JP5493286B2 - Organic-inorganic hybrid resin aqueous dispersion, curable resin composition, paint and paint - Google Patents

Description

  The present invention relates to an organic-inorganic hybrid resin aqueous dispersion, a curable resin composition containing the organic dispersion, a paint containing these, and a coated product obtained by applying the paint. More specifically, a composite resin formed by bonding a specific polymer segment and a specific polysiloxane segment is modified with a specific zirconosiloxane compound, and then the obtained zirconosiloxane-modified composite resin is dispersed in an aqueous medium, An organic-inorganic hybrid resin aqueous dispersion containing a zirconium component and a silicon component obtained by hydrolysis and condensation, and a cured product containing this aqueous dispersion, having excellent curability and excellent weather resistance, corrosion resistance, etc. Curable resin composition, paints containing these aqueous dispersions or curable resin compositions, and coating films having excellent weather resistance and corrosion resistance obtained by coating and curing this paint on various substrates It is related with the coating material provided with.

  In the polymer material field, development of highly durable water-based resins has been actively conducted as environmental measures, resource saving and energy saving measures. Taking the resin field for paints as an example, an overcoat film for an exterior material based on a silicon-modified water-based resin having excellent weather resistance has been developed (see, for example, Patent Document 1). However, the coating film based on such a silicon-modified water-based resin has insufficient corrosion resistance, and it has been difficult to apply a high degree of corrosion resistance by directly coating a metal.

Japanese Patent Laid-Open No. 10-036514

  The problem to be solved by the present invention is that a cured coating film having a high degree of weather resistance can be formed as a resin for top coating materials such as exterior materials, and a cured coating having excellent corrosion resistance as a resin for metal anticorrosion coating agents. To provide a novel organic-inorganic hybrid resin aqueous dispersion capable of forming a film, to provide a curable resin composition containing the aqueous dispersion, and to provide the aqueous dispersion or curable resin composition An object of the present invention is to provide a coating material containing the coating material and to provide a coated product obtained by coating the coating material.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a polymer segment (A) containing an acid group and / or a neutralized acid group and a hydrolyzable group bonded to a silicon atom. And / or a zirconosiloxane compound containing a composite resin (AB) in which a polysiloxane segment (B) containing a silanol group is bonded to an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom A zirconosiloxane-modified composite resin (ABC) containing a neutralized acid group obtained by modification with (C) and then neutralization or non-neutralization was dispersed in an aqueous medium. Thereafter, the hydrolyzable group and / or silanol group bonded to the silicon atom in the zirconosiloxane modified composite resin (ABC) and / or the zirconium atom By hydrolytic condensation of the combined alkoxy group and / or alkoxy group bonded to the silicon atom, the solid content concentration can be increased, and the organic component containing a zirconium component and a silicon component having excellent storage stability An aqueous inorganic hybrid resin dispersion is obtained, and a coating containing a curable resin composition containing the aqueous organic-inorganic hybrid resin dispersion thus prepared as a base resin component is used as a top coating for an exterior material. When used, it forms a cured coating film that is extremely excellent in weather resistance, and when the paint is used as a coating agent for metals, it is found that it forms a cured coating film that is extremely excellent in corrosion resistance. I came to let you.

  That is, the present invention provides a polymer segment (A) containing an acid group and / or a neutralized acid group and a polysiloxane segment (B) containing a hydrolyzable group and / or a silanol group bonded to a silicon atom. The composite resin (AB) formed by bonding is modified with a zirconosiloxane compound (C) containing an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom, and then neutralized, or A hydrolyzable group and / or silanol bonded to a silicon atom after dispersing a zirconosiloxane-modified composite resin (ABC) containing a neutralized acid group obtained without neutralization in an aqueous medium And hydrolytic condensation of the alkoxy group bonded to the zirconium atom and / or the alkoxy group bonded to the silicon atom. It relates inorganic hybrid resin aqueous dispersion - Organic, characterized in that as it is.

  The present invention also relates to a curable resin composition comprising the organic-inorganic hybrid resin aqueous dispersion and a curing agent (D), and the curable resin composition or organic-inorganic. The present invention also relates to a coating material containing an aqueous hybrid resin dispersion. Furthermore, the present invention also relates to a coated article characterized by being obtained by coating the coating material on the article to be coated.

  The organic-inorganic hybrid resin aqueous dispersion according to the present invention is a novel aqueous dispersion that can increase the solid content and is excellent in storage stability. And the said organic-inorganic hybrid resin aqueous dispersion forms the cured coating film which has high weather resistance, and is suitable as resin for top coat paints of an exterior material. In addition, when a coating agent containing the organic-inorganic hybrid resin aqueous dispersion is applied to a metal substrate, it forms a cured coating film that imparts a high degree of corrosion resistance, and is therefore suitable as a metal anticorrosion coating resin.

  The aqueous organic-inorganic hybrid resin dispersion of the present invention contains a polymer segment (A) containing an acid group and / or a neutralized acid group and a hydrolyzable group and / or silanol group bonded to a silicon atom. A composite resin (AB) formed by bonding polysiloxane segments (B) is modified with a zirconosiloxane compound (C) containing an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom, Next, the zirconosiloxane-modified composite resin (ABC) containing a neutralized acid group obtained by neutralization or non-neutralization is dispersed in an aqueous medium, and then hydrolyzed bonded to silicon atoms. Decomposable and / or silanol groups and alkoxy and / or silicon atoms bonded to zirconium atoms. It is those prepared by hydrolytic condensation of a Kokishi group.

