component (A), the content of the M unit was 6.4% by mole, the content of the T unit was 74% by mole, and the content of the Q unit was 7.2% by mole. The content of the methyl group in the solid content of the whole composition was 28% by mass.

[0178] In the component (A), the molar ratio M/Q was 0.88, and the molar ratio T/Q was 10.2.

[0179] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 0.90 N/inch. The paintability was evaluated to be 4.

Example 7

[0180] Triethoxysilane was added to isobutylene having 10 repeating units, which has a methyl group at one terminal thereof and a vinyl group at the other terminal thereof, by a hydrosilylation reaction. The resulting polymer is referred to as a polymer 1. One hundred grams of the polymer 1 and 70 g of, tetraethoxysilane were weighed, and cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container. The obtained solid substance was taken out, and water and ethanol were sufficiently removed to obtain a solid content.

[0181] In the obtained solid content, the content of the methyl group was 39%, and the content of the Q unit was 27%. The obtained solid content was emulsified in the same method as that in Example 1 and the coating force was measured to be 4.2 N/inch. The paintability was evaluated to be 4.

Example 8

[0182] A solid content was obtained by performing the reaction of the polymer 1 and tetraethoxysilane in the same method as that in Example 7 except that 40 g of tetraethoxysilane was used in Example 7.

[0183] In the obtained solid content, the content of the methyl group was 42%, and the content of the Q unit was 20%.

[0184] The obtained solid content was emulsified in the same method as that in Example 1, and the coating force was measured to be 4.0 N/inch. The paintability was evaluated to be 3.

Example 9

[0185] Triethoxysilane was added to 1-dodecene by a hydrosilylation reaction.

The obtained polymer is referred to as a polymer 2. One hundred grams of the polymer 2 and 60 g of tetraethoxysilane were weighed, and cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container. The obtained solid substance was taken out, and water and ethanol were sufficiently removed to obtain a solid content.

[0186] In the obtained solid content, the content of the methyl group was 28%, and the content of the Q unit was 28%. The obtained solid content was emulsified in the same method as that in Example 1, and the coating force was measured to be 6.8 N/inch. The paintability was evaluated to be 4.

Example 10

[0187] A solid content was obtained by performing the reaction of the polymer 2 and tetraethoxysilane in the same method as that in Example 9 except that 30 g of tetraethoxysilane was' used in Example 9.

[0188] In the obtained solid content, the content of the methyl group was 30%, and the content of the Q unit was 21%.

[0189] The obtained solid content was emulsified in the same method as that in Example 1, and the coating force was measured to be 6.3 N/inch. The paintability was evaluated to be 3.

Comparative Example 1

[0190] A PET substrate, on which no release agent composition was applied, was directly subjected to tests of release properties and paintability.

[0191] The coating force was measured, but the coating force exceeding 10 N/inch was unmeasurable. The paintability was evaluated to be 5.

[0192] The film of Comparative Example 1 was wet with the wetting reagent.

Comparative Example 2

[0193] Forty six parts by mass of an organopolysiloxane having an M unit and a D unit as the component (A), 3 parts by mass of an organopolysiloxane having an SiH group as the component (B), 5 parts by mass of a nonionic surfactant as the component (C), 0.0025 parts by mass of a platinum catalyst as the component (D), and a balance of purified water as a component (E) were used to prepare 100 parts by mass of an emulsion in the same method as that in Example 1.

[0194] In the component (A), the content of the M unit was 0.71% by mole, and the content of the methyl group was 21% by mass.

[0195] In the component (A), the molar ratio M/Q was infinity, and the molar ratio T/Q was 0.

[0196] The ratio B/A of the number by mole of the SiH group in the component (B) to the number by mole of the alkenyl group in the component (A) was 2.9.

[0197] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 0.20 N/inch. The paintability was evaluated to be 1.

Comparative Example 3

[0198] Zero point two three parts by mass of an organopolysiloxane having an M unit and a Q unit as the component (A), 44 parts by mass of an organopolysiloxane having an M unit and a D unit as the component (A), 4 parts by mass of an organopolysiloxane having an SiH group as the component (B), 5 parts by mass of a nonionic surfactant as the component (C), 0.0025 parts by mass of a platinum catalyst as the component (D), 0.072 parts by mass of an organic solvent as an optional component, and a balance of purified water as the component (E) were used to prepare 100 parts by mass of an emulsion in the same method as that in Example 1.

