JP5163888B2 - Organosilicone resin emulsion composition, two-part coating agent, method for forming cured film thereof, and article on which the cured film is formed - Google Patents

Description

  The present invention relates to a silicone resin emulsion composition suitably used as a protective coating agent for various substrates, a two-part coating agent, a method for forming a cured coating, and an article having a coating formed by the method.

  In recent years, from the viewpoint of environmental pollution and ensuring a safe working environment, in the field of paints or coating agents, it is required to change the dispersion medium from an organic solvent to an aqueous system. Based on this requirement, emulsion paints obtained by emulsion polymerization of radically polymerizable vinyl monomers typified by acrylic resins have been widely used as basic materials for coating agents because of their excellent film-forming properties and good chemical resistance. However, this type of coating has the disadvantage that it is inherently inferior in water resistance and weather resistance.

  On the other hand, silicone resins obtained by hydrolyzing and condensing silane compounds are attracting attention as coating agents because of their high hardness and ability to form films with excellent weather resistance, water resistance, heat resistance, and water repellency. . However, an emulsion polymerization method for polymerizing a silicone resin from a monomer in an emulsion has not been established.

  For this reason, a general method is to emulsify a silicone resin solution produced in an organic solvent system such as toluene or xylene as it is. However, such an organic solvent-containing silicone resin emulsion has a problem of poor stability. Furthermore, it is necessary to suppress the use of organic solvents such as toluene and xylene due to environmental problems.

  Therefore, the present inventor has proposed a silicone resin emulsion composition containing substantially no other organic solvent by using a small amount of a specific water-miscible organic solvent (Japanese Patent Laid-Open No. 2006-225629: Patent). Reference 1). However, since the silicone resin emulsion composition contains a high boiling point of the water-miscible organic solvent, it needs to be cured by heating for a long period of time, and a condensation catalyst such as an alkali metal for the purpose of shortening the curing time. When used in combination, the cured film may not be uniform and may have a crusty skin shape.

  In addition, silicone rubber compositions that are cured at room temperature by using an organic bismuth compound in combination with a silicone containing a hydroxyl group or an alkoxy group have been proposed (JP 2001-342363 A, JP 2003-119387 A). Patent Documents 2 and 3) do not describe an emulsion. Furthermore, there is also a proposal that a bismuth compound can be used as a catalyst for curing a silicone emulsion containing a hydroxyl group (JP-A-6-49210, JP-A-6-73291, JP-A-6-345972, Japanese Patent Laid-Open No. 7-179762: Patent Documents 4 to 7) have no specific description on the bismuth compound and no description on the curing of the silicone resin.

JP 2006-225629 A JP 2001-342363 A JP 2003-119387 A JP-A-6-49210 JP-A-6-73291 JP-A-6-345972 Japanese Patent Laid-Open No. 7-179762

  The present invention has been made in view of the above circumstances, and is an organosilicone resin emulsion composition, a two-part coating agent, which can be cured in a relatively short time and has excellent surface uniformity of the cured film, and the cured film. It is an object to provide a forming method and an article on which the cured film is formed by the method.

As a result of intensive studies to achieve the above object, the present inventor has (A) average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (wherein R is the same or different carbon number of 1 to 20 is a monovalent organic group, m is 0.2 to 1.0, and n is 0 to 0.8.), (B) an emulsifier, (C) an organic bismuth compound, D) After applying to the substrate an organosilicone resin emulsion composition containing water and preferably further (E) a specific amount of water miscible organic solvent having an SP value of 8.0 to 11.0 The present inventors have found that a cured film excellent in surface uniformity can be obtained in a relatively short time by drying, preferably by heating and drying at a temperature of 40 to 300 ° C., and have made the present invention.