  Typical examples of the acid group contained in the polymer segment (A) containing the acid group constituting the composite resin (AB) and / or the neutralized acid group include a carboxyl group, a sulfonic acid group, Examples thereof include a sulfinic acid group, a sulfuric acid group, a sulfite group, a phosphoric acid group, an acidic phosphoric ester group, and a phosphorous acid group. These acid groups are converted to neutralized acid groups by neutralization with a basic compound. Of these acid groups or neutralized acid groups, preferred are a carboxyl group and a carboxylate group, respectively.

  Representative examples of the polymer segment (A) containing such acid groups and / or neutralized acid groups include various polymers such as vinyl polymers, polyester polymers, polyurethane polymers, and the like. Examples of the segment include a segment derived from a vinyl polymer and a segment derived from a polyurethane polymer because the preparation is easy and the hydrolysis resistance is excellent. And, representative examples of vinyl polymers include various polymers such as acrylic polymers, carboxylic acid vinyl ester polymers, aromatic vinyl polymers, fluoroolefin polymers, Acrylic polymers are particularly preferred because of the high degree of design freedom. Moreover, these various polymers may be used alone or in combination of two or more.

  The polysiloxane segment (B) containing a hydrolyzable group and / or silanol group bonded to the silicon atom constituting the composite resin (AB) includes various polysiloxanes having a linear, branched or cyclic structure. And those containing a hydrolyzable group and / or silanol group (hydroxyl group bonded to a silicon atom) bonded to a silicon atom. Typical examples of the hydrolyzable group bonded to the silicon atom contained in the polysiloxane segment (B) include a hydrogen atom, a halogen atom, an alkoxy group, a substituted alkoxy group, and an acyloxy group bonded to the silicon atom. , Phenoxy group, aryloxy group, mercapto group, amino group, amide group, aminooxy group, iminooxy group, alkenyloxy group, etc., among these, particularly preferred are an alkoxy group bonded to a silicon atom and A substituted alkoxy group bonded to a silicon atom.

  Examples of the structure of the composite resin (AB) include a structure in which a polymer segment (A) and a polysiloxane segment (B) are bonded in a graft shape or a block shape. And the structure of the bonding portion between the polymer segment (A) and the polysiloxane segment (B) may be any bonding mode, and is not particularly limited, but particularly preferred is the following structural formula (S-1 ).

〔但し、構造式（Ｓ−１）中の炭素原子は前記重合体セグメント（Ａ）の一部分を構成し、シリコン原子と酸素原子は前記ポリシロキサンセグメント（Ｂ）の一部分を構成するものである。〕

[However, the carbon atom in the structural formula (S-1) constitutes a part of the polymer segment (A), and the silicon atom and the oxygen atom constitute a part of the polysiloxane segment (B). ]

  The polymer used as the precursor of the polymer segment (A) when the polymer segment (A) and the polysiloxane segment (B) are bonded via the bond of the structural formula (S-1) includes an acid group. And / or a polymer (a) containing neutralized acid groups and hydrolyzable silyl groups and / or silanol groups. Here, the hydrolyzable silyl group represents an atomic group in which various hydrolyzable groups are bonded to a silicon atom as represented by the following structural formula (S-2).

（但し、式中のＲ_１はアルキル基、アリール基またはアラルキル基を、Ｒ_２は水素原子、ハロゲン原子、アルコキシ基、置換アルコキシ基、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を表わすものとし、また、ｍは０、１または２なる整数を表す。）

Wherein R ₁ is an alkyl group, aryl group or aralkyl group, R ₂ is a hydrogen atom, halogen atom, alkoxy group, substituted alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group An amide group, an aminooxy group, an iminooxy group or an alkenyloxy group, and m represents an integer of 0, 1 or 2.)

Particularly preferred as R ₂ in the general formula (S-2) is an alkoxy group from the viewpoint that alcohol produced by hydrolysis can be easily removed.

  The silanol group introduced into the polymer (a) is, for example, a hydrolyzable group contained in a hydrolyzable silyl group represented by the general formula (S-2). -Si-OH generated by conversion to a hydroxyl group. Of the hydrolyzable silyl groups and / or silanol groups contained in the polymer (a), a particularly preferable one is a hydrolyzable silyl group from the viewpoint of easy introduction. That is, the polymer (a) that is a precursor of the polymer segment (A) is particularly preferably one containing a hydrolyzable silyl group in addition to the acid group and / or the neutralized acid group.

  In order to prepare a vinyl polymer (a-1) containing an acid group and a hydrolyzable silyl group and / or a silanol group in the polymer (a), for example, (1) containing an acid group A method of copolymerizing a vinyl monomer and a vinyl monomer containing a hydrolyzable silyl group and / or silanol group with a monomer copolymerizable therewith, (2) a previously prepared hydroxyl group, and A method of reacting a polycarboxylic acid anhydride with a vinyl polymer containing a hydrolyzable silyl group and / or silanol group, (3) an acid anhydride group prepared in advance and a hydrolyzable silyl group and / or silanol group Various methods such as a method of reacting a vinyl polymer contained with a compound having active hydrogen such as water, alcohol, amine, etc. can be applied. Among these, the method (1) is the simplest.

  As the vinyl monomer containing an acid group used in the method (1), a vinyl monomer containing a carboxyl group as an acid group is preferable, and typical examples thereof include (meth) Unsaturated carboxylic acids such as acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid, fumaric acid; itaconic acid monomethyl, itaconic acid mono-n-butyl, maleic acid monomethyl, maleic acid mono- monoesters of saturated dicarboxylic acids such as n-butyl, monomethyl fumarate, mono-n-butyl fumarate and saturated monohydric alcohols; monovinyl esters of saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; Of saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, etc. Addition reaction product of water and vinyl monomer containing hydroxyl group bonded to carbon atom as described later; addition reaction of carboxyl group-containing monomer and lactone as described above Monomers that can be obtained are included.

