JP2006052310A - Method for producing polysiloxane composite polymer particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably producing polysiloxane composite polymer particles which can form coating films having good stain resistant properties, excellent weather resistance, excellent dryness and excellent finish properties. <P>SOLUTION: This method for producing the polysiloxane composite polymer particles is characterized by subjecting (B) an alkoxysilyl group-containing organosilane in the presence of (A) an aqueous fatty acid-modified resin dispersion obtained by dispersing a resin comprising a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) as a copolymerization components in an aqueous medium. The aqueous fatty acid-modified resin dispersion is desirably obtained by finely dispersing a monomer component mixture (I) comprising the fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) in an average particle diameter of ≤500 nm in an aqueous medium and then polymerizing the obtained emulsion. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing polysiloxane composite polymer particles capable of forming a coating film excellent in stain resistance, finish, weather resistance, and water resistance, an aqueous resin composition comprising the particles, and the aqueous solution. The present invention relates to an aqueous coating composition comprising a resin composition.

  In recent years, the use of organic solvents has been attracting attention in the field of paints and adhesives due to the reduction of environmental impact, and the shift to water-based technology has attracted attention. Has been. Among them, various methods for producing resin particles in which polysiloxane is combined with acrylic polymer particles have been proposed as those capable of improving performance such as water resistance, solvent resistance, and durability.

  For example, in Patent Document 1, after an alkoxysilane is absorbed into an organic polymer particle such as an acrylic latex dispersed in an aqueous medium, a polysiloxane is combined by advancing a condensation reaction of the alkoxysilane. The polysiloxane composite polymer particles are described. The composite polymer particles described in the document can co-combine an acrylic polymer and polysiloxane in the same particle, but since the compatibility between the two is insufficient, a film with excellent gloss is formed. The film was not obtained and the film characteristics were not sufficiently satisfactory.

  Therefore, the present applicant in Patent Document 2 describes polysiloxane composite polymer particles obtained by grafting an acrylic polymer and polysiloxane using a hydrolyzable silane compound having chain transfer ability. In addition, one or both of an alkoxysilane mixture having a complementary functional group that reacts with a functional group in the polymer, another alkoxysilane compound, and a low molecular weight organosiloxane compound are added to the acrylic polymer. The present inventors have proposed polysiloxane composite polymer particles characterized in that the resulting polysiloxane and acrylic polymer are grafted by the reaction of complementary functional groups simultaneously with the condensation reaction. Water-based paints containing these polysiloxane composite polymer particles can form a coating film with excellent film-forming properties, stain resistance, and weather resistance, but the film-forming properties may be poor depending on the coating conditions. In some cases, it was sufficient to improve the drying property of the coating film immediately after coating.

JP-A-4-57868 JP 2001-114898 A Japanese Patent Laid-Open No. 2001-115032

  An object of the present invention is to provide a method for stably producing polysiloxane composite polymer particles having stain resistance and capable of forming a coating film having excellent weather resistance, drying property and finish. .

As a result of intensive studies to solve the above problems, the present inventors have found that a resin containing a fatty acid-modified polymerizable unsaturated monomer and another polymerizable unsaturated monomer as a copolymerization component is dispersed in an aqueous medium. The present invention has been achieved by a production method comprising adding an alkoxysilyl group-containing organosilane in the presence of the resulting aqueous fatty acid-modified resin dispersion and subjecting it to a condensation polymerization reaction. That is, the present invention
1. (A) In the presence of an aqueous fatty acid-modified resin dispersion in which a resin containing a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) as a copolymerization component is dispersed in an aqueous medium. (B) A method for producing polysiloxane composite polymer particles, characterized by adding an alkoxysilyl group-containing organosilane and subjecting the organosilane (B) to a condensation polymerization reaction,
2. The aqueous fatty acid-modified resin dispersion (A) has an average particle diameter of a mixture (I) containing a monomer component comprising a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) in an aqueous medium. Is produced by finely dispersing the resulting emulsion so as to be 500 nm or less, and polymerizing the resulting emulsion,
3. Item 3. The production method according to Item 1 or 2, wherein the fatty acid-modified polymerizable unsaturated monomer (a) is a reaction product of a fatty acid and an epoxy group-containing polymerizable unsaturated monomer or a hydroxyl group-containing polymerizable unsaturated monomer,
4). The production method according to any one of items 1 to 3, wherein the other polymerizable unsaturated monomer (b) contains an alkoxysilyl group-containing polymerizable unsaturated monomer,
5. An alkoxysilyl group-containing organosilane (B)
_{^{(R 1) n -Si- (OR}} 2) 4-n
Wherein R ¹ is the same or different and represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ² is the same or different and may be a hydrogen atom or substituted. 1 to 4 which is an organic group having 1 to 10 carbon atoms, and n is an integer of 0 to 3). The manufacturing method of any one of these,
6). The aqueous fatty acid-modified resin dispersion (A) and the alkoxysilyl group-containing organosilane (B) each have a chemically functional complementary functional group other than an alkoxysilyl group and are grafted. 6. The production method according to any one of items 5 to 5,
7). The production method according to 6, wherein the combination of complementary functional groups is a hydroxyl group and an isocyanate group, a carboxyl group and an epoxy group, or an amino group and an epoxy group,
8). Mixture (I) is
HSCH ₂ CH ₂ CH ₂ SiR ³ _m (OR ⁴ ) _3-m (2)
(Wherein R ³ is the same or different and is an organic group having 1 to 8 carbon atoms, R ⁴ is the same or different and is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, m Is an integer of 0 to 3.) The production method according to any one of 2 to 7, further comprising a mercapto group-containing organosilane (C) represented by:
9. The production method according to any one of 2 to 8, wherein the mixture (I) further contains an alkoxysilyl group-containing organosilane (D),
10. The polysiloxane composite polymer particles obtained by the production method according to any one of items 1 to 9,
11. An aqueous resin composition containing the polysiloxane composite polymer particles according to Item 10,
12 The aqueous resin composition according to claim 11, further comprising an isocyanate curing agent and / or a melamine curing agent (E),
13. An aqueous coating composition containing the aqueous resin composition according to claim 11 or 12,
14 A method for forming a coating film, characterized by coating the surface to be coated with the aqueous coating composition according to claim 13;
15. A coated article obtained by the coating film forming method according to claim 14,
About.

  According to the production method of the present invention, it is possible to stably produce composite polymer particles in which a fatty acid-modified resin component and polysiloxane coexist in the same particle. In particular, an aqueous fatty acid-modified resin dispersion obtained by finely dispersing a fatty acid-modified polymerizable unsaturated monomer and other polymerizable unsaturated monomers in an aqueous medium so as to have a specific average particle size and polymerizing the resulting emulsion. By using the product, the condensation polymerization reaction of the alkoxysilyl group-containing organosilane can be stably advanced, and the coating film formed from the composition containing it can be finished, adherence, stain resistance, weather resistance It is excellent. Further, depending on the type of the fatty acid component, the polymer particles can be imparted with oxidative curability, and the coating film formed using the composition containing the particles has very excellent drying properties.

  In the present invention, the aqueous fatty acid-modified resin dispersion (A) comprises a resin containing a fatty acid-modified polymerizable unsaturated monomer (a) and other polymerizable unsaturated monomer (b) as a copolymerization component dispersed in an aqueous medium. It is resin made.

  Examples of the aqueous medium include water or a water-organic solvent mixed solution obtained by mixing water with an organic solvent such as a water-soluble organic solvent.

  In the present invention, the aqueous fatty acid-modified resin dispersion (A) can be produced without any particular limitation by a conventionally known method. For example, after the monomer (a) and the monomer (b) are polymerized in an organic solvent, the aqueous dispersion is modified as necessary. By mixing a neutralizing agent and / or an emulsifier and dispersing in an aqueous medium, a method obtained by emulsion polymerization of the monomer (a) and the monomer (b) in the presence of an aqueous medium and an emulsifier, and the like. Obtainable.

  In the present invention, the aqueous fatty acid-modified resin dispersion (A) comprises a mixture (I) containing a monomer component comprising a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) as an aqueous medium. It is desirable that the dispersion is finely dispersed so that the average particle diameter is 500 nm or less and the resulting emulsion is polymerized.

  By this production method, the aqueous fatty acid-modified resin dispersion (A) can be stably produced without using a large amount of an organic solvent or the like, and the average particle diameter of the dispersed resin particles of the resin dispersion (A) is 500 nm or less. In particular, it can be in the range of 80 to 400 nm, more particularly 100 to 300 nm, and the condensation polymerization reaction of the alkoxysilyl group-containing organosilane (B) following the production of the fatty acid-modified resin dispersion (A) can be stably advanced. And polysiloxane composite polymer particles can be stably produced.