Accordingly, the present invention provides an organosilicone resin emulsion composition, a two-component coating agent, a method for forming a cured film thereof, and an article on which the cured film is formed, as described below.
[Claim 1]
(A) Average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (wherein R is the same or different monovalent organic group having 1 to 20 carbon atoms, and m is 0.2 to 1). 0.0, n is 0 to 0.8.) Organosilicone resin represented by: 100 parts by mass,
(B) Emulsifier: 1-50 parts by mass,
(C) Organic bismuth compound: 0.01 to 10 parts by mass,
(D) Water: An organosilicone resin emulsion composition containing 25 to 2,000 parts by mass.
[Claim 2]
Furthermore, the organosilicone resin emulsion composition of Claim 1 containing the water miscible organic solvent (E) whose SP value is 8.0-11.0 with respect to 100 mass parts of (A) component. object.
[Claim 3]
(A) Average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (wherein R is the same or different monovalent organic group having 1 to 20 carbon atoms, and m is 0.2 to 1). 0.0, n is 0 to 0.8.) Organosilicone resin represented by: 100 parts by mass,
(B) Emulsifier: 0.9999 to 49.9999 parts by mass,
(D) Water: an organosilicone resin emulsion containing 24.9975 to 1,999.975 parts by mass;
(C) Organic bismuth compound: 0.01 to 10 parts by mass,
(B) Emulsifier: 0.0001-5 parts by mass,
(D) Water: An organic bismuth compound emulsion containing 0.0025 to 200 parts by mass, and the total of the organosilicone resin emulsion component and the organic bismuth compound emulsion component is (A) component: 100 parts by mass,
Component (B): 1 to 50 parts by weight,
(C) component: 0.01-10 mass parts,
Component (D): 25-2 liquid coating agent which is a 2,000 parts by weight.
[Claim 4]
In the organosilicone resin emulsion and / or organic bismuth compound emulsion, a water-miscible organic solvent having an SP value of 8.0 to 11.0 in total of 1 to 50 parts by mass with respect to 100 parts by mass of the component (A) ( The two-component coating agent according to claim 3, wherein E) is blended.
[Claim 5]
The two-component coating agent according to claim 4, wherein 1 to 50 parts by mass of the component (E) is blended with the organosilicone resin emulsion and 0 to 10 parts by mass of the component (E) is blended with the organic bismuth compound emulsion.
[Claim 6]
A method for forming a cured film, comprising applying the organosilicone resin emulsion composition according to claim 1 or 2 to a substrate and then drying and curing the composition.
[Claim 7]
The organosilicone resin emulsion and the organic bismuth compound emulsion in the two-component coating agent according to any one of claims 3 to 5 are mixed, applied to a substrate, and then dried and cured. A method for forming a cured film.
[Claim 8]
An article having a cured coating formed on a substrate by the method for forming a cured coating according to claim 6 or 7.

  According to the present invention, a silicone resin emulsion composition or a two-component coating agent can be cured in a relatively short time to form a film having excellent surface uniformity, and excellent properties such as water resistance and weather resistance. Articles having different coatings can be provided.

The organosilicone resin emulsion composition of the present invention is
(A) Average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (wherein R is the same or different monovalent organic group having 1 to 20 carbon atoms, and m is 0.2 to 1). 0.0, n is 0 to 0.8.) Organosilicone resin represented by: 100 parts by mass,
(B) Emulsifier: 1-50 parts by mass,
(C) Organic bismuth compound: 0.01 to 10 parts by mass,
(D) Water: 25-2,000 parts by mass,
Preferably further
(E) A water-miscible organic solvent having an SP value of 8.0 to 11.0: 1 to 50 parts by mass.

The organosilicone resin as component (A) has an average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (where R is the same or different monovalent organic group having 1 to 20 carbon atoms). , M is 0.2 to 1.0, and n is 0 to 0.8).

  Here, R is the same or different monovalent organic group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl. And alkyl groups such as hexadecyl, octadecyl, cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, tolyl and naphthyl, and alkenyl groups such as vinyl and allyl.

Also included are those in which a part (one or more) of hydrogen atoms is substituted with a reactive group such as an epoxy group, a mercapto group, a methacryl group, an acrylic group, a carboxyl group, or an amino group. Examples of the organic group substituted with a reactive group include 3-glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, 3-mercaptopropyl, 3-methacryloxypropyl, 3-acryloxypropyl, 3- Aminopropyl, N- (2-aminoethyl) -3-aminopropyl, N- (1,3-dimethylbutylidene) -3-aminopropyl, N-phenyl-3-aminopropyl, 3-ureidopropyl, 3- Chloropropyl, 10-carboxydecyl, 2-carboxyethyl, 3- (2-hydroxyethoxy) propyl, —C ₂ H ₄ —CHO, —C ₃ H ₆ —S—C ₂ H ₄ —CONH—C (CH ₃ ) ₂ -CH ₂ COCH _{3 and the} like. In the present invention, it is desirable that 30 mol% or more of R is a methyl group.