  Further, typical vinyl monomers containing hydrolyzable silyl groups and / or silanol groups, which are used for introducing hydrolyzable silyl groups and / or silanol groups by the method of (1) above. Examples include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyl-methyldimethoxysilane, 3- (meth) acryloyloxypropyl- Methyldiethoxysilane, 3- (meth) acryloyloxypropyl-dimethyl-methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (meth) acryloyloxypropyl-dimethyl-hydroxy Silane, 2- Trimethoxysilyl) ethyl vinyl ether, 4- (trimethoxysilyl) butyl vinyl ether.

  Copolymerize various carboxyl group-containing vinyl monomers as described above with vinyl monomers containing hydrolyzable silyl groups and / or silanol groups, and other monomers copolymerizable therewith. By doing so, a vinyl polymer containing a carboxyl group and a hydrolyzable silyl group and / or a silanol group is prepared. Representative examples of such copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Esters of alkyl alcohols having 1 to 22 carbon atoms such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and (meth) acrylic acid;

Aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; 2-methoxyethyl (meta ) Ω-alkoxyalkyl (meth) acrylates such as acrylate and 4-methoxybutyl (meth) acrylate;

Aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; carboxylic acids such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, vinyl benzoate Vinyl esters; alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dimethyl malate, di-n-butyl malate, dimethyl fumarate, di-n-butyl fumarate, dimethyl itaconate, di-n- Dialkyl esters of unsaturated dibasic acids such as butyl itaconate;

Cyano group-containing monomers such as (meth) acrylonitrile and crotononitrile; fluoroolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene; vinyl chloride and vinylidene chloride Chlorinated olefins such as ethylene; propylene, isobutylene, 1-butene, 1-hexene and other α-olefins;

Alkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and n-hexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and 4-methylcyclohexyl vinyl ether; (meth) acrylamide, N, N-dimethyl ( Examples include amide group-containing monomers such as (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, and N-vinylpyrrolidone.

  Further, the hydrophilicity of the vinyl polymer (a-1) containing an acid group and a hydrolyzable silyl group and / or silanol group is increased, and the water of the zirconosiloxane modified composite resin (ABC) finally obtained is increased. In order to improve dispersibility, a vinyl monomer having a polyether chain can be copolymerized as a part of the other copolymerizable monomer. Typical examples of such vinyl monomers include methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate, and (meth) ethylene oxide / propylene oxide copolymer having methoxy at one end. Examples include acrylated products.

  Furthermore, monomers having various reactive functional groups can be copolymerized as a part of the other copolymerizable monomers. Typical examples of the monomer having such a reactive functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl vinyl ether. Hydroxyl group-containing vinyl monomers such as 4-hydroxybutyl vinyl ether; 2,3-carbonate propyl (meth) acrylate, 2-methyl-2,3-carbonate propyl (meth) acrylate, 3,4-carbonate butyl (meta ) Cyclocarbonate group-containing vinyl monomers such as acrylates; Epoxy group-containing vinyl systems such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl vinyl ether Such as methyl N- (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate, ethyl N- [2- (meth) acryloyloxy] ethylcarbamate, 2-carbamoyloxyethyl (meth) acrylate, etc. Carbamate group-containing vinyl monomers; N-hydroxymethylamide groups or N-alkoxymethylamide groups such as N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. Vinyl monomer having: tertiary amino group-containing vinyl monomers such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate Examples include the body.

  Among the various vinyl monomers described above, an acrylic polymer can be obtained by polymerizing a monomer mixture containing (meth) acrylic acid ester as an essential monomer. In addition, by polymerizing a monomer mixture having an aromatic vinyl monomer, a carboxylic acid vinyl ester monomer, and a fluoroolefin monomer as essential components, respectively, an aromatic vinyl polymer is obtained. Carboxylic acid vinyl ester polymers and fluoroolefin polymers can be obtained.

  In order to obtain a vinyl polymer containing a carboxyl group and a hydrolyzable silyl group and / or silanol group from the various vinyl monomers described above, various methods such as a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, etc. However, the solution radical polymerization method in an organic solvent is the simplest.

  When preparing a vinyl polymer containing a carboxyl group and a hydrolyzable silyl group and / or silanol group by a solution radical polymerization method in an organic solvent, various organic solvents can be used. Typical examples of such organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono Alcohols such as n-propyl ether; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, cyclooctane; toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons such as methyl formate, ethyl formate, ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Ters; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone; Ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether; N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate And aprotic polar solvents. Among these, it is particularly preferable to use alcohols and water-soluble compounds as essential components.

  Further, as a method for preparing the composite resin (AB) from the polymer (a) containing the acid group and / or the neutralized acid group and the hydrolyzable silyl group and / or silanol group, the method described later ( ii) That is, when applying a method of hydrolyzing and condensing a silane compound having a hydrolyzable group bonded to a silicon atom in the presence of the polymer (a), a carboxyl group in the presence of the silane compound in advance. In addition, a vinyl polymer containing a hydrolyzable silyl group and / or a silanol group may be prepared. Typical examples of such a silane compound include those described later as representative examples of the alkoxysilane compound (c-3) used in preparing the zirconosiloxane compound (C).

  Various polymerization initiators are used as the polymerization initiator used in the solution radical polymerization. Typical examples include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile). ) And other azo compounds; peroxides such as tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and di-tert-butyl peroxide And the like.

