JP6418437B2 - Aqueous composite resin composition and coating agent using the same - Google Patents

Description

  The present invention relates to an aqueous resin composition that can be used for various applications including a coating agent.

  In recent years, highly functional materials that combine the characteristics of inorganic and organic materials have been widely developed in various industrial fields. Inorganic materials have excellent durability such as weather resistance, heat resistance, and scratch resistance. It is generally known that is rich in flexibility and workability. Among these, an aqueous resin in which an inorganic material and an organic material are combined has been proposed (for example, see Patent Document 1). This water-based resin coating film has high weather resistance, but when higher durability is required, it is essential to use a curing agent, and it has been pointed out that workability is inferior. . Further, the film-forming property deteriorates with time, and there is a problem that the appearance of the obtained coating film is inferior when applied after long-term storage.

  Therefore, a material capable of forming a coating film excellent in durability with a one-component curing specification having excellent long-term storage stability and workability has been demanded.

JP-A-11-279408

  The problem to be solved by the present invention is an aqueous composite resin composition capable of forming a coating film having excellent durability such as weather resistance and water resistance with a one-part curing specification having excellent long-term storage stability and workability. The present invention provides a coating agent using the aqueous composite resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have an aqueous solution containing a composite resin obtained through a step of polymerizing a vinyl monomer mixture in a polysiloxane composite resin aqueous dispersion and an aqueous medium. The present inventors have found that the composite resin composition can form a coating film having excellent long-term storage stability and durability such as weather resistance and water resistance, and completed the present invention.

  That is, the present invention relates to an aqueous composite resin composition comprising a composite resin (C) obtained by polymerizing a vinyl monomer mixture (B) in an aqueous dispersion of a polysiloxane composite resin (A) and an aqueous medium. An aqueous composite resin composition characterized in that the polysiloxane composite resin (A) is a composite resin in which a vinyl polymer (a1) having a hydrophilic group and a polysiloxane (a2) are combined. About. The present invention also relates to a coating agent comprising the aqueous composite resin composition.

  The aqueous composite resin composition of the present invention has good adhesion to various base materials such as metal base materials, plastic base materials, inorganic base materials, fibrous base materials, cloth materials, paper, and wood base materials. Therefore, it can be used for coating agents and adhesives. In particular, since the aqueous composite resin composition of the present invention can form a coating film excellent in durability and weather resistance, it is suitably used as a primer layer forming coating agent or a top coating layer forming coating agent for various substrates. can do.

  The aqueous composite resin composition of the present invention contains a composite resin (C) obtained through a step of polymerizing the vinyl monomer mixture (B) in an aqueous dispersion of the polysiloxane composite resin (A) and an aqueous medium. In the aqueous composite resin composition, the polysiloxane composite resin (A) is a composite resin in which a vinyl polymer (a1) having a hydrophilic group and a polysiloxane (a2) are bonded.

  First, an aqueous dispersion of the polysiloxane composite resin (A) will be described. The polysiloxane composite resin (A) is obtained by bonding a vinyl polymer (a1) having a hydrophilic group and a polysiloxane (a2).

  The polysiloxane composite resin (A) may be partially dissolved in an aqueous medium, but the polysiloxane composite resin (A) dispersed in the aqueous medium has an average particle diameter of 10 to 500 nm. However, it is preferable when forming a coating film excellent in weather resistance and water resistance. Here, the average particle diameter means a value measured by a method for obtaining a particle size distribution by a measurement principle for detecting dynamic scattered light of particles.

  Moreover, when the said polysiloxane composite resin (A) forms the coating film excellent in durability and a weather resistance, 15-85 mass% polysiloxane (a2) with respect to the whole polysiloxane composite resin (A). It preferably has a derived structure.

  In addition, the mass ratio of the structure derived from the polysiloxane (a2) is generated by a hydrolysis condensation reaction of the polysiloxane (a2) or the like based on the charging ratio of the raw materials used for the production of the polysiloxane composite resin (A). It is a value calculated in consideration of the formation of by-products such as methanol and ethanol.

  The polysiloxane composite resin (A) must have a hydrophilic group in order to stably disperse in an aqueous medium.

  It is essential that the hydrophilic group is present in the vinyl polymer (a1) having the hydrophilic group that mainly constitutes the outer layer of the polysiloxane composite resin (A).

  As the hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used, and among these, an anionic group is preferably used.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used, and among them, a carboxylate group partially or wholly neutralized with a basic compound or the like Is preferable for producing a composite resin having good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. Examples thereof include metal basic compounds.

  When carboxylate groups are used as the anionic group, they are present in the range of 50 to 1000 mmol / kg with respect to the whole polysiloxane composite resin (A), and thus good water of the polysiloxane composite resin (A). It is preferable for maintaining the dispersion stability.

  Moreover, as said cationic group, a tertiary amino group etc. can be used, for example. Examples of the acid that can be used for neutralizing a part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like. You may use organic sulfonic acid and inorganic acids, such as hydrochloric acid, a sulfuric acid, orthophosphoric acid, orthophosphorous acid, individually or in combination of 2 or more types.

  Examples of the quaternizing agent that can be used for quaternizing a part or all of the tertiary amino group include dialkyl sulfuric acid such as dimethyl sulfuric acid and diethyl sulfuric acid, methyl chloride, ethyl chloride, Alkyl halides such as benzyl chloride, alkyls such as methyl methanesulfonate and methyl paratoluenesulfonate, or epoxy compounds such as ethylene oxide, propylene oxide, and epichlorohydrin may be used alone or in combination of two or more.