The molar ratio (m) of [RSiO _3/2 ] units in the silicone resin is 0.2 to 1.0, preferably 0.3 to 1.0, more preferably 0.4 to 1.0. It is. If it is less than 0.2, the film hardness becomes soft and the durability is lowered. The molar ratio of [R ₂ SiO] units in the silicone resin (n) is from 0 to 0.8, preferably from 0 to 0.7, more preferably from 0 to 0.6. When it is larger than 0.8, the coating hardness becomes soft and the durability is lowered.

Such an organosilicone resin can be produced by a known method. For example, it can be obtained by subjecting chlorosilane or alkoxysilane of the corresponding unit to hydrolysis and condensation reaction. These organosilicone resins are usually solid when the content of the [RSiO _3/2 ] unit is high, or are easily gelled when the condensation reactivity is high. Although it is handled in a state diluted with an organic solvent, in the present invention, such an organic solvent can be used by replacing it with a water-miscible organic solvent solution which is a component (E) described later. It is possible to use a water-miscible organic solvent solution, which is a component), as a solvent for producing an organosilicone resin.

  The organosilicone resin produced by the above method contains a small amount of a hydroxyl group as a terminal group and optionally further an alkoxy group (preferably having 1 to 6 carbon atoms). The organosilicone resin is cured by the dehydration condensation and dealcohol condensation of these hydroxyl groups and alkoxy groups. In addition, the quantity of a hydroxyl group is 0.1-10 mass%, the amount of alkoxy groups is 0.1-10 mass%, and the total amount of a hydroxyl group and an alkoxy group is 0.1-15 mass%.

Further, the component (A) of the present invention may contain a small amount of [R ₃ SiO _1/2 ] units (R is as described above) and / or [SiO ₂ ] units as long as the curability and film properties are not impaired. Absent. In this case, m + n is preferably 0.8 to 1.0, particularly 0.9 to 1.0. When m + n is not 1.0, the balance is [R ₃ SiO _1/2 ] units, [SiO ₂ ], And the total of them is 1.0.

  The emulsifier as the component (B) is not particularly limited as long as it is for emulsifying and dispersing the organosilicone resin in water. For example, polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkylphenyl Nonionic surfactants such as ethers and polyoxyethylene fatty acid esters, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, etc. Anionic surfactants, quaternary ammonium salts, cationic surfactants such as alkylamine acetates, and amphoteric surfactants such as alkylbetaines and alkylimidazolines.

Among these, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, and polyoxyethylene alkylphenyl ether are preferable from the viewpoint of stability.
Specific examples thereof include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene tridecyl Ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styrenated phenyl ether, etc. Is mentioned. These emulsifiers can be used alone or in combination of two or more.

  (B) As addition amount of a component, it is necessary to be 1-50 mass parts with respect to 100 mass parts of (A) component, and when less than 1 mass part, emulsification is difficult, and when more than 50 mass parts The hardness and transparency of the coating and the adhesion to the substrate will be reduced. Preferably it is 2-30 mass parts, More preferably, it is 3-20 mass parts.

The organic bismuth compound as component (C) is a catalyst for crosslinking and curing the organosilicone resin as component (A), and is represented by the general formula: Bi (OCOR ′) ₃ (wherein R ′ is 1 to 1 carbon atoms) 20 monovalent hydrocarbon group). Specific examples of R ′ in the formula include methyl, ethyl, propyl, butyl, 2-methylpropyl, pentyl, 3-methylbutyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl. , Alkyl groups such as dodecyl, tetradecyl, hexadecyl, and octadecyl. Of these, a 2-ethylhexyl group is preferable.