  Next, among the polymer (a) containing an acid group and / or a neutralized acid group and a hydrolyzable silyl group and / or silanol group, the neutralized acid group and hydrolyzable silyl group and / or Alternatively, a vinyl polymer (a-2) containing a silanol group can be prepared by, for example, (4) vinyl group containing an acid group such as a carboxyl group and a hydrolyzable silyl group and / or a silanol group. A method of neutralizing a polymer with various basic compounds, (5) a vinyl monomer containing a neutralized acid group obtained by previously neutralizing an acid group such as a carboxyl group with a basic compound; A method such as a method of copolymerizing with another copolymerizable monomer can be applied. Among these, the method (4) is particularly convenient and recommended.

  When neutralizing acid groups such as carboxyl groups and acid groups contained in vinyl polymers containing hydrolyzable silyl groups and / or silanol groups to convert them to neutralized acid groups such as carboxylate groups Various compounds can be used as the basic compound used in the preparation. Representative examples of such basic compounds include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol; ammonia, lithium hydroxide, hydroxide Inorganic basic substances such as sodium and potassium hydroxide; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide.

  The addition amount of the basic compound when converting the acid group to a neutralized acid group such as a carboxylate group is appropriately set according to the amount of the acid group contained in the vinyl polymer (a-1). The basic compound is generally 0.2 to 6.0 moles, preferably 0.3 to 5.0 moles, particularly preferably 0.5 to 3.0 moles per mole of acid group. May be added. When the acid group is neutralized, the acid group is partially neutralized by adding less than an equivalent amount of a basic compound with respect to the acid group, so that the polymer obtained is neutralized with the acid group. And a hydrolyzable silyl group and / or silanol group. Further, when an equivalent equivalent basic compound or an excess excess basic compound is added with respect to the acid group, a vinyl type containing a neutralized acid group and a hydrolyzable silyl group and / or silanol group A polymer is obtained.

  The total amount of the acid group such as carboxyl group and the neutralized acid group such as carboxylate group introduced into the vinyl polymer thus prepared has good storage stability and the water resistance and resistance of the cured coating film. Since an aqueous organic-inorganic hybrid resin dispersion having excellent alkalinity can be obtained, a range of 0.1 to 10.0 mol per 1000 g of vinyl polymer is preferable, and a range of 0.2 to 7.0 mol is more preferable. And particularly preferably in the range of 0.3 to 5.0 mol.

  The amount of the hydrolyzable silyl group and / or silanol group introduced into the vinyl polymer as the polymer (a) is good in the transparency of the cured product, and in the preparation process of the aqueous hybrid resin dispersion Since thickening and gelation hardly occur, the range of 0.01 to 1.5 mol per 1000 g of the vinyl polymer is preferable, more preferably 0.02 to 1.3 mol, and particularly preferably 0. The range is from 0.05 to 1.0 mol.

  In addition, the weight average molecular weight of the vinyl polymer as the polymer (a) is such that when modified with the zirconosiloxane compound (C), the viscosity becomes high and the workability is not inferior or gelled. A range of 2,000 to 150,000 is preferable, and more preferably 3,000 to 100, since an organic-inorganic hybrid resin aqueous dispersion that gives a cured coating film having good storage stability and excellent water resistance can be obtained. In the range of 4,000 to 50,000.

  Of the polymer (a), preparation of a polyurethane polymer containing an acid group and / or a neutralized acid group and a hydrolyzable silyl group and / or silanol group will be described. A system polymer refers to a polymer containing at least two urethane bonds in one molecule. In order to prepare a polyurethane-based polymer containing such acid groups and / or neutralized acid groups and hydrolyzable silyl groups, for example, (6) acid groups and / or neutralized acid groups and isocyanate groups And (7) acid group and / or neutralization, wherein a urethane prepolymer (P-1) having a reaction with an active hydrogen-containing group that reacts with an isocyanate group and a compound having both a hydrolyzable silyl group and / or a silanol group (8) a method of reacting a compound having both an isocyanate group and a hydrolyzable silyl group and / or silanol group with a prepolymer (P-2) containing an acid group and a hydroxyl group, and (8) a carboxyl group and / or neutralized Epoxy group and hydrolyzable silyl group and / or silanol A method of reacting a compound having both a method and the like can be applied. Among the hydrolyzable silyl groups and / or silanol groups introduced into the polyurethane polymer, a particularly preferable one is hydrolyzed from the viewpoint of easy availability of raw materials and ease of preparation of the polyurethane polymer. It is a sex silyl group.

  In order to prepare the urethane prepolymer (P-1) having an acid group and / or a neutralized acid group and an isocyanate group used in the method of (6), for example, a polymer polyol and an acid group are contained. A polyol and / or a polyisocyanate containing a neutralized acid group may be reacted at a ratio such that the isocyanate group becomes excessive with respect to the hydroxyl group.

  Typical polymer polyols used in preparing the urethane prepolymer (P-1) include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyester amide polyols, polythioether polyols, polybutadiene polyols. Polyolefin polyols and the like. These may be used alone or in combination of two or more.

  Among these polymer polyols, polyester polyol is an esterification reaction of, for example, a low molecular weight polyhydric alcohol and a low molecular weight polycarboxylic acid or a reactive derivative thereof in such a ratio that the hydroxyl group is excessive with respect to the carboxyl group. Prepared. Typical examples of the low molecular weight polyhydric alcohol used in this case include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. -L, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-bishydroxyethoxybenzene, Examples include dihydric alcohols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. Representative examples of the low molecular weight polycarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid: polycarboxylic acids having 3 or more valences such as trimellitic acid and pyromellitic acid An acid etc. are mentioned. Of the various types of polyhydric alcohols described above, dihydric alcohols are preferably used as the main component. Of the various polycarboxylic acids described above, dicarboxylic acid is preferably used as the main component.