  Examples of the nonionic group include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Groups can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

  As the polysiloxane composite resin (A), the bond between the vinyl polymer (a1) and the polysiloxane (a2) is a hydrolyzable silyl group and / or silanol group possessed by the vinyl polymer (a1). It is preferable that the polysiloxane (a2) is formed by a reaction with a hydrolyzable silyl group and / or a silanol group in order to form a coating film having superior durability and weather resistance.

  Next, the vinyl polymer (a1) having the hydrophilic group constituting the polysiloxane composite resin (A) will be described.

  As the vinyl polymer (a1) having a hydrophilic group, those having a number average molecular weight of 3,000 to 100,000 are preferably used, and those having a number average molecular weight of 5,000 to 25,000 are used. Is more preferable for forming a coating film excellent in durability and weather resistance.

  The vinyl polymer (a1) having a hydrophilic group must have a hydrophilic group in order to impart water dispersibility to the polysiloxane composite resin (A). The hydrophilic group is preferably present in the range of 50 to 1,000 mmol / kg with respect to the entire vinyl polymer (a1) having the hydrophilic group, in order to impart better water dispersibility.

  As the vinyl polymer (a1) having a hydrophilic group, for example, those produced by polymerizing various vinyl monomers in the presence of a polymerization initiator can be used.

  The hydrophilic group of the vinyl polymer (a1) having a hydrophilic group is obtained by polymerizing, for example, a vinyl monomer having a carboxyl group, a vinyl monomer having a tertiary amino group, or the like. By neutralizing, it can introduce | transduce into the vinyl polymer (a1) which has the said hydrophilic group easily.

  Examples of the vinyl monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid and fumaric acid; maleic anhydride , Anhydrides of unsaturated polycarboxylic acids such as itaconic anhydride; anhydrides of unsaturated monocarboxylic acids such as acrylic acid and methacrylic anhydride; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; and acetic acid and propionic acid Acid anhydrides with saturated carboxylic acids such as benzoic acid; monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate Various monoesters (half-esters) of saturated dicarboxylic acids such as, and saturated monohydric alcohols; adipine Monovinyl esters of saturated dicarboxylic acids such as monovinyl and monovinyl succinate; containing anhydrides of saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, and hydroxyl groups bonded to carbon atoms Addition reaction product with a vinyl monomer; various monomers obtained by addition reaction of the carboxyl group-containing monomer and a lactone compound, and the like can be easily introduced into a vinyl polymer. Therefore, unsaturated carboxylic acids such as (meth) acrylic acid are preferred. These monomers may be used alone or in combination of two or more.

Examples of the vinyl monomer having a tertiary amino group include 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3 -(Meth) acrylic acid ester having a tertiary amino group such as dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, N- [2- (meth) acryloyloxy] ethylmorpholine; vinylpyridine, Aromatic vinyl monomers having a tertiary amino group such as N-vinylcarbazole, N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide N- (2-di-n-propylamino) ethyl (meth) acrylate (Meth) acrylamide having tertiary amino group such as ruamide; Crotonic acid amide having tertiary amino group such as N- (2-dimethylamino) ethylcrotonic acid amide, N- (4-dimethylamino) butylcrotonic acid amide A vinyl ether having a tertiary amino group such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, and the like. These monomers may be used alone or in combination of two or more.

  The vinyl polymer (a1) having a hydrophilic group may have other functional groups as necessary in addition to the hydrophilic group as described above. Examples include hydrolyzable silyl groups, silanol groups, amino groups, imino groups, and hydroxyl groups that can react with siloxane (a2). Among them, a hydrolyzable silyl group is a coating film that has excellent long-term weather resistance. Since it can form, it is preferable.

  The hydrolyzable silyl group that the vinyl polymer (a1) having a hydrophilic group may have is a functional group in which the hydrolyzable group is directly bonded to a silicon atom. For example, the following general formula (I ).

（式中、Ｒ^１はアルキル基、アリール基またはアラルキル基等の１価の有機基を、Ｒ^２はハロゲン原子、アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基またはアルケニルオキシ基である。また、ｘは０〜２の整数である。）

(Wherein R ¹ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, R ² is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group, amide) A group, an aminooxy group, an iminooxy group or an alkenyloxy group, and x is an integer of 0 to 2.)

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, hexyl, and isohexyl groups. It is done.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

  Examples of the acyloxy group include acetoxy, propanoyloxy, butanoyloxy, phenylacetoxy, acetoacetoxy, and the like. Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like. Examples of the group include an allyloxy group, a 1-propenyloxy group, and an isopropenyloxy group.

R ² is preferably independently an alkoxy group, since it is easy to remove a leaving component such as the general formula R ² OH that can be generated by hydrolysis.

  The silanol group which the vinyl polymer (a1) having a hydrophilic group may have is a functional group in which a hydroxyl group is directly bonded to a silicon atom, and the hydrolyzable silyl group described above is mainly hydrolyzed. It is a functional group generated by decomposition.

  The hydrolyzable silyl group that the vinyl polymer (a1) having the hydrophilic group may have is obtained by polymerizing a vinyl monomer having a hydrolyzable silyl group, for example. It can be easily introduced into the vinyl polymer (a1).

  Examples of the vinyl monomer having a hydrolyzable silyl group include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meth) acryloyloxypropylmethyl. Dimethoxysilane or the like can be used, and among them, 3- (meth) acryloyloxypropyltrimethoxysilane is preferably used.