  Component (C) should be added in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of component (A). If the amount is less than 0.01 parts by mass, it will take a long time to crosslink and cure the organosilicone resin. This is uneconomical because the catalytic effect does not change even if the amount exceeds 10 parts by mass. Preferably it is 0.03-8 mass parts, More preferably, it is 0.05-5 mass parts.

  Since the organosilicone resin (A) is a solid to a viscous liquid, it is difficult to emulsify as it is. Therefore, for the purpose of improving the emulsifiability of the organosilicone resin, it is preferable to use a water-miscible organic solvent having an SP value of 8.0 to 11.0 as the component (E). The water-miscible organic solvent having an SP value of 8.0 to 11.0, which is the component (E), is used for providing fluidity when emulsifying the organosilicone resin which is the component (A). It has an SP value (solubility parameter) of 8.0 to 11.0 and is miscible with water.

  The SP value here is a solubility parameter, and is a characteristic value that is also called a solubility coefficient and is a measure of the mixing property between liquids proposed by Hildebrand. When the SP value is less than 8.0, the organosilicone resin cannot be uniformly dissolved. When the SP value is greater than 11.0, the stability of the emulsion when emulsified is lowered. Is 8.0 to 11.0. Preferably it is 8.5-10.5. Moreover, this organic solvent is miscible with water, and if it is not miscible with water, the stability of the emulsion when emulsified is lowered. The water miscibility is such that the solubility in 100 g of water at 20 ° C. is 1 g or more, preferably 2 g or more.

  Examples of such water-miscible organic solvents include alcohol compounds, ketone compounds, ester compounds, and ether compounds. Specifically, cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, methyl carbitol, carbitol, propyl carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, propylene Examples include glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate, and the like. Of these, butyl cellosolve, butyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate are preferable.

  (E) As an addition amount when mix | blending a component, it is preferable that it is 1-50 mass parts with respect to 100 mass parts of (A) component, and when less than 1 mass part, the viscosity of an organosilicone resin solution is high, It is difficult to emulsify and the emulsion stability may be poor. If it is more than 50 parts by mass, it may take a long time to dry the emulsion. More preferably, it is 3-40 mass parts, More preferably, it is 5-30 mass parts.

  In the present invention, the water-miscible organic solvent solution of the component (E) can be used when diluting the organosilicone resin of the component (A) as described above, and the organodiluted with the water-miscible organic solvent. The viscosity of the silicone resin solution is preferably 500 to 200,000 mPa · s, particularly 1,000 to 100,000 mPa · s at 25 ° C. The viscosity can be measured with a rotational viscometer.

  In the emulsion composition of the present invention, water is blended as the component (D), and the above-described organosilicone resin water-miscible organic solvent solution, emulsifier, organic bismuth compound and water are mixed and emulsified and dispersed according to a conventional method. Can be prepared.

  In this case, the water content of the component (D) is 25 to 2,000 parts by mass and preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the component (A).

  Moreover, it is preferable that the non volatile matter (solid content) of the obtained emulsion composition is 5-80 mass%, especially 10-70 mass%.

  Furthermore, the average particle size of the obtained emulsion composition is preferably 50 to 1,000 nm, particularly preferably 100 to 800 nm. In the present invention, the average particle size can be measured by a particle size distribution measuring device N4Plus manufactured by Coulter.

  Here, the above-mentioned organosilicone resin emulsion composition is a one-component type, but it is preferably used as a two-component coating agent comprising the following organosilicone resin emulsion and organic bismuth compound emulsion as a two-component type. Is preferable from the viewpoint of storage stability. In addition, organosilicone resin water-miscible organic solvent solution, emulsifier, water organosilicone resin emulsion and organic bismuth compound, emulsifier, water and organic bismuth compound emulsion are prepared separately and then mixed uniformly. It is also possible to obtain the emulsion composition of the present invention.