  In this specification, the average particle size is obtained by diluting a sample with deionized water, and using “SALD-3100” (trade name, manufactured by Shimadzu Corporation, laser diffraction particle size distribution analyzer) at 20 ° C. It is a value when measured, and the measurement of the average particle size of the emulsion of the finely divided mixture (I) and the aqueous fatty acid-modified resin dispersion (A) is performed at the time when 30 minutes have passed after the production, respectively. To do.

  The fatty acid-modified polymerizable unsaturated monomer (a) used in the present invention gives a feeling of meatiness to a coating film formed using a composition containing polysiloxane composite polymer particles, and adheres to a substrate. In the case of improving oxidation and imparting oxidative curability to the formed coating film, it is possible to introduce an oxidatively hardened group into the particles, and a polymer having a polymerizable unsaturated group at the end of a hydrocarbon chain derived from a fatty acid. Unsaturated monomers are included. Here, examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is particularly preferable.

  Examples of the fatty acid-modified polymerizable unsaturated monomer (a) include a reaction product of a fatty acid (a1) and an epoxy group-containing polymerizable unsaturated monomer (a2) or a hydroxyl group-containing polymerizable unsaturated monomer (a3). Can do.

  Examples of the fatty acid (a1) include those having a structure in which a carboxyl group is bonded to the end of a hydrocarbon chain, and examples thereof include a dry oil fatty acid, a semi-dry oil fatty acid, and a non-dry oil fatty acid. Dry oil fatty acids and semi-dry oil fatty acids are not strictly distinguishable, but usually dry oil fatty acids are unsaturated fatty acids that are iodinated 130 or more, and semi-dry oil fatty acids are iodinated 100 or more and less than 130. Of unsaturated fatty acids. On the other hand, non-drying oil fatty acids are usually fatty acids having an iodine value of less than 100.

  Examples of the dry oil fatty acid and the semidry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, grape Nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, hydienoic acid fatty acid, etc., and non-drying oil fatty acid include, for example, coconut oil fatty acid , Hydrogenated coconut oil fatty acid, palm oil fatty acid and the like. These can be used alone or in combination of two or more. Furthermore, these fatty acids can be used in combination with caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like.

  In the present invention, for the purpose of improving the initial drying property of the formed coating film, the fatty acid (a1) is preferably a dry oil fatty acid and / or a semi-dry oil fatty acid.

  The epoxy group-containing polymerizable unsaturated monomer (a2) that can be reacted with the fatty acid (a1) to produce the fatty acid-modified polymerizable unsaturated monomer (a) is one epoxy group and one in one molecule. Specifically, for example, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4- Examples thereof include epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether. These can be used alone or in combination of two or more.

  The fatty acid (a1) and the epoxy group-containing polymerizable unsaturated monomer (a2) have an equivalent ratio of a carboxyl group in the fatty acid (a1) and an epoxy group in the epoxy group-containing monomer (a2) of 0.75: 1 to 1. The reaction can be carried out in such a ratio that it is in the range of 1.25: 1, preferably 0.8: 1 to 1.2: 1.

  The reaction between the fatty acid (a1) and the epoxy group-containing polymerizable unsaturated monomer (a2) is usually carried out in the presence of a polymerization inhibitor without causing a problem such as gelation in the fatty acid component. The reaction can be carried out under conditions that allow the group and the epoxy group in the epoxy group-containing polymerizable unsaturated monomer to react smoothly, and is usually heated at a temperature of about 100 to about 180 ° C. for about 0.5 to about 10 hours. Is suitable.

  In this reaction, an esterification reaction catalyst such as a tertiary amine such as N, N-dimethylaminoethanol, a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used. An inert organic solvent may be used.

  Examples of the polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4- Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone, and phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, and the like Examples thereof include radical polymerization inhibitors known per se such as nitroso compounds, and these can be used alone or in combination of two or more.

  The fatty acid-modified polymerizable monomer (a) can also be obtained by esterifying the fatty acid (a1) with the hydroxyl group-containing polymerizable unsaturated monomer (a3). Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a3) include a compound having one hydroxyl group and one polymerizable unsaturated group in one molecule. Specifically, for example, 2-hydroxyethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, C2-C8 hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, allyl alcohol, C2- (Meth) acrylate having a hydroxyl group, such as an ε-caprolactone modified product of C8 hydroxyalkyl (meth) acrylate; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end, and the like. It can be used in combination of more than one species.

  The fatty acid (a1) and the hydroxyl group-containing polymerizable unsaturated monomer (a3) usually have an equivalent ratio of 0.4: 1 to the carboxyl group in the fatty acid (a1) to the hydroxyl group in the hydroxyl group-containing monomer (a3). The reaction can be carried out in such a ratio that it is in the range of 1.25: 1, preferably 0.5: 1 to 1.2: 1.

  The reaction between the fatty acid (a1) and the hydroxyl group-containing polymerizable unsaturated monomer (a3) is usually carried out in the fatty acid (a1) component in the presence of a polymerization inhibitor without causing a reaction problem such as gelation. In the presence of an esterification catalyst at a temperature of about 100 to about 180 ° C. in the presence of an esterification catalyst. It is suitable to carry out by heating for 5 to about 10 hours. Examples of the esterification catalyst include sulfuric acid, aluminum sulfate, potassium hydrogen sulfate, alkyl-substituted benzene, hydrochloric acid, methyl sulfate, phosphoric acid, and the like. These catalysts usually contain the fatty acid (a1) to be reacted and a hydroxyl group. It can be used in the range of about 0.001 to about 2.0% by weight, based on the total amount of the polymerizable unsaturated monomer (a3). Furthermore, an organic solvent inert to the reaction can also be used.

  Examples of the polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4- Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone, and phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, and the like Examples thereof include radical polymerization inhibitors known per se such as nitroso compounds, and these can be used alone or in combination of two or more.

  In the present invention, since the secondary hydroxyl group is formed by the reaction of the carboxyl group of the fatty acid (a1) and the epoxy group of the epoxy group-containing polymerizable unsaturated monomer (a2), the fatty acid-modified polymerizable unsaturated monomer (A ) Is preferably a reaction product of a fatty acid (a1) and an epoxy group-containing polymerizable unsaturated monomer. When the fatty acid-modified polymerizable unsaturated monomer (a) has a secondary hydroxyl group, the adhesion of the formed coating film can be improved, and the alkoxysilyl group-containing organosilane (B) described below reacts with the hydroxyl group. In the case of having a functional group, the polysiloxane based on the organosilane (B) can be grafted with the aqueous fatty acid-modified resin dispersion (A), which is preferable.

  In the aqueous fatty acid-modified resin dispersion (A) in the present invention, the other polymerizable unsaturated monomer (b) is a polymerizable unsaturated monomer copolymerizable with the fatty acid-modified polymerizable unsaturated monomer (a), Examples of the compound include one or more, preferably one polymerizable unsaturated group in the molecule. Examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group. Specific examples of the other polymerizable unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n -Propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meta ) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), cyclohexyl ( (Meta) acrylate Alkyl or cycloalkyl (meth) acrylate such as methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate and cyclododecyl (meth) acrylate; isobornyl group-containing polymerization such as isobornyl (meth) acrylate Unsaturated monomer; adamantyl group-containing polymerizable unsaturated monomer such as adamantyl (meth) acrylate; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3, Epoxy group-containing polymerizable unsaturated monomers such as 4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; styrene, α-methylstyrene , Aromatic vinyl monomers such as vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltri An alkoxysilyl group-containing polymerizable unsaturated monomer such as ethoxysilane; a siloxane macromonomer such as polydimethylsiloxane macromonomer; a perfluoroalkyl (meth) such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate Acrylates; alkyl fluorine group-containing polymerizable unsaturated monomers such as fluoroolefins; N-((meth) acryloxyethyl) -N, N′-ethyleneurea and N- (acrylamidoethyl)- Copolymerizable ethylene urea derivatives such as N′-ethylene urea; polymerizable unsaturated monomers having a photopolymerizable functional group such as maleimide group; N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc. (Meth) acrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and other carboxyl group-containing polymerizable unsaturated monomers; maleic anhydride, itaconic anhydride and other unsaturated carboxylic acids Acid anhydrides; Amide group-containing polymerizable unsaturated monomers such as (meth) acrylonitrile, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate and amines Amino group-containing polymerizable substances such as adducts Saturated monomer: hydroxy having 2 to 8 carbon atoms such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylates such as alkyl (meth) acrylates, allyl alcohols, and ε-caprolactone modified products of the above hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms; having a polyoxyethylene chain whose molecular terminal is a hydroxyl group Hydroxyl group-containing polymerizable unsaturated monomers such as (meth) acrylate: polyoxyethylene chain-containing (meth) acrylate whose molecular terminal is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, sodium styrenesulfonate Salt, sulfo Sulphonic acid group-containing polymerizable unsaturated monomers such as til methacrylate and its sodium salt and ammonium salt; isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, or a compound having two isocyanate groups Isocyanate group-containing polymerizable unsaturated monomer such as a product obtained by addition reaction of the hydroxyl group-containing polymerizable unsaturated monomer in an equimolar amount; 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4 -(3- 2,4-dihydroxybenzophenone such as (acryloxy-2-hydroxypropoxy) benzophenone, addition reaction products of hydroxybenzophenones such as 2,2 ′, 4-trihydroxybenzophenone and glycidyl (meth) acrylate, or 2- (2 Polymerizable unsaturated monomer having an ultraviolet-absorbing functional group such as' -hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole; 4- (meth) acryloyloxy-1,2,2,6,6- Pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (Meth) acryloyl-4- (meth) acryloylamino-2,2, , 6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6 UV stability of 6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, etc. Polymerizable unsaturated monomer having a functional group; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone) Carbonyl group such as vinyl butyl ketone) Synthetic unsaturated monomers: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1 , 3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1, 1,1-trishydroxymethylethanedi (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) At least two polymerizable groups in one molecule such as acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc. And the like. These may be used alone or in combination of two or more depending on the desired performance.