  Moreover, as a raw material of the vinyl polymer (a1) having the hydrophilic group, the vinyl monomer having the carboxyl group, the vinyl monomer having a tertiary amino group, and the vinyl monomer having a hydrolyzable silyl group. Other vinyl monomers other than the body can be used. Examples of other vinyl monomers include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Acrylic ester compound; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol- Vinyl monomers having a hydroxyl group such as polypropylene glycol (meth) acrylate and glycerol mono (meth) acrylate; methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene Len glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolyethyleneglycol-polypropyleneglycol (meth) acrylate phenoxypolyethyleneglycol-polypropyleneglycol (meth) acrylate, etc. are terminated with an alkoxy group or Vinyl monomer having a polyoxyalkylene group sealed with a phenoxy group; Vinyl monomer having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate; N-methylaminoethyl (meth) Vinyl monomer having secondary amino group such as acrylate; Vinyl monomer having group having basic nitrogen atom such as vinyl monomer having primary amino group such as aminomethyl acrylate Vinyl monomers having fluorine atoms such as 2,2,2-trifluoroethyl (meth) acrylate; vinyl ester compounds such as vinyl acetate; vinyl ether compounds such as methyl vinyl ether; unsaturated carboxylic acids such as (meth) acrylonitrile; Nitrile compounds; vinyl compounds having an aromatic ring such as styrene; α-olefin compounds such as isoprene; vinyl monomers having an epoxy group such as glycidyl (meth) acrylate; vinyls having an amide group such as (meth) acrylamide Monomer; Vinyl monomer having a methylolamide group such as N-methylol (meth) acrylamide and its alkoxy product; Vinyl monomer having an aziridinyl group such as 2-aziridinylethyl (meth) acrylate; ) Isocyanates such as acryloyl isocyanate Monomer having a group and / or blocked isocyanate group; vinyl monomer having an oxazoline group such as 2-isopropenyl-2-oxazoline; vinyl having a cyclopentenyl group such as dicyclopentenyl (meth) acrylate Monomer; vinyl monomer having a carbonyl group such as acrolein; vinyl monomer having an acetoacetyl group such as acetoacetoxyethyl (meth) acrylate; (meth) acrylic acid, maleic acid, or a half ester thereof; One or more monomers having a carboxyl group such as these salts can be used.

  Examples of the polymerization initiator that can be used for producing the vinyl polymer (a2) include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, and 4,4′-azobis ( An azo initiator such as 4-cyanovaleric acid) or 2,2′-azobis (2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid.

  Examples of the persulfate that is a representative of the polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Specific examples of the organic peroxide include benzoyl peroxide. , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxyesters such as laurate and t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, paramentane hydroperoxide, and t-butyl hydroperoxide can be used.

  The polymerization initiator may be used in an amount that allows the polymerization to proceed smoothly, but should be 10% by mass or less based on the total amount of vinyl monomers used in the production of the vinyl polymer (a2). Is preferred.

  Next, the polysiloxane (a2) constituting the polysiloxane composite resin aqueous dispersion (A) will be described.

  The polysiloxane (a2) has a chain structure composed of a silicon atom and an oxygen atom, and has a hydrolyzable silyl group, a silanol group or the like as required. Examples of the polysiloxane (a2) include a polysiloxane having one or more structures selected from the group consisting of the following general formulas (II) and (III), and an alkyl group having 1 to 3 carbon atoms. A reaction product with a condensate of a certain alkyltrialkoxysilane is exemplified.

（一般式（Ｉ）及び（ＩＩ）中のＲ^１はケイ素原子に結合した炭素原子数が４〜１２の有機基、Ｒ^２及びＲ^３は、それぞれ独立にメチル基またはエチル基を表す。）

(R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ each independently represents a methyl group or an ethyl group.)

  The hydrolyzable silyl group is an atomic group in which the hydrolyzable group is directly bonded to the silicon atom. For example, the hydrolyzable silyl group is represented by the general formula (in the description of the vinyl polymer (a1) having the hydrophilic group ( Those having a structure as shown in I) can be used.

  The hydrolyzable group is capable of forming a hydroxyl group under the influence of water. For example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group Group, iminooxy group, alkenyloxy group and the like, among which an alkoxy group and a substituted alkoxy group are preferable.

  The silanol group indicates an atomic group in which a hydroxyl group is directly bonded to the silicon atom, and is formed when the hydrolyzable silyl group is hydrolyzed.

  Moreover, as said polysiloxane (a2), what has alkyl groups, such as a methyl group, a phenyl group, etc. other than what was mentioned above as needed can be used, for example, polysiloxane (a2 1 type selected from the group consisting of an aromatic cyclic structure such as a phenyl group, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. In order to maintain good water dispersion stability of the aqueous composite resin composition, it is more preferable to use the above-mentioned ones that are directly bonded.

  As said polysiloxane (a2), what is obtained by hydrolyzing and condensing the silane compound mentioned later completely or partially can be used, for example.

  Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, and phenyl. Organotrialkoxysilanes such as trimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloyloxypropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxy Diorganodialkoxysilanes such as silane, diphenyldimethoxysilane, methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane Compound; various chlorosilane compounds such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or diphenyldichlorosilane, and the like The partial hydrolysis-condensation product can be used, and among them, organotrialkoxysilane and diorganodialkoxysilane are preferably used. These silane compounds may be used alone or in combination of two or more.

  The polysiloxane (a2) is preferably formed through a two-step reaction process in the process for producing the polysiloxane composite resin (A). Specifically, a polysiloxane structure is formed by reacting a hydrolyzable group or the like of the vinyl polymer (a1) with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then the reaction. By reacting the product with a condensate such as methyltrimethoxysilane or ethyltrimethoxysilane, a structure composed of polysiloxane (a2) can be formed. Thereby, the aqueous composite resin composition which can form the coating film excellent in water resistance and a weather resistance further can be obtained.