Organosilicone resin emulsion (A) Organosilicone resin: 100 parts by mass
(B) Emulsifier: 0.9999 to 49.9999 parts by mass, in particular 1.995 to 29.995 parts by mass,
(D) Water: 24.9975 to 1,999.975 parts by mass, particularly 49.99 to 999.99 parts by mass
Organic bismuth compound emulsion (C) Organic bismuth compound: 0.01 to 10 parts by mass, preferably 0.03 to 8 parts by mass, more preferably 0.05 to 5 parts by mass,
(B) Emulsifier: 0.0001-5 parts by mass, especially 0.005-5 parts by mass,
(D) Water: 0.0025 to 200 parts by mass, particularly 0.01 to 200 parts by mass

In this case, the components (A) to (D) are as described above, and the total amount of these components (A) to (D) in the two-component coating agent is as described above.
(A) component: 100 mass parts,
(B) component: 1-50 mass parts, preferably 2-30 mass parts, more preferably 3-20 mass parts,
Component (C): 0.01 to 10 parts by mass, preferably 0.03 to 8 parts by mass, more preferably 0.05 to 5 parts by mass,
Component (D): 25 to 2,000 parts by mass, preferably 50 to 1,000 parts by mass.

  Moreover, it is preferable to mix | blend the said (E) component with the said organosilicone resin emulsion and / or the said organic bismuth compound emulsion, and (E) component is 1-50 mass parts especially in organosilicone resin emulsion, especially 3-40 mass. Part of the organic bismuth compound emulsion is 0 to 10 parts by weight, particularly 0 to 8 parts by weight, and the total amount of the component (E) as a two-component coating agent is 100 parts by weight of the component (A). 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, still more preferably 5 to 30 parts by mass.

  Furthermore, the non-volatile content (solid content) of the organosilicone resin emulsion and the organic bismuth compound emulsion is 5 to 80% by mass, particularly 10 to 70% by mass, respectively, and the non-volatile content in the mixture when these two emulsions are mixed is also It is preferably 5 to 80% by mass, particularly 10 to 70% by mass. The average particle size of each emulsion is 50 to 1,000 nm, particularly 100 to 800 nm, and the average particle size of the emulsion in the mixture when both emulsions are mixed is also 50 to 1,000 nm, particularly 100 to It is preferable that it is 800 nm.

The organosilicone resin emulsion composition of the present invention is applied to the surface of transparent or opaque substrates such as metals, ceramic inorganic materials, glass, wood, paper products, plastics, rubber, etc., and dried to form a cured protective film. In this case, heat treatment can also be performed.
In the case of a two-component coating agent, the organosilicone resin emulsion and the organic bismuth compound emulsion can be uniformly mixed to form a mixture, which can be similarly applied to the substrate surface, dried and cured.

  In addition, as a coating method to a base material, conventionally well-known various coating methods, such as a dipping method, a spray method, a roll coat method, and a brush coating method, are possible. The coating amount of the organosilicone resin emulsion composition is not particularly limited, but is usually an amount such that the film thickness after drying is 0.1 to 1,000 μm, particularly 1 to 100 μm.

  As temperature at the time of forming a cured film, it is preferable to heat to 40-300 degreeC. When the temperature is lower than 40 ° C., the water-miscible organic solvent having an SP value of 8.0 to 11.0 as the component (E) does not completely volatilize, so the curing reaction may not proceed completely. . When the temperature is higher than 300 ° C., the silicone resin may be decomposed. More preferably, it is 50-250 degreeC, More preferably, it is 60-200 degreeC. The heating time is preferably 0.5 minutes to 50 hours, more preferably 1 minute to 24 hours.

  This cured protective coating is high in hardness, rich in flexibility, has good adhesion and weather resistance, and can also impart water repellency, so that the base treatment agent for exterior building materials such as metal, ceramic, and wood, It is suitable for paints such as topcoat agents, protective coating agents for metal surfaces such as precoat metals, charge control coating agents for electrophotographic carriers, or adhesives.