  In the aqueous fatty acid-modified resin dispersion (A), the ratio of the monomer (a) and the monomer (b) used is not particularly limited, and desired performance and use of the desired polysiloxane composite polymer particles. However, from the viewpoint of the weather resistance, finish, and drying properties of the formed coating film, the monomer (a) is generally based on the total weight of the monomer (a) and the monomer (b). ) Is in the range of 5 to 50 wt%, preferably 10 to 40 wt%, more preferably 10 to 35 wt%, and monomer (b) is 50 to 95 wt%, preferably 60 to 90 wt%, more preferably Can be in the range of 65-90% by weight.

  In the present invention, the other polymerizable unsaturated monomer (b) contains at least a polymerizable unsaturated monomer containing a linear or branched hydrocarbon group having 6 or more carbon atoms as the monomer (a ) And monomer (b) based on the total weight, it is desirable to comprise 1 to 30% by weight, preferably 5 to 20% by weight, more preferably 6 to 18% by weight.

  Examples of the polymerizable unsaturated monomer containing a linear or branched hydrocarbon group having 6 or more carbon atoms include n-hexyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.) and the like. It can be used in combination of more than one species.

  By using a polymerizable unsaturated monomer containing a linear or branched hydrocarbon group having 6 or more carbon atoms as at least a part of the other polymerizable unsaturated monomer (b), an aqueous fatty acid-modified resin In the production of the dispersion (A), the polymerization stability of the emulsion obtained by atomizing the mixture (I) can be maintained, and the coating formed using a composition containing polysiloxane composite polymer particles is used. The water resistance of the film can be improved.

  Further, the other polymerizable unsaturated monomer (b) preferably contains a cycloalkyl group-containing polymerizable unsaturated monomer as at least a part thereof. The cycloalkyl group-containing polymerizable unsaturated monomer is preferably a compound having one cycloalkyl group having 6 or more carbon atoms and one polymerizable unsaturated bond in one molecule. For example, cyclohexyl (meta ) Acrylate, methyl cyclohexyl (meth) acrylate, t-butyl cyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, etc., and these may be used alone or in combination of two or more. Can be used. Of these, cyclohexyl (meth) acrylate is preferred.

  Using at least a part of the other polymerizable unsaturated monomer (b), an aqueous resin composition containing polysiloxane composite polymer particles by using one containing a cycloalkyl group-containing polymerizable unsaturated monomer The weather resistance of the coating film formed can be improved, and the water resistance and stain resistance can be improved. The content in the case of improving the weather resistance is 1 to 70% by weight, preferably 10 to 60% by weight, more preferably 25 to 25% based on the total weight of the monomer (a) and the monomer (b). A range of 45% by weight is preferred.

  Further, the other polymerizable unsaturated monomer (b) preferably contains a carbonyl group-containing polymerizable unsaturated monomer as at least a part thereof.

  The carbonyl group-containing polymerizable unsaturated monomer includes a compound having one carbonyl group and one polymerizable unsaturated bond in one molecule, and specifically includes, for example, acrolein, diacetone acrylamide, diacetone. Examples thereof include methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like. These can be used in combination. Of these, diacetone (meth) acrylamide is particularly preferred.

  Using at least a part of the other polymerizable unsaturated monomer (b) that contains a carbonyl group-containing polymerizable unsaturated monomer and blending a hydrazine derivative described later, the carbonyl group and the hydrazine derivative Crosslinking can be advanced, the drying property of the coating film can be further improved, and a coating composition that forms a coating film having excellent physical properties such as weather resistance and water resistance can be prepared.

  Such carbonyl group-containing polymerizable unsaturated monomers are generally used in the range of 0.5 to 35% by weight, preferably 2 to 20% by weight, based on the total weight of monomer (a) and monomer (b). It is suitable to do.

  Moreover, it is desirable that the other polymerizable unsaturated monomer (b) contains an alkoxysilyl group-containing polymerizable unsaturated monomer as at least a part thereof.

  Examples of the alkoxysilyl group-containing polymerizable unsaturated monomer include compounds having one alkoxysilyl group and one polymerizable unsaturated bond in one molecule. Specific examples thereof include vinyltrimethoxysilane and vinyl. Triethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and these monomers and alkoxysilyl group-containing organosilanes. Examples thereof include a macromonomer obtained by the condensation reaction. By using an alkoxysilyl group-containing polymerizable unsaturated monomer as at least a part of the other polymerizable unsaturated monomer (b), the alkoxysilyl group in the aqueous fatty acid-modified resin dispersion (A) particles is used. Can be grafted with an alkoxysilyl group in the alkoxysilyl group-containing organosilane (B) described later, and a polysiloxane based on the organosilane (B) is further dispersed. (A) It can be combined with particles.

The alkoxysilyl group-containing polymerizable unsaturated monomer is generally in the range of 0.3 to 20% by weight, preferably 0.5 to 15% by weight, based on the total weight of monomer (a) and monomer (b). Suitable for use within.

  In the present invention, the other polymerizable unsaturated monomer (b) can contain a hydroxyl group-containing polymerizable unsaturated monomer. Examples of the monomer include (meth) acryl such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Hydroxyl group-containing (meth) acrylates such as hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms of acid, allyl alcohol, and ε-caprolactone modified products of the above hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms; And polyoxyethylene chain-containing (meth) acrylate having a hydroxyl group. A polymerization step of a finely divided emulsion or a desired aqueous resin dispersion by using one containing a hydroxyl group-containing polymerizable unsaturated monomer as at least a part of the other polymerizable unsaturated monomer (b) It is possible to ensure the stability of the particles in the storage stage. In addition, a coating formed by using the composition of the present invention as a functional group that reacts with the curing agent by using the aqueous resin acid derivative in combination with a curing agent having a functional group capable of reacting with a hydroxyl group described below. The curability of the film can be improved.

  Such a hydroxyl group-containing polymerizable unsaturated monomer is generally in the range of 0.1 to 30% by weight, preferably 0.5 to 25% by weight, based on the total weight of the monomer (a) and the monomer (b). Suitable to use.

  Further, the other polymerizable unsaturated monomer (b) preferably comprises an acid group-containing polymerizable unsaturated monomer. Examples of the polymerizable unsaturated monomer containing an acid group include a carboxyl group-containing polymerizable unsaturated monomer such as (meth) acrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, and β-carboxyethyl acrylate; 2 -Acrylic acid-2-methylpropane sulfonic acid, allyl sulfonic acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylate and sulfonic acid group-containing polymerizable unsaturated monomers such as sodium salt and ammonium salt thereof, etc. Carboxy group-containing polymerizable unsaturated monomers are preferred.

  By using an acid group-containing polymerizable unsaturated monomer as at least a part of the other polymerizable unsaturated monomer (b), the stability and mechanical stability of the obtained aqueous resin dispersion particles in an aqueous medium are ensured. In addition, when the aqueous resin composition containing the same is applied to an enamel paint, the toning property of the paint can be improved.

  Such an acid group-containing polymerizable unsaturated monomer is used in the range of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, based on the total weight of the monomer (a) and the monomer (b). It is suitable to do.

  In the production method of the present invention, as the alkoxysilyl group-containing organosilane (B), a conventionally known one can be used without limitation, and when the aqueous fatty acid-modified resin dispersion (A) has an alkoxysilyl group, the graft point to the group In addition, it improves the stain resistance of the coating film formed using the composition containing the polysiloxane composite polymer particles of the present invention.