  Next, the manufacturing method of the water dispersion of the polysiloxane composite resin (A) used by this invention is demonstrated. The method for producing an aqueous dispersion of a polysiloxane composite resin (A) includes a step of producing a polysiloxane composite resin (A) and a step of dispersing the polysiloxane composite resin (A) in an aqueous medium.

  First, the process for producing the polysiloxane composite resin (A) will be described.

  The polysiloxane composite resin (A) can be produced, for example, by the following steps (I) to (II).

  The step (I) is a step of obtaining an organic solvent solution of the vinyl polymer (a1) by polymerizing the vinyl monomer in the presence of the polymerization initiator in an organic solvent.

  Such a reaction is performed, for example, by sequentially or collectively supplying the vinyl monomer in an organic solvent containing a polymerization initiator, and then performing stirring at a temperature of 20 to 120 ° C. for about 0.5 to 24 hours. Is preferred.

  In the step (II), a reactive functional group such as a hydrolyzable silyl group possessed by the vinyl polymer (a1) and a hydrolysis possessed by the silane compound under an organic solvent solution of the vinyl polymer (a1). Polysiloxane composite resin (A) in which a vinyl polymer (a1) and a polysiloxane (a2) are bonded together by a reaction with a reactive silyl group or a silanol group and a hydrolysis condensation reaction between the silane compounds. This is a step of obtaining an organic solvent solution.

  In the reaction, for example, following the step (I), the silane compound capable of forming the polysiloxane (a3) is sequentially supplied or collectively supplied into the organic solvent solution of the vinyl polymer (a2), and then Under stirring, it is preferably carried out in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

  The step (II) preferably further undergoes a two-step reaction step. Specifically, the step of reacting the hydrolyzable silyl group or silanol group of the vinyl polymer (a1) with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then the reaction product And a step of reacting a methyltrialkoxysilane such as methyltrimethoxysilane or ethyltrimethoxysilane and a condensate obtained by condensing ethyltrialkoxysilane in advance. By performing the structure formation of the polysiloxane (a2) in the above-described two steps, an aqueous composite resin composition capable of forming a coating film having further excellent durability can be obtained.

  The organic solvent solution of the polysiloxane composite resin (A) obtained by the above steps (I) to (II) is preferably made aqueous by the following step (III).

  Step (III) is, for example, a step of neutralizing the hydrophilic group of the polysiloxane composite resin (A) following the step (II) and dispersing the neutralized product in an aqueous medium.

  Neutralization of the hydrophilic group is not necessarily performed, but is preferably performed from the viewpoint of improving the water dispersion stability of the polysiloxane composite resin (A). In particular, when the hydrophilic group is an anionic group such as a carboxyl group or a sulfonic acid group, all or a part thereof is neutralized with a basic compound to form a carboxylate group or a sulfonate group. Is preferable for further improving the water dispersion stability.

  The neutralization can be performed, for example, by sequentially or collectively supplying a basic compound or the like into the organic solvent solution of the polysiloxane composite resin (A) and stirring.

  After the neutralization, an aqueous medium is supplied into the organic solvent solution of the neutralized product of the polysiloxane composite resin (A), and then the organic solvent is removed, whereby the polysiloxane composite resin (A ) Aqueous dispersion.

  The removal of the organic solvent can be performed, for example, by distillation.

  Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohol compounds such as methanol, ethanol, n- and isopropanol; ketone compounds such as acetone and methyl ethyl ketone; polyalkylene glycol compounds such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ether compounds; lactam compounds such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  Next, the vinyl monomer mixture (B) will be described. As a vinyl monomer contained in this vinyl monomer mixture (B), what was illustrated as a vinyl monomer which can be used when manufacturing the said vinyl polymer (a1) is mentioned, for example.

  Since the vinyl monomer mixture (B) improves the water dispersibility of the aqueous composite resin composition of the present invention, polyoxyethylene mono (meth) acrylate, polyoxyethylene-polyoxypropylene (meth) acrylate, Methoxypolyoxyethylene (meth) acrylate, ethoxypolyoxyethylene (meth) acrylate, phenoxypolyoxyethylene (meth) acrylate, methoxypolyoxyethylene-polyoxypropylene (meth) acrylate, phenoxypolyoxyethylene-polyoxypropylene (meta It is preferable to contain a vinyl monomer having a polyoxyethylene group such as acrylate.

  In addition, the vinyl monomer mixture (B) improves the water dispersibility of the aqueous composite resin composition of the present invention and the weather resistance of the resulting coating film, so that 3- (meth) acryloyloxypropyltrimethoxy is improved. It is preferable to contain a vinyl monomer having a hydrolyzable silyl group such as silane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meth) acryloyloxypropylmethyldimethoxysilane.

  Next, the composite resin (C) will be described. This composite resin (C) is obtained through a step of polymerizing the vinyl monomer mixture (B) in an aqueous dispersion of the polysiloxane composite resin (A).

  Examples of the step include a method in which the vinyl monomer mixture (B) and the polymerization initiator are sequentially or collectively supplied into the polysiloxane composite resin aqueous dispersion (A) to cause a polymerization reaction.

  When supplying the vinyl monomer mixture (B), there are a method of supplying the vinyl monomer mixture (B) as it is, a method of supplying the vinyl monomer mixture (B) as an emulsion, and the like. Can be mentioned.