  When the base material is metal, it is used for surface treatment of iron, stainless steel building structure materials, aluminum sash building materials, etc., surface treatment such as anticorrosion treatment coating, electrodeposition coating for automobiles or electrical appliances, or electrophotographic carrier It can be suitably used for the surface protective coating of magnetic powder. When the substrate is a plastic, it can be suitably used as a plastic plate, a magnetic or heat-sensitive recording film, a packaging film, a surface protective coating such as vinyl cloth, or a function-imparting binder. When the substrate is a wood or paper product, it can be applied to a surface protective coating for plywood, a surface protection for thermal recording, a water-resistant coating for treating the printed surface, and the like. Moreover, since it also has water repellency, it can also be applied as a surface protective coating for synthetic leather or the like. It can also be applied as a water-soluble binder for water-resistant printing inks. When the base material is inorganic material, mortar, concrete or cement exterior wall material or ceramic panel, ALC plate, sizing board, gypsum board, brick, glass, ceramics, artificial marble surface protection coating, surface treatment It can be applied as a paint. It can also be used as a base polymer for adhesives, and by adding other organic resins or silane coupling agents, it is possible to obtain an adhesive effective for adhesion between different kinds of substrates.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part and% show a mass part and mass%, respectively.

[Production Example 1]
Average composition formula: [(CH ₃ ) SiO _3/2 ] _0.67 [(C ₆ H ₅ ) SiO _3/2 ] _0.33 solution of ethylene glycol monobutyl ether acetate (SP value 8.9) of organosilicone resin (silicone) Resin / ethylene glycol monobutyl ether acetate = 83/17 mass ratio) 530 parts, “Neugen XL40” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, HLB10.5) as an emulsifier, “Neugen XL400D” (Trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, 65% aqueous solution of HLB18.4), 38.5 parts, “New Coal 291M” (trade name, manufactured by Nippon Emulsifier Co., Ltd., sodium alkylsulfosuccinate 75) % Liquid) 5 parts and deionized water 401.5 parts using a homodisper And a nonvolatile content of 47% at 0.99 ° C. / 3 hours, the average particle diameter (measured by Coulter particle size distribution measuring apparatus N4Plus) to obtain a 200nm blue white organosilicone resin emulsion (A-1).

[Production Example 2]
Average composition formula: [(CH ₃ ) SiO _3/2 ] _0.67 [(CH ₃ ) ₂ SiO _2/2 ] _0.33 solution of an organosilicone resin in ethylene glycol monobutyl ether acetate (SP value 8.9) (silicone resin) / Ethylene glycol monobutyl ether acetate = 93/7 mass ratio) 530 parts, “Neugen XL40” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, HLB10.5) as an emulsifier, “Neugen XL400D” (Trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, 65% aqueous solution of HLB18.4) 38.5 parts, “New Coal 291M” (trade name, manufactured by Nippon Emulsifier Co., Ltd., sodium alkylsulfosuccinate 75% Liquid) 5 parts and 401.5 parts deionized water are emulsified and dispersed using a homodisper. A nonvolatile content of 47% at 0.99 ° C. / 3 hours, to obtain an average particle size of the blue white organosilicone resin emulsion (manufactured by Coulter particle size measured by distribution analyzer N4Plus) is 190nm (A-2).

[Production Example 3]
"Octop Bismuth" (trade name, manufactured by Hope Pharmaceutical Co., Ltd., 37% mineral terpene solution of bismuth 2-ethylhexanoate), "Neugen XL40" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene) Decyl ether, HLB 10.5) 35 parts, "Neugen XL400D" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, 65% aqueous solution of HLB 18.4), 23 parts "New Coal 291M" (trade name) 8 parts by sodium emulsifier, 75% sodium alkylsulfosuccinate, and 434 parts deionized water were emulsified and dispersed using a homomixer, and further treated once with a high-pressure homogenizer at a pressure of 30 MPa. Non-volatile content in 3 hours is 24%, average particle size (measured with Coulter particle size distribution analyzer N4Plus) To obtain an emulsion of a white organic bismuth compound of 430nm (B-1).

[Production Example 4] (Comparative Production Example)
"Octope zinc" (trade name, manufactured by Hope Pharmaceutical Co., Ltd., 44% mineral terpene solution of zinc 2-ethylhexanoate), "Neugen XL40" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl) Ether, HLB10.5) 35 parts, "Neugen XL400D" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, 65% aqueous solution of HLB18.4), 23 parts "Newcol 291M" (trade name, Nippon Emulsifier Co., Ltd. (8% sodium alkylsulfosuccinate 75% solution) and 434 parts deionized water were emulsified and dispersed using a homomixer, and further treated once with a high pressure homogenizer at a pressure of 30 MPa, 70 ° C / 3 Nonvolatile content in time is 26%, average particle size (measured with Coulter particle size distribution analyzer N4Plus) is 620 To obtain emulsion (B-2) of a white organic zinc compound m.