[0199] In the component (A), the content of the M unit was 0.86% by mole, and the content of the Q unit was 0.17% by mole. The content of the methyl group in the solid content of the whole composition was 22% by mass.

[0200] In the component (A), the molar ratio M/Q was 5.1, and the molar ratio T/Q was 0.

[0201] The ratio B/A of the number by mole of the SiH group in the component (B) to the number by mole of the alkenyl group in the component (A) was 2.9.

[0202] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 0.51 N/inch. The paintability was evaluated to be 2.

Comparative Example 4

[0203] Hydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container using tetraethoxysilane. The obtained solid substance was taken out, and water and ethanol were sufficiently removed to obtain a solid content. This solid content was used as the component (A).

[0204] The foregoing solid content was used together with the components (C) and (E) to prepare an emulsion in the same method as that in Example 3 except that the component (B) and the component (D) were not used in Example 3.

[0205] In the component (A), the content of the Q unit was 100%. The content of the methyl group in the solid content of the whole composition was 0%.

[0206] In the component (A), the molar ratio M/Q was 0, and the molar ratio T/Q was 0.

[0207] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 8.8 N/inch. The paintability was evaluated to be 5.

Comparative Example 5

[0208] Cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container using vinyltrimethoxysilane, tetraethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane and vinylmethyldimethoxysilane. The obtained solid substance was taken out, and water, methanol, and ethanol were sufficiently removed to obtain a solid content. This solid content was used as the component (A).

[0209] The aforementioned solid content was weighed so that 40 parts by mass of the total amount of respective silanes as the raw material of the component (A) was used. The weighed solid content was used together with the components (B) to (E) to prepare an emulsion in the same method as that in Example 3 except that 0.41 parts by mass of an organopolysiloxane having an SiH group was used as the component (B).

[0210] In the component (A), the content of the M unit was 0.043% by mole, the content of the T unit was 99.7% by mole, and the content of the Q unit was 0.17% by mole. The content of the methyl group in the solid content of the whole composition was 16% by mass.

[0211] In the component (A), the molar ratio M/Q was 0.88, and the molar ratio T/Q was 20,000.

[0212] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 5.0 N/inch. The paintability was evaluated to be 2.

Comparative Example 6

[0213] Cohydrolysis was performed in an aqueous hydrochloric acid solution in a reaction container using vinyltrimethoxysilane, tetraethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane and vinylmethyldimethoxysilane. The obtained solid substance was taken out, and water, methanol, and ethanol were sufficiently removed to obtain a solid content. This solid content was used as the component (A).

[0214] The aforementioned solid content was weighed so that 40 parts by mass of the total amount of respective silanes as the raw material of the component (A) was used. The weighed solid content was used together with the components (B) to (E) to prepare an emulsion in the same method as that in Example 3 except that 0.47 parts by mass of an organopolysiloxane having an SiH group was used as the component (B).

[0215] In the component (A), the content of the M unit was 0.040% by mole, the content of the T unit was 99.7% by mole, and the content of the Q unit was 0.46% by mole. The content of the methyl group in the solid content of the whole composition was 0.18% by mass.

[0216] In the component (A), the molar ratio M/Q was 0.88, and the molar ratio T/Q was 100,000.

[0217] The obtained emulsion was diluted with purified water to have a predetermined solid content concentration, and the coating force was measured to be 8.4 N/inch. The paintability was evaluated to be 2.