Examples of the organosilane (B) include at least one selected from the group consisting of an organosilane represented by the following formula (1) and a hydrolysis condensate of the organosilane.
_{^{(R 1) n -Si- (OR}} 2) 4-n (1)
Wherein R ¹ is the same or different and represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ² is the same or different and may be a hydrogen atom or substituted. A good C1-C10 organic group is shown, and n is an integer of 0-3.)
Specific examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, and t-pentyl. A linear group such as a group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 2,2,4-trimethylpentyl group, n-nonyl group, n-decyl group, n-dodecyl group, and / or Or a branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cycloheptyl group, a norbornyl group, and a methylcyclohexenyl group; a phenyl group, a biphenylyl group, a naptyl group, an antonyl group, phenanthryl Aryl groups such as groups; alkaryl groups, o-, m-, p-tolyl groups, xylyl groups and ethylphenyl Alkaryl groups such as benzyl groups; aralkyl groups such as benzyl groups, α- and β-phenylethyl groups; epoxy group derivatives such as glycidoxy groups and epoxycyclohexyl groups; (meth) acrylic group derivatives such as methacrylic groups and acrylic groups; amino Group, phenylamino group, amino group derivative such as dibutylamino group; sulfur-containing group derivative such as mercapto group, tetrasulfide group; alkyl ether group derivative such as (polyoxyalkylene) alkyl ether group; carboxyl group, sulfonyl group, etc. Anionic group derivatives; halogen atoms such as fluorine and chlorine may be mentioned, and these may be partially substituted with a quaternary ammonium salt structure-containing group derivative, a hydroxyl group, an isocyanate group, or the like.

Specific examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, Examples thereof include linear / branched alkyl groups such as a t-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group, and aryl groups such as a phenyl group. A methyl group is particularly preferable.

  Specific examples of such organosilane (B) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Tris such as ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane Alkoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldipropoxysilane, dipropoxydimethoxysilane Dialkoxy silanes such as dipropoxydiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane; trimethylethoxysilane, trimethylpropoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylpropoxysilane, etc. Mono-alkoxysilanes; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane and other organosilanes having an isocyanate group; γ-glycid Xylpropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Organosilanes having an epoxy group such as lan, γ-glycidoxypropylmethyldiethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane; N-β- (aminoethyl) aminopropyltrimethoxysilane, N-β- ( Aminosilane) organosilane having amino group such as aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane; γ-mercaptopropyltri Examples thereof include organosilanes having a mercapto group such as methoxysilane and γ-mercaptopropyltriethoxysilane, and these can be used alone or in combination.

  In addition, as the hydrolyzed condensate of the above organosilane, in the above formula (1), n is an organosilane having 1 and / or 2 or n is an organosilane having 1 and / or 2 as a main component. Mention may be made of organopolysiloxanes produced by hydrolytic condensation of silane and having an alkoxysilyl group and a three-dimensional structure. At this time, an organosilane in which n is 0 and / or 3 can be appropriately mixed as a raw material.

  In addition, a linear organopolysiloxane produced by hydrolytic condensation of an organosilane mainly composed of an organosilane having n = 2 is appropriately mixed as a raw material, and a polysiloxane skeleton having a three-dimensional structure in the molecule and An organopolysiloxane having both a linear polysiloxane skeleton; a linear, branched or cyclic organopolysiloxane produced by hydrolytic condensation of an organosilane composed mainly of an organosilane having n = 0 Can also be used.

  Commercially available products of the above alkoxysilyl group-containing organopolysiloxane include “SR2406”, “SR2410”, “SR2420”, “SR2416”, “SR2402”, “AY42-161” (above Toray Dow Corning Silicone Co., Ltd.) ), "FZ-3704", "FZ-3511" (manufactured by Nihon Unicar), "KC-89S", "KR-500", "X-40-9225", "X-40-9246", " X-40-9250 "," KR-217 "," KR-9218 "," KR-213 "," KR-510 "," X-40-9227 "," X-40-9247 "," X- 41-1053 "," X-41-1056 "," X-41-1805 "," X-41-1810 "," X-40-2651 "," X-40-2308 "," X-40-9238 "," X-40-2239 "," X-40-2327 "," KR-400 "," X-40-175 "," X-40-9740 "," X-40- " 2651 ”,“ KC-89S ”(manufactured by Shin-Etsu Chemical Co., Ltd.),“ ethyl silicate 48 ”,“ ethyl silicate 40 ”(manufactured by Colcort),“ MKC silicate MS51 ”,“ MKC silicate MS56 ”(and above) , Manufactured by Mitsubishi Chemical Corporation).

  In the present invention, the aqueous fatty acid-modified resin dispersion (A) and the organosilane (B) are each other than an alkoxysilyl group for the purpose of suppressing three-dimensional crosslinking in the particles in the production stage of the polysiloxane composite polymer. It is desirable to graft with complementary functional groups that can be chemically bonded.

  The complementary functional group is a combination of functional groups that can be bonded to each other, such as a hydroxyl group and an isocyanate group, a carboxyl group and an epoxy group, an amino group and an epoxy group, an amide group and an epoxy group, a carbonyl group and a hydrazide group. In particular, a hydroxyl group and an isocyanate group, a carboxyl group and an epoxy group, or a combination of an epoxy group and an amino group is preferable.

  Specific examples of the polymerizable unsaturated monomer having a complementary functional group used as the other polymerizable unsaturated monomer in the aqueous fatty acid-modified resin dispersion (A) include acrylic acid, methacrylic acid, itaconic acid, Carboxyl group-containing polymerizable unsaturated monomers such as maleic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Hydroxyl-containing (meth) acrylates such as hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms, allyl alcohol, and ε-caprolactone modified products of hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms; Polyoxyethylene chain-containing (meth) a terminated with a hydroxyl group Hydroxyl group-containing polymerizable unsaturated monomers such as relate; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, Epoxy group-containing polymerizable unsaturated monomers such as 3,4-epoxycyclohexylpropyl (meth) acrylate and allyl glycidyl ether; N, N-dimethylaminoethyl (meth) acrylate, adducts of glycidyl (meth) acrylate and amines Amino group-containing polymerizable unsaturated monomers such as isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, or a compound having two isocyanate groups and a hydroxyl group-containing polymerizable unsaturated monomer An isocyanate group-containing polymerizable unsaturated monomer such as a product obtained by addition reaction of monomers at an equimolar amount can be exemplified.

  In the present invention, when the epoxy group-containing polymerizable unsaturated monomer is used as a complementary functional group, the amount used is 0.1 based on the total weight of the monomer (a) and the monomer (b). It can be included in the range of -30% by weight, preferably 0.5-25% by weight.

  On the other hand, specific examples of the organosilane having a complementary functional group in the alkoxysilyl group-containing organosilane (B) include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-isocyanatopropylmethyl. Organosilanes having an isocyanate group such as dimethoxysilane and γ-isocyanatopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Organosilane having an epoxy group such as γ-glycidoxypropylmethyldiethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane; N-β- (aminoethyl) aminopropyltrimethoxy Lan, N-β- (aminoethyl) aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, “X-40-2651 ”(Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., alkoxysilane oligomer having amino group) and the like.

  When the organosilane having the above-mentioned complementary functional group is used, the amount used is in the range of 0.1 to 15% by weight, preferably 0.3 to 10% by weight in the alkoxysilyl group-containing organosilane (B). It is desirable that

  In the present invention, the aqueous fatty acid-modified resin dispersion (A) contains, in an aqueous medium, a mixture (I) containing a monomer component comprising a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b). The mixture (I) further contains a mercapto group-containing organosilane (C) when it is obtained by polymerizing an emulsion obtained by fine dispersion so that the average particle size is 500 nm or less. It is desirable to do.

  As the mixture (I), by using a mixture in which the mercapto group-containing organosilane (C) is further added to the monomer component, the organosilane (C) is adjusted while appropriately adjusting the molecular weight of the polysiloxane composite polymer particles. Can have an alkoxysilyl group, the group can act as a grafting point with the organosilane (B), and the polysiloxane component based on the organosilane (B) is more complexed with the aqueous fatty acid-modified resin dispersion particles. can do.

Such mercapto group-containing organosilane (C) can be represented by the following formula (2).
HSCH ₂ CH ₂ CH ₂ SiR ³ _m (OR ⁴ ) _3-m (2)
In the formula, R ³ is the same or different and is an organic group having 1 to 8 carbon atoms, R ⁴ is the same or different and is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and m is It is an integer of 0-3, preferably 0-2.

Examples of R ³ include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Examples of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, Examples thereof include alkyl groups such as sec-butyl group and t-butyl group, and acyl groups such as acetyl group.