[Examples 1 and 2 and Comparative Examples 1 to 6]
The organosilicone resin emulsion obtained in Production Example 1 or 2 above is represented by the organic bismuth compound emulsion obtained in Production Example 3, the organic zinc compound emulsion obtained in Production Example 4, and a 20% sodium acetate aqueous solution. After mixing with the formulation shown in 1, coated on a Migaki steel plate to a thickness of 15 μm using a wire bar and cured under the conditions shown in Table 1, the appearance of the coating surface was visually observed, and the curability was tacky by touch. And confirmed by a xylene resistance test. The results are shown in Table 1.

(Appearance) ○: Uniform, ×: Uneven (Yuzu skin) (Tacky feeling) ○: None, ×: Available (xylene resistance test) Evaluation by the time from dropping one drop of xylene on the coating until the coating dissolves
○: 60 seconds or more, Δ: 11 to 59 seconds, ×: 10 seconds or less

  As shown in Table 1, when the organosilicone resin emulsion containing the organic bismuth compound is cured by heating, a uniform cured film can be obtained. When an organozinc catalyst is used, a uniform film can be obtained, but the film is not completely cured. When a sodium acetate catalyst is used, it becomes a non-uniform film in which the skin is distorted and is not completely cured.

Claims (8)

(A) Average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (wherein R is the same or different monovalent organic group having 1 to 20 carbon atoms, and m is 0.2 to 1). 0.0, n is 0 to 0.8.) Organosilicone resin represented by: 100 parts by mass,
(B) Emulsifier: 1-50 parts by mass,
(C) Organic bismuth compound: 0.01 to 10 parts by mass,
(D) Water: An organosilicone resin emulsion composition containing 25 to 2,000 parts by mass.   Furthermore, the organosilicone resin emulsion composition of Claim 1 containing the water miscible organic solvent (E) whose SP value is 8.0-11.0 with respect to 100 mass parts of (A) component. object. (A) Average composition formula: [RSiO _3/2 ] _m [R ₂ SiO] _n (wherein R is the same or different monovalent organic group having 1 to 20 carbon atoms, and m is 0.2 to 1). 0.0, n is 0 to 0.8.) Organosilicone resin represented by: 100 parts by mass,
(B) Emulsifier: 0.9999 to 49.9999 parts by mass,
(D) Water: an organosilicone resin emulsion containing 24.9975 to 1,999.975 parts by mass;
(C) Organic bismuth compound: 0.01 to 10 parts by mass,
(B) Emulsifier: 0.0001-5 parts by mass,
(D) Water: An organic bismuth compound emulsion containing 0.0025 to 200 parts by mass, and the total of the organosilicone resin emulsion component and the organic bismuth compound emulsion component is (A) component: 100 parts by mass,
Component (B): 1 to 50 parts by weight,
(C) component: 0.01-10 mass parts,
Component (D): 25-2 liquid coating agent which is a 2,000 parts by weight.   In the organosilicone resin emulsion and / or organic bismuth compound emulsion, a water-miscible organic solvent having an SP value of 8.0 to 11.0 in total of 1 to 50 parts by mass with respect to 100 parts by mass of the component (A) ( The two-component coating agent according to claim 3, wherein E) is blended.   The two-component coating agent according to claim 4, wherein 1 to 50 parts by mass of the component (E) is blended with the organosilicone resin emulsion and 0 to 10 parts by mass of the component (E) is blended with the organic bismuth compound emulsion.   A method for forming a cured film, comprising applying the organosilicone resin emulsion composition according to claim 1 or 2 to a substrate and then drying and curing the composition.   The organosilicone resin emulsion and the organic bismuth compound emulsion in the two-component coating agent according to any one of claims 3 to 5 are mixed, applied to a substrate, and then dried and cured. A method for forming a cured film.   An article having a cured coating formed on a substrate by the method for forming a cured coating according to claim 6 or 7.