TABLE-US-00001 TABLE 1 COMPAR- COMPAR- COMPAR- COMPAR- COMPAR- COMPAR- ATIVE ATIVE ATIVE ATIVE ATIVE ATIVE EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 PLE 1 PLE 2 PLE 3 PLE 4 PLE 5 PLE 6 AMOUNT ORGANOPOLYSILOXANE 34 29 0 0 34 0 — 0 0.2 0 0 0 IN PARTS (A) HAVING M UNIT AND BY MASS Q UNIT ORGANOPOLYSILOXANE 6.0 12 0 0 5.9 0 — 46 44 0 0 0 (A) HAVING M UNIT AND D UNIT ORGANOPOLYSILOXANE 0 0 0 0 0 0 — 0 0 0 0 0 (A) HAVING M UNIT AND T UNIT SYNTHESIZED PRODUCT 0 0 26 36 0 27 — 0 0 40 40 40 (A) FROM SILANES ORGANOPOLYSILOXANE 7.4 6.7 21 9.0 7.3 20 — 3.0 4.3 0 7.0 6.5 (B) HAVING SH GROUP POLYETHER-MODIFIED 0 0 0 0 1.1 0 — 0 0 0 0 0 SILICONE (OPTIONAL COMPONENT) NONIONIC SURFACTANT (C) 3.4 3.7 3.4 3.4 3.4 3.4 — 5.2 5.1 3.4 3.4 3.4 PLATINUM CATALYST (D) 0.0025 0.0025 0.0025 0.0025 0.0025 0.0025 — 0.0025 0.0025 0 0.0025 0.0025 PURIFIED WATER (E) 38 39 38 38 38 38 — 45.7 46.3 38 38 38 ORGANIC SOLVENT 11 9.1 11 11 11 11 — 0.0 0.072 11 11 11 (OPTIONAL COMPONENT) SUM 100 100 100 100 100 100 — 100 100 100 100 100 MOLAR RATIO M/Q IN COMPONENT (A) 0.88 0.88 3.1 0.48 0.9 0.9 — INFINITY 5.1 0 0.9 0.9 MOLAR RATIO T/Q IN COMPONENT (A) 0 0 0 0 0 10.2 — 0 0 0 20,000 100,000 CONTENT OF METHYL GROUP IN 15 16 23 11 15 28 — 21 22 0 16 0 ALL COMPONENTS (% BY MASS) TEST RELEASE FORCE (N/inch) 4.2 1.9 1.0 5.3 4.5 0.90 >10 0.20 0.51 8.8 5.0 8.4 RESULTS PASS: 7 OR LESS PAINTABILITY OF INK 4 4 3 3 5 4 5 1 2 5 2 2 PASS: 3 OR MORE REACTION PRODUCT OF Q UNIT WITH ORGANIC MATERIAL EXAMPLE 7 EXAMPLE 8 EXAMPLE 9 EXAMPLE 10 CONTENT OF METHYL GROUP IN 39 42 28 30 ALL COMPONENTS (% BY MASS) CONTENT Q UNIT IN ALL 27 20 28 21 COMPONENTS (% BY MASS) TEST RELEASE FORCE 4.2 4.0 6.8 6.3 RESULTS (N/inch) PASS: 7 OR LESS PAINTABILITY OF INK 4 3 4 3 PASS: 3 OR MORE

[0218] From the results of Examples and Comparative Examples and Table 1, the following is found.

[0219] In the release agent compositions containing silicone as a main component in Examples 1 to 6 and Comparative Example 1, favorable coating properties and release properties could be simultaneously achieved by adjusting the molar ratios M/Q and T/Q. In Example 5 where the polyether-modified silicone was added to the release agent composition, further favorable coating properties were obtained.

[0220] In Comparative Examples 2 to 6 where the molar ratio M/Q or T/Q was out of the predetermined range, the coating properties and/or the release properties were not passed.

[0221] In all Examples and Comparative Examples, as the amount of methyl group in the solid content of the whole composition is larger, the release properties are better. In Examples, favorable values of coating properties and release properties could be simultaneously achieved by adjusting the molar ratio M/Q and the content of methyl group.

[0222] In Examples 7 to 10, the coating properties and the release properties could be independently adjusted by the content of the Q unit and the content of methyl group in the release agent composition.

[0223] From the results in Examples 1 and 2, the surface tension of the release film is estimated to be less than 22.6 mN/m. In the release film containing silicone as a main component of which the surface free energy was estimated to be less than 25, sufficient coating properties were exerted.

INDUSTRIAL APPLICABILITY

[0224] According to an oil-in-water silicone emulsion composition for a release film, a release film and a method for producing the release film, and a method for adjusting the coating properties and release properties of the release film according to the present invention, favorable coating properties and favorable release properties can be simultaneously achieved and the coating properties and the release properties can be independently adjusted even when a high polar coating material is applied to a surface of the release film so that the film thickness is thin. Therefore, the release film can meet a requirement of formation of light, thin, and small device in use of a multilayer ceramic capacitor (MLCC) or the like. In use for formation of a polar thin film such as a semiconductor interlayer insulating film, a capacitor film, or a thermal conduction film on a silicone film or the like or another use, it is possible that a new requirement is met by adjusting the coating properties and the release properties.