  As the polyester polyol, a polyester polyol obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone in the presence of a low molecular weight polyhydric alcohol as described above can also be used.

  As the polyether polyol, for example, one obtained by ring-opening polymerization of alkylene oxide using one or more compounds having two or more active hydrogen-containing groups as a polymerization initiator can be used. . As a representative compound having two or more active hydrogen atom-containing groups used as a polymerization initiator, in addition to the polyhydric alcohol and polycarboxylic acid described above as used when preparing a polyester polyol, , Phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine and the like. Of these, a compound having two active hydrogen-containing groups is preferably used as the main component of the polymerization initiator.

  Typical examples of the alkylene oxide used in the preparation of the polyether polyol include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. Representative examples of polyether polyols obtained by ring-opening polymerization of such alkylene oxides include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene-polyoxypropylene copolymer glycol, Examples thereof include oxyethylene-polyoxybutylene copolymer glycol.

  Typical examples of the polycarbonate polyol include various polycarbonate diols obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanedimethanol with diphenyl carbonate and phosgene. Etc.

  Among the various polymer polyols described above, it is preferable to use a polyether polyol or a polycarbonate polyol because an aqueous organic-inorganic hybrid resin dispersion having excellent hydrolysis resistance can be obtained. The number average molecular weight of the polymer polyol is preferably in the range of 300 to 10,000, and more preferably in the range of 500 to 5,000.

  Typical examples of polyols containing acid groups and neutralized acid groups used in preparing the urethane prepolymer (P-1) include 2,2-dimethylolpropionic acid. A low molecular weight diol containing a carboxyl group, such as 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid; Carboxyl group-containing polyester polyols obtained by reacting with various polycarboxylic acids; containing carboxylate groups obtained by neutralizing the low molecular weight diol containing carboxyl groups or carboxyl group-containing polyester polyols with various bases Polyol; 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfur Polyester polyols containing sulfonic acid groups obtained by reacting dicarboxylic acids containing sulfonic acid groups such as phthalic acid and 5- (4-sulfophenoxy) isophthalic acid with low molecular weight polyhydric alcohols as described above; Polyester containing a sulfonate group obtained by reacting a dicarboxylic acid containing a sulfonate group obtained by neutralizing a sulfonic acid group of a dicarboxylic acid containing a sulfonic acid group with a base and a low molecular weight polyhydric alcohol. A polyol etc. are mentioned. Typical examples of bases used for neutralizing acid groups such as carboxyl groups and sulfonic acid groups described above are used for preparing vinyl polymers having neutralized acid groups. The various compounds illustrated as a typical thing are mentioned.

  Among the polyols containing acid groups and the polyols containing neutralized acid groups, a low molecular weight diol containing a carboxyl group is used because it is easy to prepare a urethane prepolymer (P-1). It is particularly preferred.

  Typical polyisocyanates used in preparing the urethane prepolymer (P-1) include metaphenylene diisocyanate, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5- Aromatic diisocyanates such as diisocyanates; aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic diisocyanates such as cyclohexane-1,3-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate; Examples include aralkylene diisocyanate such as α, α, α ′, α′-tetramethylxylylene diisocyanate. And these may be used independently and may use 2 or more types together.

  Among the polyisocyanates described above, aliphatic diisocyanate, alicyclic diisocyanate and aralkylene diisocyanate are used from the viewpoint of maintaining the water resistance of a cured product obtained from the composition containing the organic-inorganic hybrid resin aqueous dispersion of the present invention. It is preferable to use one or more diisocyanates selected from:

  A urethane prepolymer having an acid group and / or a neutralized acid group and an isocyanate group by reacting the above-described polymer polyol, a polyol containing an acid group and / or a polyol containing a neutralized acid group and a polyisocyanate. A polymer (P-1) can be prepared. At that time, in order to adjust the performance such as strength, elongation, heat resistance and the like of the cured product obtained from the organic-inorganic hybrid resin of the present invention, as a chain extender, amino group, hydroxyl group, mercapto group, carboxyl group, etc. A low molecular weight compound having two or more active hydrogen-containing groups in one molecule can be used in combination.

  Typical low molecular weight compounds having active hydrogen-containing groups used as chain extenders include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, and 2,5-dimethylpiperazine. , Isophoronediamine, 4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 2- (ethylamino) ethylamine, 3- (methylamino) propylamine, and the like; hydrazine, N, N'-dimethylhydrazine, etc. Low molecular weight polyhydric alcohols exemplified as used in preparing the polyester polyol; 1,2-ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc. A dithiol compound etc. are mentioned.

  When preparing the urethane prepolymer (P-1), for example, a hydroxyl group contained in a polyol containing a polymer polyol and an acid group and / or a polyol containing a neutralized acid group, and if necessary Ratio of the number of equivalents of isocyanate groups contained in polyisocyanate to the total number of equivalents of active hydrogen-containing groups contained in the chain extender used (number of equivalents of isocyanate groups / hydroxyl groups and active hydrogen-containing groups in the chain extender) The raw material components may be reacted at a ratio such that the total number of equivalents) is in the range of 1.05-2.5, more preferably in the range of 1.1-2.0. A urethane prepolymer (P-1) having an isocyanate group at the molecular end can be obtained by reacting the polyol and the polyisocyanate at an equivalent ratio in the above range. In order to prepare such a urethane prepolymer (P-1), the reaction may be carried out at 30 to 130 ° C., preferably 50 to 100 ° C. in the absence of a solvent or in the presence of an organic solvent.