  Specific examples of the mercapto group-containing organosilane (C) include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. These can be used alone or in combination of two or more.

  When such mercapto group-containing organosilane (C) is used, the amount used is 0.1 to 15% by weight, preferably 0.3 to 10%, based on the total weight of monomer (a) and monomer (b). The range of% by weight is preferred.

  For the purpose of further improving the weather resistance and stain resistance of the coating film formed using the polysiloxane composite polymer particles of the present invention, the mixture (I) further contains an alkoxysilyl group-containing organosilane (D). be able to. As this organosilane (D), the thing similar to what was listed by description of the said organosilane (B) can be used. By using a mixture in which the organosilane (D) is further added to the monomer component as the mixture (I), aqueous fatty acid-modified resin dispersion particles encapsulating the organosilane (D) can be produced. As a result, the organosilane (D) can be uniformly dispersed in the coating film formed using the resulting aqueous dispersion, and an alkoxysilyl group can be introduced into the resin particles. By setting the graft point with B), the polysiloxane component based on the organosilane (B) and the organosilane (D) can be more complexed with the aqueous fatty acid-modified resin dispersion.

  When the organosilane (D) is used, the amount used is preferably in the range of 1 to 100% by weight, preferably 5 to 80% by weight, based on the total weight of the monomer (a) and the monomer (b). It is.

  The mixture (I) is an epoxy resin, a fatty acid-modified epoxy resin, an acrylic resin, a polyester resin, a polyurethane resin, an alkyd resin, a polyorganosiloxane not containing an alkoxysilyl group, an ultraviolet absorber, an ultraviolet stabilizer, and a metal. Additives for coating materials such as dryers; curing agents such as isocyanate compounds, blocked isocyanate compounds, and melamine; colorants such as pigments and dyes.

  When the mixture (I) is finely dispersed in an aqueous medium, it can contain an emulsifier, if necessary. As the emulsifier, an anionic emulsifier and a nonionic emulsifier are suitable. Examples of the anionic emulsifier include sodium salts and ammonium salts such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylphosphoric acid. Nonionic emulsifiers include, for example, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl Phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monos Areto, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, and the like.

  Also, a polyoxyalkylene group-containing anionic emulsifier having an anionic group and a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group in one molecule, or the anionic group and polymerizable unsaturated in one molecule Reactive anionic emulsifiers having groups may be used.

  The emulsifier can be used in the range of 0.1 to 15% by weight, preferably 0.5 to 12% by weight, based on the total weight of monomer (a) and monomer (b).

  The mixture (I) may contain a chain transfer agent for the purpose of adjusting the molecular weight of the resulting aqueous fatty acid-modified resin dispersion. Examples of the chain transfer agent include compounds having a mercapto group other than the organosilane (C), specifically, for example, lauryl mercaptan, t-dodecyl mercaptan, octyl mercaptan, 2-ethylhexyl thioglycolate, Examples include 2-methyl-5-tert-butylthiophenol, mercaptoethanol, thioglycerol, mercaptoacetic acid (thioglycolic acid), mercaptopropionate, and n-octyl-3-mercaptopropionate. The chain transfer agent is generally used in an amount of 0.05 to 10% by weight, particularly 0.1 to 5% by weight, based on the total weight of monomer (a) and monomer (b). is there.

  In the aqueous fatty acid-modified resin dispersion (A) obtained by the specific production method in the present invention, the component contained in the mixture (I) in the polymerization stage is a polymerization field due to the fatty acid-modified polymerizable unsaturated monomer (a) and the like. Diffusion from finely dispersed particles can be suppressed and the product can be stably produced. If necessary, the mixture (I) can be mixed with a long-chain saturated hydrocarbon solvent such as hexadecane, hexadecanol, etc. Hydrophobic organic solvents generally used in miniemulsion polymerization such as long-chain alcohol solvents may be blended.

  The mixture (I) described above is finely dispersed in an aqueous medium to form an emulsion (hereinafter sometimes abbreviated as “emulsion”) which is a particle dispersion containing the mixture (I). Can do.

  The concentration of the mixture (I) in the aqueous medium is generally 10 to 70% by weight from the viewpoint of atomization suitability of the emulsion to be formed, stability in the polymerization stage, practicality when applied to an aqueous paint, and the like. The preferred range is 20 to 60% by weight.

  The fine dispersion of the mixture (I) in the aqueous medium is not particularly limited, and can be performed using a disperser having a high energy shearing ability. Examples of the disperser that can be used in this case include a high-pressure emulsifier, an ultrasonic emulsifier, a high-pressure colloid mill, and a high-pressure homogenizer. These dispersers can usually be operated under a high pressure of about 10 to 1000 MPa, preferably about 50 to 300 MPa. In addition, the monomer mixture may be pre-emulsified with a disper or the like in advance before being dispersed by the machine.

  The average particle size of the emulsion is desirably 500 nm or less, 50 to 500 nm, more preferably 100 to 300 nm.

  Polymerization of the emulsion thus obtained is carried out by, for example, charging the entire amount of the finely dispersed emulsion into a reactor equipped with a stirrer, adding a polymerization initiator, and heating with stirring according to the miniemulsion polymerization method. be able to.

  The polymerization initiator may be either oil-soluble or water-soluble, and examples of the oil-soluble polymerization initiator include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide. Organic peroxides such as oxides; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile); and water-soluble initiators such as cumene hydroperoxide , Organic peroxides such as tert-butyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobis (2-methylpropiononitrile) A Bis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl)- Azo compounds such as propionamide] and azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}; and persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate. . These can be used alone or in combination of two or more. Further, if necessary, a reducing agent such as sugar, sodium formaldehyde sulfoxylate, or iron complex may be used in combination with the polymerization initiator to form a redox polymerization system.

  In general, the polymerization initiator is preferably used in an amount of 0.1 to 5% by weight, particularly 0.2 to 3% by weight, based on the total weight of the monomer (a) and the monomer (b). The method for adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount thereof. For example, it may be previously contained in the mixture (I) or the aqueous medium, or may be added all at once during the polymerization, or may be added dropwise.

Polysiloxane composite polymer particles The present invention is characterized in that an alkoxysilyl group-containing organosilane (B) is added in the presence of the aqueous fatty acid-modified resin dispersion (A), and the organosilane is subjected to a condensation polymerization reaction. To do.

  The amount of organosilane (B) to be added in the presence of the aqueous fatty acid-modified resin dispersion (A) is determined from the viewpoint of the weather resistance, stain resistance, and production stability of the formed coating film. A) 0.1 to 200 parts by weight, preferably 10 to 80 parts by weight is appropriate for 100 parts by weight of the solid content.

  In the production method of the present invention, the organosilane (B) is preferably added in the presence of the aqueous fatty acid-modified resin dispersion (A) and absorbed by the dispersion (A) particles.

  As a method of absorbing the organosilane (B) in the aqueous fatty acid-modified resin dispersion (A) particles, the organosilane (B) is easily added to the aqueous dispersion in which the particles are dispersed and stirred well. Achieved. Examples of the addition method include a method in which the whole amount is added all at once, or a part or the whole amount is added continuously or intermittently. In this case, the aqueous fatty acid-modified resin dispersion (A) has a pH of 5 to 9, preferably, because it suppresses the progress of condensation polymerization or grafting reaction in a state where the absorption of organosilane (B) is not sufficient. The temperature is adjusted to 6 to 8, and the temperature is 90 ° C. or lower, preferably 70 ° C. or lower, more preferably 50 ° C. or lower, particularly preferably 30 ° C. or lower. .

  The organosilane (B) can be subjected to a condensation polymerization reaction and a grafting reaction after being absorbed into the aqueous fatty acid-modified resin dispersion (A) particles. Such a reaction can be easily controlled by changing the reaction temperature, and the degree of polymerization of polysiloxane based on organosilane (B) and / or organosilane (D) can be controlled. The condensation polymerization reaction can be carried out at a temperature of 30 ° C. or higher, preferably 50 ° C. or higher, more preferably 70 ° C. or higher. The graft reaction of the aqueous fatty acid-modified resin dispersion (A) particles and the organosilane (B) or the polysiloxane based on the (B) can also proceed under the above conditions.

Aqueous Resin Composition The aqueous resin composition of the present invention contains the polysiloxane composite polymer particles described above.

  In the present invention, when the resin in the aqueous resin composition has a crosslinkable functional group such as a hydroxyl group, a curing agent having a crosslinkable functional group capable of reacting with the functional group, for example, an isocyanate-based curing agent and / or melamine A system hardening | curing agent (E) can be contained.