  Examples of the emulsifier when the vinyl monomer mixture (B) is used as an emulsion include nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene copolymer, Alkyl sulfate salt, alkyl benzene sulfonate, polyoxyethylene alkyl phenyl ether sulfonate, polyoxyethylene distyrenated phenyl ether sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate And anionic emulsifiers such as quaternary ammonium salts. Among these, it is preferable to use an emulsifier having a reactive double bond because the water resistance and weather resistance of the resulting coating film are improved. These emulsifiers may be used alone or in combination of two or more.

  These emulsifiers are preferably used in an amount of 15 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (B) monomer.

  Examples of the polymerization initiator include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis ( An azo initiator such as 2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid.

  Examples of the persulfate that is a representative of the polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Specific examples of the organic peroxide include benzoyl peroxide. , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxyesters such as laurate and t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, paramentane hydroperoxide, and t-butyl hydroperoxide can be used.

  The polymerization initiator may be used in such an amount that the polymerization proceeds smoothly, but it should be 10% by mass or less with respect to the total amount of vinyl monomers used in the production of the vinyl polymer (a1). Is preferred.

  Moreover, it is preferable to perform the said polymerization reaction in the range of 20-100 degreeC for about 0.5 to 24 hours, stirring.

  Since the storage stability of the aqueous composite resin composition of the present invention and the water resistance and weather resistance of the resulting coating are improved, the mass of the polysiloxane composite resin (A) and the vinyl monomer mixture (B) is improved. The ratio [(A) / (B)] is preferably in the range of 10/90 to 80/20, more preferably in the range of 15/85 to 75/25.

  Moreover, since the water resistance and weather resistance of the coating film obtained improve, the mass% of the polysiloxane structure in the composite resin (C) is preferably in the range of 3 to 60%, and in the range of 5 to 50%. More preferred.

  The aqueous composite resin composition of the present invention contains the composite resin (C) and an aqueous medium, and this aqueous medium is used for producing an aqueous dispersion of the polysiloxane composite resin (A). What was illustrated as a possible aqueous medium is mentioned, From the point of safety | security and the load with respect to an environment, only water or a mixture with water and the organic solvent mixed with water is preferable, and only water is especially preferable.

  The aqueous composite resin composition of the present invention suppresses a sudden increase in viscosity during production, and from the viewpoint of improving the productivity of the aqueous composite resin composition, ease of coating, drying properties, etc. It is preferable to have a non-volatile content of 20 to 65% by mass, and more preferably in the range of 30 to 60% by mass.

  The aqueous composite resin composition of the present invention can contain a thermosetting resin as necessary. Examples of such thermosetting resins include vinyl resins, polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, or modified resins thereof.

  In the aqueous composite resin composition of the present invention, various inorganic particles such as clay mineral, metal, metal oxide, and glass can be used as necessary. Examples of the metal include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, and metal oxides thereof.

  The aqueous composite resin composition of the present invention includes a photocatalytic compound, inorganic pigment, organic pigment, extender pigment, wax, surfactant, stabilizer, flow regulator, dye, leveling agent, rheology control agent, if necessary. Various additives such as an ultraviolet absorber, an antioxidant, and a plasticizer can be used.

  Since the aqueous composite resin composition of the present invention is excellent in storage stability, it can be used for various applications such as a coating agent and an adhesive. Especially, since the aqueous composite resin composition of the present invention can form a coating film excellent in durability and weather resistance, it is preferably used for a coating agent. A coating agent for forming a top layer or a coating agent for forming a primer layer. It is more preferable to use it.

  As a base material which can apply | coat the said coating agent and can form a coating film, an inorganic base material, a metal base material, a plastic base material, a glass base material, paper, a wood base material, a fiber base material etc. are mentioned, for example.

  The coating agent of the present invention forms, for example, a coating film excellent in appearance, durability, weather resistance and the like after the exposure test by directly applying the coating agent to the surface of the substrate, followed by drying and curing. can do.

  A coated product can be obtained by applying and curing the coating agent on various substrates as described above. At that time, (1) the coating agent is directly applied to the substrate, (2) the primer coating is applied on the substrate in advance, and then the coating agent is applied as the top coating. (3) the substrate A coated product can be obtained by a coating method such as applying the coating agent as a base coat and then applying another top coat to form a coating film.

  Examples of the method for applying the coating agent of the present invention include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, and electrodeposition coating.

  Moreover, when obtaining the coating material which has the coating film which consists of the said coating agent with the coating method of said (2) or (3), conventionally known acrylic resin-type paint and polyester resin as undercoat paint and topcoat paint Paints, alkyd resin paints, epoxy resin paints, fatty acid-modified epoxy resin paints, silicone resin paints, polyurethane resin paints, and the like can be used.

  The method for drying and curing may be a method of curing for about 1 to 10 days at room temperature. From the viewpoint of rapidly curing, the temperature is 50 to 250 ° C. for 1 to 600 seconds. A method of heating to a certain extent is preferred. Moreover, when using the plastic base material which deform | transforms and discolors easily at comparatively high temperature, it is preferable to perform curing at comparatively low temperature of about 30-100 degreeC.

  The film thickness of the coating film formed using the coating agent of the present invention can be set to 0.5 to 1,000 μm depending on the use of the substrate.

  As an article having a coating film formed by using the coating agent of the present invention by the method as described above, for example, interior and exterior materials of buildings such as outer walls, roofs, glass, decorative boards; soundproof walls, drainage grooves Civil engineering materials such as: Housings for home appliances such as TVs, refrigerators, washing machines, and air conditioners; Housings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game consoles; Housings for OA equipment such as printers and facsimiles Body: Interior and exterior materials of various vehicles such as automobiles and railway vehicles; industrial machinery and the like.