  Typical examples of the organic solvent used when preparing the urethane prepolymer (P-1) in the presence of an organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; Examples include acetates such as ethyl and butyl acetate; amides such as dimethylformamide and N-methylpyrrolidone.

  Activity to react with isocyanate group used in preparing polyurethane polymer containing acid group and / or neutralized acid group and hydrolyzable silyl group and / or silanol group by the method of (6) Typical examples of the active hydrogen-containing group containing a compound having both a hydrogen-containing group and a hydrolyzable silyl group include an amino group, a mercapto group, a hydroxyl group, and a carboxyl group.

  Among the compounds having both an active hydrogen-containing group that reacts with an isocyanate group and a hydrolyzable silyl group, a typical example of a compound containing an amino group as an active hydrogen-containing group is 3-aminopropyltrimethoxysilane. 1 amino such as 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane Coupling agent containing a group and a hydrolyzable silyl group; 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, 3- (2-aminoethyl) Amino) propyldimethylmethoxysilane, 3- Silane coupling agents having two amino groups and hydrolyzable silyl groups such as 2-aminoethylamino) propyltriethoxysilane and 3- (2-aminoethylamino) propylmethyldiethoxysilane; 1 molecule represented by N, N-bis [(3-trimethoxysilyl) propyl] amine and N, N-bis [(3-triethoxysilyl) propyl] amine as disclosed in US Pat. Examples thereof include a compound containing one amino group and two hydrolyzable silyl groups.

  Among compounds having both an active hydrogen-containing group that reacts with an isocyanate group and a hydrolyzable silyl group, typical compounds containing a mercapto group as an active hydrogen-containing group include 3-mercaptopropyltrimethoxysilane, 3 Examples include silane coupling agents containing a mercapto group such as -mercapropropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyldimethylmethoxysilane.

  Of the compounds having both an active hydrogen-containing group that reacts with an isocyanate group and a hydrolyzable silyl group, representative examples of the compound containing a hydroxyl group as the active hydrogen-containing group include 3-hydroxypropyltrimethoxysilane, 3- Examples thereof include silane compounds containing a hydroxyl group such as hydroxypropyltriethoxysilane and 3-hydroxypropyldimethylmethoxysilane.

  Among compounds having both an active hydrogen-containing group that reacts with an isocyanate group and a hydrolyzable silyl group, representative examples of the compound containing a carboxyl group as an active hydrogen-containing group include 3-carboxypropyltrimethoxysilane, 3 Examples thereof include silane compounds containing a carboxyl group such as carboxypropyltriethoxysilane and 3-carboxypropyldimethylmethoxysilane.

  Among the compounds having both an active hydrogen-containing group that reacts with the isocyanate group and a hydrolyzable silyl group, it has one or two amino groups because of its high reactivity with the isocyanate group and easy availability. A silane coupling agent is particularly preferred.

  By reacting a compound having both an active hydrogen-containing group that reacts with the isocyanate group and a hydrolyzable silyl group and a urethane prepolymer (P-1), an acid group and / or a neutralized acid group and a hydrolyzable group are reacted. A polyurethane-based polymer containing a silyl group can be prepared. For example, a polyurethane polymer having a hydrolyzable silyl group at the main chain end is prepared by reacting a urethane prepolymer (P-1) with a compound having one amino group and a hydrolyzable silyl group. It is possible to prepare a polyurethane polymer having a structure in which a hydrolyzable silyl group is pendant inside the main chain by reacting two amino groups and a compound having both hydrolyzable silyl groups. . Moreover, by using together the compound which has one amino group and a hydrolyzable silyl group, and the compound which has two amino groups and a hydrolyzable silyl group together, it is made to react with a urethane prepolymer (P-1). A polyurethane-based polymer having hydrolyzable silyl groups at both the main chain terminal and the main chain can be prepared.

  The reaction between the urethane prepolymer (P-1) and a compound having both an active hydrogen-containing group that reacts with an isocyanate group and a hydrolyzable silyl group can be allowed to proceed by, for example, mixing and stirring both. Such a reaction may be performed under conditions of 10 to 100 ° C., preferably 30 to 80 ° C.

  A polyurethane-based polymer containing an acid group and a hydrolyzable silyl group can be prepared by the above-described method using a polyol containing an acid group as a raw material component. Thus, the acid group and the neutralized acid group can be hydrolyzed with the acid group by neutralizing a part of the acid group contained in the polyurethane polymer containing the acid group and hydrolyzable silyl group thus prepared. A polyurethane-based polymer containing a decomposable silyl group can be prepared. Moreover, the neutralized acid group and the hydrolyzable silyl group are also contained by neutralizing 100 mol% of the acid group contained in the polyurethane polymer containing the acid group and the hydrolyzable silyl group. A polyurethane-based polymer can be prepared.

  Acid groups and / or neutralized acid groups used in preparing a polyurethane polymer containing an acid group and / or a neutralized acid group and a hydrolyzable silyl group by the method of (7) Typical examples of the prepolymer (P-2) containing a hydroxyl group include polyester-based polymers and polyurethane-based polymers. An organic-inorganic hybrid resin aqueous dispersion having excellent hydrolysis resistance is obtained. Therefore, a polyurethane polymer is preferable.

  In order to prepare the prepolymer (P-2), for example, a polymer polyol, a polyol containing an acid group, and / or a polymer polyol listed above as used in preparing the urethane prepolymer (P-1) and / or What is necessary is just to make the polyol and polyisocyanate containing the neutralized acid group react at a ratio such that the equivalent number of hydroxyl groups is excessive with respect to the equivalent number of isocyanate groups. A preferable range of the ratio of the number of equivalents (the number of equivalents of hydroxyl groups / the number of equivalents of isocyanate groups) is 1.05 to 2.5, and a more preferable range is 1.1 to 2.0. And the polymer polyol used when preparing the prepolymer (P-2), the polyol containing an acid group and / or the polyol and polyisocyanate containing a neutralized acid group, each preferred one is urethane Examples thereof are those preferably used when preparing the prepolymer (P-1).