  When the isocyanate curing agent and / or melamine curing agent (E) is blended, the blending amount is generally 1 to 100% by weight, preferably 3 to 3% based on the resin solid content of the polysiloxane composite polymer. It can be in the range of 80% by weight.

  Further, the aqueous resin composition of the present invention can further contain a hydrazine derivative. Specific examples of the hydrazine derivatives include saturated carboxylic acid dihydrazides having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and the like. Monoolefinic unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid dihydrazide, terephthalic acid dihydrazide or isophthalic acid dihydrazide, pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; Citric acid trihydrazide, 1,2,4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid Lahydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride); a compound having a hydrazide group such as dihydrazide carbonate; bissemicarbazide; hexamethylene diisocyanate or isophorone A polyfunctional semicarbazide obtained by excessively reacting a diisocyanate such as diisocyanate and a polyisocyanate compound derived therefrom with an N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazide exemplified above; Excess dihydrazide exemplified above is added to an isocyanate group in a reaction product of an active hydrogen compound containing a hydrophilic group such as polyether and polyol or polyethylene glycol monoalkyl ether. Response is not water-based polyfunctional semicarbazide obtained; compound having a semicarbazide group, such as a mixture of polyfunctional semicarbazide and aqueous polyfunctional semicarbazide, compounds and the like having a hydrazone group such as bis-acetyl-di hydrazone.

  By containing the hydrazine derivative, the formed coating film is useful because it can adsorb and remove harmful substances in the air, such as formaldehyde, and it reacts when the polysiloxane complex polymer has a carbonyl group. It is also possible to act as a crosslinking agent.

  The blending amount of the hydrazine derivative can be generally in the range of 0.01 to 10% by weight, particularly 0.1 to 5% by weight, based on the solid content of the polysiloxane composite polymer.

  The aqueous resin composition can contain a metal dryer in order to accelerate the curing of the coating film. Examples of the metal dryer include salts of at least one metal selected from the group consisting of aluminum, calcium, cerium, cobalt, iron, lithium, magnesium, manganese, zinc, and zirconium with an acid. Examples include capric acid, caprylic acid, isodecanoic acid, linolenic acid, naphthenic acid, neodecanoic acid, octenoic acid, oleic acid, palmitic acid, resin acid, ricinoleic acid, soybean oil fatty acid, stearic acid, tall oil fatty acid and the like. . The metal dryer is used in an amount of 0.1 to 10% by weight, preferably 0.5 to 7% by weight, based on the resin solid content of the polysiloxane composite polymer.

  In addition to the above components, the aqueous resin composition of the present invention is a water-soluble or emulsion-type acrylic resin, alkyd resin, silicone resin, fluororesin, epoxy resin, urethane resin, polyester resin, amino resin, or other modified resin; Additives such as wetting agents, antifoaming agents, plasticizers, film-forming aids, organic solvents, thickeners, preservatives, fungicides, pH adjusters, curing catalysts, and surface adjusters are selected and combined as appropriate. Can be contained.

  Thus, the above-mentioned aqueous resin composition is used for coatings such as automotive outer panels, automotive parts, automotive repairs, cans, PCMs, architectural coatings, printing inks, non-woven fabrics, etc. It can be used for various applications such as an agent, a filler, a molding material, and a resist.

Aqueous coating composition The aqueous coating composition of the present invention comprises the aqueous resin composition described above.

  When the aqueous resin composition is applied to an aqueous coating composition, it can be applied to either a clear coating or an enamel coating.

  When applied as an enamel paint, conventionally known color pigments, extender pigments, rust preventive pigments and the like can be blended as the pigment component.

  In the aqueous coating composition, pigment dispersant, surfactant, surface conditioner, plasticizer, anti-settling agent, antistatic agent, antibacterial agent, fragrance, ultraviolet absorber, ultraviolet stabilizer, curing catalyst, dispersant, Antifoaming agent, thickener, film-forming aid, preservative, antifungal agent, antifreezing agent, pH adjuster, flash last inhibitor, aldehyde scavenger, layered viscosity mineral, powdered or fine particle activated carbon, photocatalyst Additives such as titanium dioxide and low-contaminating agents such as alkylene glycol-modified alkyl silicate can be appropriately selected and contained in combination.

  Moreover, although the water-based coating composition of this invention can be provided as a one-pack type, it can also be provided as a two-pack type paint according to the kind of hardening | curing agent mix | blended as needed. In the case of the two-component type, it is usually mixed immediately before use and used for coating.

  The present invention is a coating method characterized by coating the surface to be coated with the water-based coating composition.

  The surface to be coated is not particularly limited. Metals such as iron and aluminum; Organic base materials such as plastics; Base materials such as inorganic base materials such as concrete blocks, wood and stones; A coating film can be mentioned. Examples of the old coating film include acrylic resin, acrylic urethane resin, polyurethane resin, fluororesin, silicon acrylic resin, vinyl acetate resin, epoxy resin, alkyd resin, and the like. Further, these coated surfaces may be subjected to chemical conversion treatment, undercoating, intermediate coating, or the like. It is also possible to apply a known paint after applying the aqueous paint composition of the present invention.

  The aqueous coating composition can be applied using a method such as air spray, airless spray, lysine gun, universal gun, roller, brush, electrostatic coating or the like. Moreover, as a drying method, any of heat drying, forced drying, and normal temperature drying may be sufficient, and it can adjust suitably according to a composition. In this specification, the drying condition of less than 40 ° C. is normal temperature drying, the drying condition of 40 ° C. or more and less than 80 ° C. is forced drying, and the drying condition of 80 ° C. or more is heat drying.

Hereinafter, the present invention will be described more specifically with reference to examples. “Parts” and “%” are “parts by weight” and “% by weight”.

Production of fatty acid-modified polymerizable unsaturated monomer Production Example 1
A four-necked flask is charged with 560 parts of safflower oil fatty acid, 284 parts of glycidyl methacrylate, and 0.65 part of hydroquinone, and reacted with stirring at 140 ° C. to an acid value of 5 or less, fatty acid-modified polymerizable unsaturated having a secondary hydroxyl group. Monomer (a-1) was obtained.

Production Example 2
A four-necked flask was charged with 560 parts of soybean oil fatty acid, 0.45 part of hydroquinone, 0.65 part of methyl sulfuric acid, and 36 parts of toluene, and the temperature was raised to 120 ° C. A mixture of 325 parts of 2-hydroxyethyl methacrylate, 0.45 parts of hydroquinone, 1.4 parts of methylsulfuric acid, and 58.5 parts of toluene was added dropwise over 2 hours. After completion of dropping, the temperature was raised to 150 ° C., and the reaction was continued until the acid value was 8.7 or less while removing condensed water. Thereafter, toluene was removed under reduced pressure until the heating residue was 95% or more to obtain a fatty acid-modified polymerizable unsaturated monomer (a-2).

Production of curing agent Production Example 3
Into a flask, 55 parts of a one-terminal methoxypolyethylene glycol having a number average molecular weight of 550 and 504 parts of “Takenate D170HN” (trade name, manufactured by Mitsui Takeda, trimer of hexamethylene diisocyanate) were added and reacted at 70 ° C. until an NCO value of 218 was reached. To obtain a water-dispersible polyisocyanate.
Production Example 4
In a flask, 275 parts of one-end methoxypolyethylene glycol having a number average molecular weight of 550 and 504 parts of “Takenate D170HN” (made by Mitsui Takeda, hexamethylene diisocyanate trimer) were reacted at 70 ° C., with an NCO value of 135, 50 parts of methyl isobutyl ketone was added, the temperature was raised to 120 ° C., 219 parts of methyl ethyl ketoxime was added dropwise over 1 hour, and the reaction was further advanced to an NCO value of 1 or less. After completion of the reaction, the mixture was diluted with 60 parts of propylene glycol monomethyl ether to obtain a water-dispersible block polyisocyanate having a solid content of 90%.