  Next, the present invention will be specifically described with reference to examples and comparative examples.

Synthesis Example 1: Production of methyltrimethoxysilane condensate (a2′-1)
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen gas inlet, 1,421 parts by mass of methyltrimethoxysilane (hereinafter abbreviated as “MTMS”) was charged, and the temperature was raised to 60 ° C. Warm up. Next, a mixture of 0.17 parts by mass of iso-propyl acid phosphate (“A-3” manufactured by Sakai Chemical Co., Ltd.) and 207 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, and then 80 ° C. The mixture was stirred at temperature for 4 hours to cause hydrolysis and condensation reaction.
The condensate obtained by the above hydrolysis condensation reaction is subjected to a temperature of 40 to 60 ° C. and a reduced pressure of 40 to 1.3 kPa (the reduced pressure condition at the start of the distillation of methanol is 40 kPa, and finally becomes 1.3 kPa) (Hereinafter the same shall apply)), and the methanol and water produced in the above reaction process are removed to remove the MTMS condensate (a2′-1) having a number average molecular weight of 1,000. 1,000 parts by weight of a liquid (70% by mass of active ingredient) was obtained.
The effective component is a value obtained by dividing the theoretical yield (parts by mass) when all the methoxy groups of silane monomers such as MTMS undergo a condensation reaction by the actual yield (parts by mass) after the condensation reaction [the methoxy of the silane monomer. The theoretical yield when all the groups undergo a condensation reaction (parts by mass) / the actual yield after the condensation reaction (parts by mass)] is calculated.

(Synthesis Example 2: Production of aqueous dispersion of polysiloxane composite resin (A-1))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 111 parts by mass of isopropyl alcohol (hereinafter abbreviated as “IPA”), phenyltrimethoxysilane (hereinafter referred to as “PTMS”). (Abbreviated) 54 parts by mass and 32 parts by mass of dimethyldimethoxysilane (hereinafter abbreviated as “DMDMS”) were charged and heated to 80 ° C.
Next, 112 parts by mass of methyl methacrylate (hereinafter abbreviated as “MMA”), 92 parts by mass of butyl methacrylate (hereinafter abbreviated as “BMA”), and butyl acrylate (hereinafter abbreviated as “BA”) at the same temperature. .) 52 parts by mass, acrylic acid (hereinafter abbreviated as “AA”) 16 parts by mass, 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as “MPTS”) 8 parts by mass, IPA 51 parts by mass And a mixture containing 14 parts by mass of tert-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as “TBPEH”) is dropped into the reaction vessel over 4 hours. The organic solution of the acrylic polymer (a1-1) having a number average molecular weight of 10,200 having a carboxyl group and a hydrolyzable silyl group by reacting at a temperature for 20 hours. An agent solution was obtained.
Next, a mixture of 0.9 parts by mass of iso-propyl acid phosphate (“A-3” manufactured by Sakai Chemical Co., Ltd.) and 24 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 5 hours. The composite resin in which the hydrolyzable silyl group possessed by the acrylic polymer (a1-1) and the hydrolyzable silyl group and silanol group possessed by the polysiloxane derived from PTMS and DMDMS are bonded by hydrolytic condensation reaction. A liquid containing was obtained. Next, 11 parts by mass of triethylamine (hereinafter abbreviated as “TEA”) was added to this solution to obtain a neutralized product obtained by neutralizing the carboxyl group in the composite resin, and then obtained in Synthesis Example 1. A hydrocondensation reaction was performed by adding 93 parts by mass of a liquid containing MTMS condensate (a2′-1) (active ingredient 70% by mass) and further adding 570 parts by mass of deionized water. As a result, a composite resin composition in which an MTMS condensate (a2′-1) was further bonded to the composite resin was obtained.
Subsequently, the aqueous dispersion 1 of the polysiloxane composite resin (A-1) whose non volatile matter is 40 mass% by distilling on the conditions similar to the synthesis example 4 for 4 hours, and removing the produced | generated methanol, an organic solvent, and water. 1,000 parts by mass were obtained.

(Synthesis Example 3: Production of aqueous dispersion of polysiloxane composite resin (A-2))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 30 parts by mass of IPA, 135 parts by mass of PTMS and 80 parts by mass of DMDMS were charged and heated to 80 ° C.
Subsequently, a mixture containing 20 parts by mass of MMA, 33 parts by mass of BMA, 38 parts by mass of BA, 6 parts by mass of AA, 3 parts by mass of MPTS, 18 parts by mass of IPA and 5 parts by mass of TBPEH at the same temperature is added into the reaction vessel. The solution was dropped in 4 hours, and after completion of the dropping, the reaction was further carried out at the same temperature for 20 hours to prepare an organic solvent solution of an acrylic polymer (a1-2) having a carboxyl group and a hydrolyzable silyl group and having a number average molecular weight of 10,200. Got.
Next, a mixture of 2 parts by mass of iso-propyl acid phosphate (“A-3” manufactured by Sakai Chemical Co., Ltd.) and 60 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 5 hours to add water. Contains a composite resin in which the hydrolyzable silyl group possessed by the acrylic polymer (a1-2) and the hydrolyzable silyl group and silanol group possessed by the polysiloxane derived from PTMS and DMDMS are bonded by a decomposition condensation reaction. A liquid to be obtained was obtained.
Next, 233 parts by mass of a liquid (active ingredient 70% by mass) containing the MTMS condensate (a2′-1) obtained in Synthesis Example 1 and 60 parts by mass of deionized water were added to this liquid at the same temperature. After stirring for 5 hours to cause a hydrolytic condensation reaction and distilling under the same conditions as in Synthesis Example 1, by mixing 20 parts by mass of TEA and 455 parts by mass of deionized water, a polysiloxane composite having a nonvolatile content of 40% by mass 1,000 parts by mass of an aqueous dispersion of resin (A-2) was obtained.