  It has both an isocyanate group and a hydrolyzable silyl group used when preparing a polyurethane polymer containing an acid group and / or a neutralized acid group and a hydrolyzable silyl group by the method of (7). A representative compound includes a silane coupling agent containing an isocyanate group. Typical examples of such silane coupling agents containing isocyanate groups include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, and 3-isocyanatopropyl. Examples include alkoxysilanes having an isocyanate group such as triethoxysilane and 3-isocyanatopropylmethyldiethoxysilane.

  By reacting the compound having both the isocyanate group and the hydrolyzable silyl group with the prepolymer (P-2), a polymer having a hydrolyzable silyl group at the polymer terminal can be obtained. The ratio of the number of equivalents of isocyanate groups to the number of equivalents of hydroxyl groups when reacting both components (equivalent number of isocyanate groups / number of hydroxyl groups) is 0.5 to 2.0, preferably 0.8 to 1.2. is there. The reaction of these two components may be performed in the absence of a solvent or in the presence of an organic solvent. A typical solvent used in the reaction in the presence of an organic solvent is used for preparing a polyurethane polymer as a polymer (a) from a urethane prepolymer (P-1). The above-mentioned thing is mentioned as a thing. Moreover, although reaction of both components advances also at room temperature, Preferably it carries out at 40-100 degreeC, More preferably, it carries out at 50-80 degreeC.

  The carboxyl group used in preparing the polyurethane polymer containing the carboxyl group and / or neutralized carboxyl group and hydrolyzable silyl group as the polymer (a) by the method of (8) and / or Or as a polyurethane-type polymer containing the neutralized carboxyl group, it is the prepolymer (P-2) used by the method of said (7), Comprising: A carboxyl group and / or the neutralized carbosil A polyurethane-based polymer containing a group and a hydrolyzable silyl group can be used as it is, and the isocyanate group contained in the urethane prepolymer (P-1) prepared by the method of (6) above is 1 per molecule. It can be easily prepared by reacting with a compound having one active hydrogen-containing group.

  Polyurethane-based polymer containing a carboxyl group and / or a neutralized carboxyl group by a reaction between an isocyanate group contained in the urethane prepolymer (P-1) and a compound having one active hydrogen-containing group in one molecule. Typical examples of the compound having an active hydrogen-containing group used in preparing the coal are methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene. Alcohols such as glycol monomethyl ether, benzyl alcohol, cyclohexanol; primary amines such as ethylamine, n-propylamine, n-butylamine; dimethylamine, diethylamine, di-n-butylamine, morpholine, pyrrolidi , Secondary amines such as piperidine and N-methylpiperazine; N, N-disubstituted hydrazines such as N, N-dimethylhydrazine and N, N-diethylhydrazine; active methylene groups such as acetylacetone and methyl acetoacetate Compound; and ammonia and the like. These compounds having an active hydrogen-containing group may be used alone or in combination of two or more.

  When preparing a polyurethane-based polymer containing a carboxyl group and / or a neutralized carboxyl group from both of these components, the use ratio of both components is (equivalent number of active hydrogen-containing groups) / [urethane prepolymer (P -1) The number of equivalents of isocyanate groups] The ratio of the number of equivalents is 0.8 or more, preferably 1.0 or more. There is no problem even if the compound having an active hydrogen-containing group is used in a large excess, but the reaction may be carried out while keeping the ratio of the number of equivalents to about 10.0. The reaction of both components may be performed in the absence of a solvent or in the presence of an organic solvent. Typical examples of the solvent used in the reaction in the presence of an organic solvent include a carboxyl group and / or a neutralized carboxyl group and hydrolyzable silyl group from the urethane prepolymer (P-1). What was mentioned above as what is used when preparing the polyurethane-type polymer to contain is mentioned. Moreover, although the preferable reaction temperature of both components changes with kinds of compound which has an active hydrogen containing group, it is 10-100 degreeC in general, Preferably it is the range of 30-80 degreeC.

  By reacting a compound having both an epoxy group and a hydrolyzable silyl group with the polyurethane polymer containing the carboxyl group and / or the neutralized carboxyl group, the carboxyl group and / or the neutralized carboxyl group is reacted. A polyurethane-based polymer containing a group and a hydrolyzable silyl group can be prepared. Typical examples of compounds having both an epoxy group and a hydrolyzable silyl group used in this case include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidide. Examples include alkoxysilanes containing an epoxy group such as xylpropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. In such a reaction of both components, an acid group and / or a neutralized acid group obtained by the reaction of both components and an acid group and a neutralized acid contained in a polyurethane polymer containing a hydrolyzable silyl group are obtained. What is necessary is just to make both components react by the ratio that the total amount of group and the quantity of a hydrolyzable silyl group become in the following preferable range. Such reaction of both components may be carried out in the absence of a solvent or in the presence of an organic solvent. The reaction temperature is preferably in the range of 50 to 130 ° C, particularly preferably 70 to 110 ° C.

  When the polyurethane polymer containing an acid group and / or a neutralized acid group and a hydrolyzable silyl group prepared by the method of (6), (7) or (8) has an acid group A polyurethane polymer containing an acid group neutralized with a basic compound and a hydrolyzable silyl group can be obtained.