Production of polysiloxane composite resin dispersion Example 1
Fatty acid-modified polymerizable unsaturated monomer (a-1) 30 parts, n-butyl methacrylate 25 parts, i-butyl methacrylate 27 parts, 2-ethylhexyl methacrylate 17 parts, methacrylic acid 1 part, n-octyl mercaptopropionate To 0.5 part of the monomer mixture, 10 parts of “New Coal 707SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier having a polyoxyethylene chain, 30% active ingredient) and 90 parts of water are mixed. For 15 minutes to make a preliminary emulsion. This preliminary emulsion was subjected to a high pressure treatment of 100 MPa with a high pressure emulsifier to obtain a fine monomer dispersion having an average particle size of 186 nm. Next, this monomer fine dispersion was transferred to a flask and heated to 80 ° C. with stirring. An initiator aqueous solution in which 0.24 part of ammonium persulfate was dissolved in 10 parts of water was dropped into the flask over 1 hour, and then the reaction was allowed to proceed at 80 ° C. for 2 hours, cooled, and adjusted to pH 7 with aqueous ammonia. A fatty acid-modified acrylic emulsion having an average particle diameter of 191 nm was obtained. Next, the temperature of the fatty acid-modified acrylic emulsion inside the flask was adjusted to 25 ° C., 5 parts of water, 5 parts of methyltrimethoxysilane and 15 parts of phenyltrimethoxysilane were added, and stirring was continued for 1 hour. Then, it heated up at 80 degreeC and stirred for 3 hours and made it react. The solid content of the resulting dispersion was measured (Note 1). Based on this measured value, the solid content concentration was adjusted to 48% with water, and an aqueous resin dispersion in which polysiloxane and a fatty acid-modified acrylic emulsion were combined ( A-1) was obtained.
(Note 1) The sample is dried at 130 ° C. for 1 hour with a dryer, and the solid content concentration is measured from the weight before and after this.

Examples 2 to 6 and Comparative Example 1
In Example 1, the aqueous resin dispersions (A-2) to (A-6) were prepared in the same manner as in Example 1 except that the composition of the monomer emulsion and the organosilane to be added were changed to the following Table 1. And (A-15) was obtained.

Example 7
30 parts of fatty acid-modified polymerizable unsaturated monomer (a-1), 22 parts of n-butyl methacrylate, 27 parts of i-butyl methacrylate, 17 parts of 2-ethylhexyl methacrylate, 1 part of methacrylic acid, 3 parts of 2-hydroxyethyl methacrylate In a monomer mixed solution of 0.5 parts of n-octyl mercaptopropionate, 10 parts of “New Coal 707SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., anionic emulsifier having polyoxyethylene chain, active ingredient 30%), 90 parts of water was mixed and stirred with a disper for 15 minutes to prepare a preliminary emulsion. This preliminary emulsion was subjected to a high pressure treatment of 100 MPa with a high pressure emulsifier to obtain a fine monomer dispersion having an average particle diameter of 175 nm. Next, this monomer fine dispersion was transferred to a flask and heated to 80 ° C. An initiator aqueous solution in which 0.24 part of ammonium persulfate was dissolved in 10 parts of water was dropped into the flask over 1 hour. Thereafter, the reaction was allowed to proceed at 80 ° C. for 2 hours, cooled, and adjusted to pH 7 with aqueous ammonia to obtain a fatty acid-modified acrylic emulsion having an average particle size of 188 nm. Next, the temperature of the fatty acid-modified acrylic emulsion in the flask was adjusted to 25 ° C., 10 parts of water, 25 parts of methyltrimethoxysilane and 15 parts of phenyltrimethoxysilane were added, and stirring was continued for 1 hour. . Further, 5 parts of 3-isocyanatopropyltriethoxysilane was added and stirred at this temperature for 30 minutes. Thereafter, the temperature was raised to 80 ° C., and the reaction was conducted by stirring for 3 hours. The solid content of the resulting dispersion was measured (Note 1), and the solid content concentration was adjusted to 48% with water based on this value. An aqueous resin dispersion (A-7) in which a modified acrylic emulsion and polysiloxane were combined was obtained.

Examples 8-10
In Example 7 above, aqueous resin dispersions (A-8) to (A-10) were prepared in the same manner as in Example 7 except that the composition of the monomer emulsion and the organosilane to be added were changed to Table 1. Obtained.

Example 11
30 parts of fatty acid-modified polymerizable unsaturated monomer (a-1), 22 parts of n-butyl methacrylate, 27 parts of i-butyl methacrylate, 17 parts of 2-ethylhexyl methacrylate, 3 parts of vinyltrimethoxysilane, 1 part of methacrylic acid, To a monomer mixture of 0.5 parts of n-octyl mercaptopropionate, 10 parts of “Newcol 707SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier having a polyoxyethylene chain) and 90 parts of water are mixed. Then, stir with a disper for 15 minutes to prepare a preliminary emulsion. This preliminary emulsified liquid was subjected to a high pressure treatment of 100 MPa with a high pressure emulsifying apparatus to obtain a fine monomer dispersion having an average particle diameter of 198 nm. The monomer fine dispersion was transferred to a flask and heated to 80 ° C. An initiator aqueous solution in which 0.24 part of ammonium persulfate was dissolved in 10 parts of water was dropped into this flask over 1 hour. Thereafter, the reaction was allowed to proceed at 80 ° C. for 2 hours, cooled, adjusted to pH 7 with aqueous ammonia, and a fatty acid-modified acrylic emulsion having an average particle size of 215 nm was obtained. Next, the temperature of the fatty acid-modified acrylic emulsion in the flask was adjusted to 25 ° C., 10 parts of water, 25 parts of methyltrimethoxysilane and 15 parts of phenyltrimethoxysilane were added, and stirring was continued for 1 hour. . Thereafter, the temperature was raised to 80 ° C. and reacted for 3 hours, and the solid content of the resulting dispersion was measured (Note 1). Based on this value, the solid content concentration was adjusted to 48% with water, and the fatty acid-modified acrylic emulsion An aqueous resin dispersion (A-11) in which polysiloxane and polysiloxane were combined was obtained.

Example 12
30 parts of fatty acid-modified polymerizable unsaturated monomer (a-1), 22 parts of n-butyl methacrylate, 27 parts of i-butyl methacrylate, 17 parts of 2-ethylhexyl methacrylate, 3 parts of 3-mercaptopropyltrimethoxysilane, methacrylic acid 1 part of the monomer mixture is mixed with 10 parts of “New Coal 707SF” (trade name, anionic emulsifier having a polyoxyethylene chain, active ingredient 30%) and 90 parts of water, and stirred with a disper for 15 minutes. Create an emulsion. This preliminary emulsified liquid was subjected to a high pressure treatment of 100 MPa with a high pressure emulsifying apparatus to obtain a fine monomer dispersion having an average particle diameter of 189 nm. The monomer fine dispersion was transferred to a flask and heated to 80 ° C. An initiator aqueous solution in which 0.24 part of ammonium persulfate was dissolved in 10 parts of water was dropped into this flask over 1 hour. Thereafter, the reaction was allowed to proceed at 80 ° C. for 2 hours, cooled, and adjusted to pH 7 with aqueous ammonia to obtain a fatty acid-modified acrylic emulsion having an average particle size of 215 nm. Next, the temperature of the fatty acid-modified acrylic emulsion in the flask was adjusted to 25 ° C., 10 parts of water, 25 parts of methyltrimethoxysilane and 15 parts of phenyltrimethoxysilane were added, and stirring was continued for 1 hour. . Then, the temperature was raised to 80 ° C. and reacted for 3 hours, and the solid content of the resulting dispersion was measured (Note 1). Based on this value, the solid content concentration was adjusted to 48% with water, and fatty acid-modified acrylic An aqueous resin dispersion (A-12) in which an emulsion and polysiloxane were combined was obtained.

Example 13
In Example 12 above, an aqueous resin dispersion (A-13) was obtained in the same manner as in Example 12 except that the monomer emulsion composition and the composition of the organosilane to be added were changed to the following Table 1.

Example 14
Fatty acid-modified monomer (a-1) 30 parts, n-butyl methacrylate 22 parts, i-butyl methacrylate 27 parts, 2-ethylhexyl methacrylate 17 parts, 3-mercaptopropyltrimethoxysilane ("KBM-803", trade name) (Shin-Etsu Chemical Co., Ltd.) 3 parts, methacrylic acid 1 part monomer mixture solution, 20 parts of "X-40-9250" (Note 2) is dissolved, and "New Coal 707SF" (trade name, Japan) 12 parts of an anionic emulsifier having a polyoxyethylene chain, active ingredient 30%) and 108 parts of water are mixed and stirred with a disper for 15 minutes to prepare a preliminary emulsion. This preliminary emulsion was subjected to a high-pressure treatment of 100 MPa with a high-pressure emulsifier to obtain a fine monomer dispersion having an average particle diameter of 238 nm. The monomer fine dispersion was transferred to a flask and heated to 80 ° C. An initiator aqueous solution prepared by dissolving 0.288 parts of ammonium persulfate in 12 parts of water was dropped into this flask over 1 hour. Thereafter, the reaction was allowed to proceed at 80 ° C. for 2 hours, cooled, and adjusted to pH 7 with aqueous ammonia to obtain a fatty acrylic emulsion having an average particle size of 246 nm. Next, the temperature of the fatty acid-modified acrylic emulsion in the flask was adjusted to 25 ° C., 5 parts of methyltrimethoxysilane and 15 parts of phenyltrimethoxysilane were added, and stirring was continued for 1 hour. Then, the temperature was raised to 80 ° C. and reacted for 3 hours, and the solid content of the resulting dispersion was measured (Note 1). Based on this value, the solid content concentration was adjusted to 48% with water, and fatty acid-modified acrylic An aqueous resin dispersion (A-14) in which an emulsion and polysiloxane were combined was obtained.