(Synthesis Example 4: Preparation of acrylic resin aqueous dispersion (W-1))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 360 parts by mass of deionized water was charged and heated to 80 ° C.
Next, at the same temperature, 70 parts by mass of deionized water, 35 parts by mass of 25% aqueous solution of polyoxyethylene-1- (allyloxymethyl) alkylsulfate ammonium salt (Aqualon KH-1025 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Polymeric monomer emulsion composed of 115 parts by mass of MMA, 167 parts by mass of 2EHA, 175 parts by mass of CHMA, 1 part by mass of MPTS, and 30 parts by mass of polyoxyethylene monomethacrylate (“Blenmer PME-400” manufactured by NOF Corporation) An aqueous solution in which 1 part by mass of sodium persulfate was dissolved in 40 parts by mass of deionized water was added dropwise over 5 hours.
After dropping, the mixture is reacted at the same temperature for 1 hour, added with 0.2 parts by mass of TBPEH, and further reacted at the same temperature for 10 hours, whereby an acrylic resin water dispersion (W-1) having a nonvolatile content of 45.0% ) 1000 parts by mass were obtained.

(Example 1: Preparation of aqueous composite resin composition (1))
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet is charged with 208 parts by mass of an aqueous dispersion of the polysiloxane composite resin (A-1) and 220 parts by mass of deionized water. The temperature was raised to ° C.
Next, at the same temperature, 100 parts by mass of deionized water, 30 parts by mass of polyoxyethylene-1- (allyloxymethyl) alkyl sulfate ammonium salt 25% aqueous solution (“AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 115 parts by mass of MMA, 121 parts by mass of 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”), 145 parts by mass of cyclohexyl methacrylate (hereinafter abbreviated as “CHMA”), 1 part by mass of MPTS, polyoxyethylene An aqueous solution in which 1 part by mass of sodium persulfate was dissolved in 33 parts by mass of a polymerizable monomer emulsion and 25 parts by mass of monomethacrylate (“Blenmer PME-400” manufactured by NOF Corporation) in 5 hours. It was dripped.
After dripping, it is made to react at the same temperature for 30 minutes, 0.2 mass part of TBPEH is added, and also it is made to react at the same temperature for 10 hours, The aqueous | water-based composite resin composition (1) 1000 whose non volatile matter is 45.0% A mass part was obtained.

[Evaluation of storage stability]
The minimum film-forming temperature of the aqueous composite resin composition (1) obtained above (hereinafter abbreviated as “initial MFT”) and the aqueous composite resin composition (1) are left in an environment of 50 ° C. for 30 days. The minimum film-forming temperature (hereinafter abbreviated as “time-lapse MFT”) is measured, and the difference in the minimum film-forming temperature (° C.) (“time-lapse MFT” − “initial MFT”) is determined according to the following evaluation criteria. Storage stability was evaluated.
○: Less than 5 ° C Δ: 5 ° C or more and less than 10 ° C ×: 10 ° C or more

[Preparation of coating agent]
94.3 parts by mass of the aqueous composite resin composition (1) obtained above and 5.7 parts by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate are mixed, and the coating agent (1) was prepared.

[Evaluation of water resistance]
The coating agent (1) obtained above was coated on a glass plate so as to have a film thickness of 50 μm, and dried for 7 days in an environment of 23 ° C. and 50% RH. The appearance immediately after taking out from water after immersion for 24 hours was visually evaluated according to the following evaluation criteria.
○: No whitening Δ: Whitening is observed.
X: Peeling from the substrate is observed.

[Evaluation of weather resistance]
The coating agent (1) obtained above was applied onto a chromate-treated aluminum plate (manufactured by Engineering Test Service Co., Ltd.) so as to have a film thickness of 30 μm. Dew panel light weather meter (manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 70 ° C .; wetting: humidity 90% or more, 50 ° C., light irradiation / wetting cycle = 8 (Hour / 4 hours) was subjected to a 2500 hour exposure test, and the appearance of the coating film was evaluated according to the following evaluation criteria.
○: No cracks are observed on the coating surface.
(Triangle | delta): Generation | occurrence | production of a crack is seen in a part of coating-film surface.
X: Generation | occurrence | production of a crack is seen in the whole coating-film surface.

(Example 2: Preparation of aqueous composite resin composition (2))
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet is charged with 417 parts by mass of the composition of the aqueous composite resin (A-1) and 100 parts by mass of deionized water up to 80 ° C. The temperature rose.
Next, at the same temperature, 65 parts by mass of deionized water, 22 parts by mass of 25% aqueous solution of polyoxyethylene-1- (allyloxymethyl) alkylsulfate ammonium salt (“AQUALON KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) MMA 90 parts by mass, 2EHA 100 parts by mass, CHMA 115 parts by mass, MPTS 1 part by mass, polyoxyethylene monomethacrylate (“Blenmer PME-400” manufactured by NOF Corporation) 20 parts by mass An aqueous solution in which 1 part by mass of sodium persulfate was dissolved in 27 parts by mass of the liquid and deionized water was added dropwise over 5 hours.
After dripping, it is made to react at the same temperature for 1 hour, 0.2 mass part of TBPEH is added, and also it is made to react at the same temperature for 10 hours, and the water-based composite resin composition (2) 1000 with a non-volatile content of 50.0% A mass part was obtained.