Comparative Example 2
In a container, add 30 parts of fatty acid-modified polymerizable unsaturated monomer (a-1), 25 parts of n-butyl methacrylate, 27 parts of i-butyl methacrylate, 17 parts of 2-ethylhexyl methacrylate and 1 part of methacrylic acid, Cole 707SF "(trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier having a polyoxyethylene chain, 30% active ingredient) is mixed with 90 parts of water, and stirred with a disper for 15 minutes to prepare a preliminary emulsion. . This preliminary emulsion was subjected to a high pressure treatment of 100 MPa with a high pressure emulsifier to obtain a fine monomer dispersion having an average particle size of 186 nm. The monomer fine dispersion was then transferred to a flask and heated to 80 ° C. An initiator aqueous solution in which 0.24 part of ammonium persulfate was dissolved in 10 parts of water was dropped into this flask over 1 hour. Thereafter, the reaction was allowed to proceed at 80 ° C. for 2 hours, cooled, and adjusted to pH 7 with aqueous ammonia to obtain an aqueous resin dispersion (A-16) having an average particle diameter of 191 nm.

(Note 2) “X-40-9250”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy group-containing organopolysiloxane oligomer having a linear dimethylpolysiloxane skeleton and a three-dimensional polysiloxane skeleton (Note 3) “X-40-2651”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., methoxy group-containing organopolysiloxane oligomer having a three-dimensional structure polysiloxane skeleton and amino group (Note 4) “KC-89S”: trade name, Shin-Etsu Chemical Industrial company alkoxysilyl group-containing organopolysiloxane oligomer (Note 5) “X-40-9227”: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., alkoxysilyl group-containing organopolysiloxane oligomer having a methyl group and a phenyl group.

Production of aqueous resin composition Example 15
In a container, 208 parts of the 48% aqueous resin dispersion (A-1), 2.2 parts of “DICNATE 1000W” (Note 6) and 10 parts of “TEXNOL” (Note 7) are mixed and stirred to obtain an aqueous resin composition. Got.

Examples 16-30 and Comparative Examples 3-4
In Example 15 above, each aqueous resin composition was obtained in the same manner as in Example 15 except that the formulation was changed to Table 2 below.

（注６）「ＤＩＣＮＡＴＥ１０００Ｗ」：商品名、大日本インキ化学工業社製、水性金属ドライヤー、Ｃｏ含有率３．６％
（注７）「ＴＥＸＮＯＬ」：商品名、イーストマンケミカル社製、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、造膜助剤
（注８）「サイメル３２５」：商品名、日本サイテックインダストリーズ社製、メチルエーテル基、イミノ基含有メラミン樹脂、有効成分８０％、親水性メラミン樹脂。

(Note 6) “DICnate 1000W”: trade name, manufactured by Dainippon Ink & Chemicals, water-based metal dryer, Co content 3.6%
(Note 7) “TEXNOL”: trade name, manufactured by Eastman Chemical Co., Ltd., 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, film-forming aid (Note 8) “Cymel 325”: Product Name, manufactured by Nippon Cytec Industries, Inc., methyl ether group, imino group-containing melamine resin, active ingredient 80%, hydrophilic melamine resin.

Preparation of test coated plate Each aqueous resin composition was spray-coated on a steel plate to a dry film thickness of 40 μm, dried under various conditions in the table, and finished, water-resistant and accelerated weather-resistant. It used for the test. The results are shown in Table 2.
(* 1) Finishability:
Each test coated plate was visually evaluated.
○: Finishing property is very good, Δ: Finishing property is slightly good, X: Finishing property is poor (* 2) Water resistance:
Each obtained test coating plate was immersed in a constant temperature water bath at room temperature of 20 ° C. for 7 days, and the state of the coating film was visually observed.
◎: No abnormality ○: Slight swelling and discoloration, but no practical trouble △: Swelling and discoloration, practical difficulty ×: Significant swelling and discoloration (* 3) Accelerated weather resistance:
Each of the obtained test coated plates was subjected to a 3000-hour accelerated weather resistance test for a sunshine weather meter, and the state of the coating film was visually observed.
◎: No abnormality ○: Slight swelling, discoloration, gloss change, peeling, etc. are observed, but there is no practical problem. Δ: Swelling, discoloration, gloss change, peeling, etc. are observed. ×: Buffing, discoloration, gloss change, peeling (* 4) Curability:
The free film was peeled off from each test coated plate obtained above, cut to a size of 4 × 4 cm, and immersed in acetone for 6 hours under reflux conditions. The coating film extraction residue was calculated from the coating film weight before and after extraction.
Paint film extraction residue (%) = (weight of film after extraction / weight of film before extraction) × 100 (%)
(* 5) An outdoor stain-resistant slate plate (90 x 300 x 6 mm) with "VP sealer white" (manufactured by Kansai Paint Co., Ltd., solvent type sealer) dried with a roller so that the coating amount is 100 g / m ^2. As a coated plate, each of the aqueous resin compositions of Examples 15 to 20, 23 to 30 and Comparative Examples 3 to 4 was applied by spraying twice so that the coating amount was 150 g / m ² , and 20 ° C. And dried for 7 days to obtain a test plate for resistance to outdoor contamination. Each test plate was subjected to an outdoor exposure test for 4 months with the coating surface tilted 30 degrees upward from the horizontal plane toward the south surface in Hiratsuka city, and the dirt after the test was visually evaluated.
◎: Dirt is hardly seen ○: Dirt is slightly seen Δ: Dirty x: Dirt is remarkable

Claims (15)

(A) In the presence of an aqueous fatty acid-modified resin dispersion in which a resin containing a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) as a copolymerization component is dispersed in an aqueous medium. (B) A method for producing polysiloxane composite polymer particles, which comprises adding an alkoxysilyl group-containing organosilane and subjecting the organosilane (B) to a condensation polymerization reaction. The aqueous fatty acid-modified resin dispersion (A) has an average particle diameter of a mixture (I) containing a monomer component comprising a fatty acid-modified polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b) in an aqueous medium. The production method according to claim 1, which is obtained by finely dispersing the emulsion so as to be 500 nm or less and polymerizing the resulting emulsion. The production method according to claim 1 or 2, wherein the fatty acid-modified polymerizable unsaturated monomer (a) is a reaction product of a fatty acid and an epoxy group-containing polymerizable unsaturated monomer or a hydroxyl group-containing polymerizable unsaturated monomer. The production method according to any one of claims 1 to 3, wherein the other polymerizable unsaturated monomer (b) contains an alkoxysilyl group-containing polymerizable unsaturated monomer. An alkoxysilyl group-containing organosilane (B)
_{^{(R 1) n -Si- (OR}} 2) 4-n
Wherein R ¹ is the same or different and represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ² is the same or different and may be a hydrogen atom or substituted. 5. An organic group having 1 to 10 carbon atoms, wherein n is an integer of 0 to 3.) and at least one selected from the group of condensates of the organosilane. The manufacturing method of any one of these. The aqueous fatty acid-modified resin dispersion (A) and the alkoxysilyl group-containing organosilane (B) each have a chemically functionally complementary complementary functional group other than the alkoxysilyl group and are grafted. Item 6. The manufacturing method according to any one of Items 1 to 5. The production method according to claim 6, wherein the combination of complementary functional groups is a hydroxyl group and an isocyanate group, a carboxyl group and an epoxy group, or an amino group and an epoxy group. Mixture (I) is
HSCH ₂ CH ₂ CH ₂ SiR ³ _m (OR ⁴ ) _3-m (2)
(Wherein R ³ is the same or different and is an organic group having 1 to 8 carbon atoms, R ⁴ is the same or different and is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, m Is an integer of 0 to 3.) The production method according to any one of claims 2 to 7, further comprising a mercapto group-containing organosilane (C) represented by: The production method according to any one of claims 2 to 8, wherein the mixture (I) further contains an alkoxysilyl group-containing organosilane (D). Polysiloxane composite polymer particles obtained by the production method according to any one of claims 1 to 9. An aqueous resin composition containing the polysiloxane composite polymer particles according to claim 10. The aqueous resin composition according to claim 11, further comprising an isocyanate curing agent and / or a melamine curing agent (E). An aqueous coating composition containing the aqueous resin composition according to claim 11 or 12. A method of forming a coating film, comprising applying the aqueous coating composition according to claim 13 to a surface to be coated. The coated article obtained by the coating-film formation method of Claim 14.