  The aqueous composite resin composition (2) obtained above was operated in the same manner as in Example 1 to evaluate the storage stability. Moreover, it operated similarly to Example 1, the coating agent (2) was prepared, and the coating-film characteristic (water resistance and weather resistance) was evaluated.

(Example 3: Preparation of aqueous composite resin composition (3))
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 860 parts by mass of the aqueous dispersion of the polysiloxane composite resin (A-2) and 15 parts by mass of deionized water were charged. The temperature was raised to ° C.
Next, at the same temperature, 15 parts by mass of deionized water, 25 parts of a polyoxyethylene-1- (allyloxymethyl) alkyl sulfate ammonium salt 25% aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd. “AQUALON KH-1025”) 6 parts by mass , 20 parts by mass of MMA, 25 parts by mass of 2EHA, 30 parts by mass of CHMA, 0.3 parts by mass of MPTS, 8 parts by mass of polyoxyethylene monomethacrylate (“Blemmer PME-400” manufactured by NOF Corporation) An aqueous solution in which 0.3 parts by mass of sodium persulfate was dissolved in 10 parts by mass of the body emulsion and deionized water was added dropwise over 5 hours.
After dripping, it is made to react at the same temperature for 1 hour, 0.1 mass part of TBPEH is added, and also it is made to react at the same temperature for 10 hours, The aqueous | water-based composite resin composition (3) 1000 whose non volatile matter is 43.0% A mass part was obtained.

  The aqueous composite resin composition (3) obtained above was operated in the same manner as in Example 1 to evaluate the storage stability. Moreover, it operated similarly to Example 1, the coating agent (3) was prepared, and the coating-film characteristic (water resistance and weather resistance) was evaluated.

(Comparative Example 1: Preparation of aqueous resin composition (R-1))
The acrylic resin aqueous dispersion (W-1) produced in Synthesis Example 4 was used as the aqueous resin composition (R-1).

  The aqueous resin composition (R-1) obtained above was operated in the same manner as in Example 1 to evaluate the storage stability. Moreover, it operated similarly to Example 1, the coating agent (R-1) was prepared, and the coating-film characteristic (water resistance and weather resistance) was evaluated.

(Comparative Example 2: Preparation of aqueous resin composition (R-2))
The aqueous dispersion of polysiloxane composite resin (A-1) produced in Synthesis Example 2 was used as the aqueous resin composition (R-2).

  The aqueous resin composition (R-2) obtained above was operated in the same manner as in Example 1 to evaluate the storage stability. Moreover, it operated similarly to Example 1, the coating agent (R-2) was prepared, and the coating-film characteristic (water resistance and weather resistance) was evaluated.

(Comparative Example 3: Preparation of aqueous resin composition (R-3))
By mixing 83 parts by mass of the aqueous dispersion of the polysiloxane composite resin (A-1) produced in Synthesis Example 2 and 148 parts by mass of the acrylic resin aqueous dispersion (W-1) produced in Synthesis Example 4, An aqueous resin composition (R-3) was prepared.

  About the aqueous resin composition (R-3) obtained above, it operated similarly to Example 1 and evaluated storage stability. Moreover, it operated similarly to Example 1, the coating agent (R-3) was prepared, and the coating-film characteristic (water resistance and weather resistance) was evaluated.

  Table 1 shows the resin compositions and evaluation results of the aqueous composite resin compositions (1) to (3) of Examples 1 to 3 and the aqueous resin compositions (R-1) to (R-3) of Comparative Examples 1 to 3. Show. The mass ratio [polysiloxane structure / whole resin] was calculated in consideration of the generation of by-products such as methanol and ethanol that can be generated when the polysiloxane structure is formed.

  It was confirmed that the water-based composite resin compositions of Examples 1 to 3 of the present invention were excellent in storage stability and excellent in water resistance and weather resistance of the resulting coating film.

  Although the comparative example 1 is an example which used the acrylic resin water dispersion as an aqueous resin composition, it was confirmed that the weather resistance of the coating film obtained is inadequate.

  Comparative Example 2 is an example in which an aqueous dispersion of a polysiloxane composite resin was used as an aqueous resin composition, but it was confirmed that the storage stability was poor and the water resistance of the resulting coating film was insufficient.

  Comparative Example 3 is an example of an aqueous resin composition obtained by mixing an aqueous dispersion of a polysiloxane composite resin and an aqueous dispersion of an acrylic resin, but the storage stability is poor and the water resistance of the resulting coating film is poor. Was also confirmed to be insufficient.

Claims (3)

An aqueous composite resin composition containing a composite resin (C) obtained by polymerizing the vinyl monomer mixture (B) in an aqueous dispersion of a polysiloxane composite resin (A) and an aqueous medium, The polysiloxane composite resin (A) is a composite resin in which a vinyl polymer (a1) having a hydrophilic group and a polysiloxane (a2) are bonded , and the vinyl polymer (a1), the polysiloxane (a2), and Reaction between the hydrolyzable silyl group and / or silanol group of the vinyl polymer (a1) having the hydrophilic group and the hydrolyzable silyl group and / or silanol group of the polysiloxane (a2). The aqueous composite resin composition is characterized in that the polysiloxane structure in the composite resin (C) is in the range of 3 to 60% by mass . Weight ratio of said polysiloxane composite resin (A) and the vinyl monomer mixture (B) [(A) / (B)] is 10 / 90-80 / 20 aqueous claim 1 Symbol placement in the range of Composite resin composition. Coating agent characterized by containing the claims 1 or 2 aqueous hybrid resin composition.