  The acid groups and / or neutralized acid groups thus prepared and the acid groups introduced into the polyurethane-based polymer containing hydrolyzable silyl groups and / or silanol groups and neutralized acid groups The total amount is 0.1 to 0.1 g per 1,000 g of the polyurethane polymer because an aqueous organic-inorganic hybrid resin dispersion that gives a cured coating film having good storage stability and excellent water resistance and alkali resistance is obtained. The range of 2.0 mol is preferable, the range of 0.15 to 1.5 mol is more preferable, and the range of 0.3 to 1.0 mol is particularly preferable.

  In addition, the amount of silicon atoms derived from the hydrolyzable silyl group and silanol group introduced into the polyurethane-based polymer described above is good in transparency of the cured product, and increases the viscosity in the preparation process of the hybrid resin aqueous dispersion. Since gelation hardly occurs, the range of 0.01 to 1.5 mol per 1,000 g of the polyurethane polymer is preferable, more preferably 0.02 to 1.3 mol, and particularly preferably 0. The range is from 0.05 to 1.0 mol.

  In addition, the weight average molecular weight of the polyurethane-based polymer described above is excellent in storage stability without increasing the viscosity when it is modified with the zirconosiloxane compound (C), resulting in poor workability or gelation. From the viewpoint of obtaining an organic-inorganic hybrid resin aqueous dispersion excellent in water resistance, the range of 2,000 to 200,000 is preferable, the range of 3,000 to 100,000 is more preferable, and the range of 4 is particularly preferable. , 50,000 to 50,000.

  In order to prepare the composite resin (AB) from the polymer (a) containing the acid group and / or the neutralized acid group and the hydrolyzable silyl group and / or silanol group thus prepared, i) a method of reacting the polymer (a) with a polysiloxane (b) containing a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom, (ii) the polymer (a) A method of hydrolyzing and condensing a silane compound having a hydrolyzable group bonded to a silicon atom in the presence of can be applied. As the silane compound having a hydrolyzable group bonded to a silicon atom used in the method (ii), various silane compounds can be used. Particularly preferred are zirconosiloxane compounds (C ) Are various alkoxysilane compounds which will be described later.

  In order to prepare the composite resin (AB) by the method (i), for example, water and a catalyst are added to the mixture of the polymer (a) and the polysiloxane (b) as necessary, and the temperature is 20 to 150 ° C. The reaction may be performed at a temperature of about 30 minutes to 30 hours, preferably at 50 to 130 ° C. for 1 to 20 hours. As a catalyst, various silanol condensation catalysts, such as an acidic compound, a basic compound, and a metal containing compound, can be added. In order to prepare the composite resin (AB) by the method (ii), for example, water and a silanol condensation catalyst are added to the mixture of the polymer (a) and the alkoxysilane compound, and the temperature is 20 to 150 ° C. The hydrolysis condensation may be performed at a temperature of about 30 minutes to 30 hours, preferably at 50 to 130 ° C. for about 1 to 20 hours. In this way, a composite resin (AB) can be prepared.

  Next, a zirconosiloxane containing an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom, which is used in the reaction with the composite resin (AB) to obtain a zirconosiloxane composite resin (ABC). The siloxane compound (C) will be described. Note that zirconosiloxane is a general term for compounds containing a Zr-O-Si bond in the molecule.

  Typical examples of the alkoxy group contained in the zirconosiloxane compound (C) include unsubstituted alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and an octoxy group; a cyclopentyloxy group And an unsubstituted cycloalkoxy group such as a cyclohexyloxy group; an alkoxy group or a cycloalkoxy group having a substituent such as an alkoxy group, a cycloalkyl group, an aryl group, a halogen atom or an alkoxycarbonyl group as a substituent. Of these various alkoxy groups, a C1-C4 unsubstituted alkoxy group or a C1-C4 alkoxy group having a methoxy group or an ethoxy group as a substituent is particularly preferable.

  The zirconosiloxane compound (C), for example, partially cohydrolyzes and condenses an alkoxyzirconium compound (c-1) and / or a partially hydrolyzed condensate thereof (c-2) and an alkoxysilane compound (c-3). It is prepared by.

  Typical examples of the alkoxyzirconium compound (c-1) used in this case include tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetrakis. Examples include tetraalkoxyzirconium such as (2-ethylhexanoxy) zirconium. Moreover, with the partial hydrolysis-condensation product (c-2) of the alkoxyzirconium compound, the main chain obtained by partial hydrolysis-condensation of the alkoxyzirconium compound (c-1) described above is linked with a Zr—O—Zr bond. Oligomers. Specific examples thereof include tetra-n-butoxyzirconium dimer, trimer, tetramer and the like.

  In addition, as the alkoxyzirconium compound (c-1) or the partial hydrolysis condensate thereof (c-2), a part of the alkoxy groups in the various alkoxyzirconium compounds or partial hydrolysis condensates thereof may be acetylacetone or acetoacetic acid. A 1,3-dicarbonyl compound such as an ester or a compound substituted with a monocarboxylic acid can also be used. Specific examples of such alkoxyzirconium compounds include triisopropoxyzirconium monoacetylacetonate, di-n-butoxyzirconium bisacetylacetonate, triisopropoxyzirconium monoethylacetoacetate, triisopropoxyzirconium monoacetate, tri- Examples thereof include n-butoxyzirconium monoacetate.

  Of the various alkoxyzirconium compounds (c-1) and partial hydrolysis condensates (c-2) thereof, tetraalkoxyzirconium is particularly preferable.

  The alkoxyzirconium compound (c-1) and its partial hydrolysis condensate (c-2) may be used alone or in combination of two or more.

  Representative examples of the alkoxysilane compound (c-3) used in preparing the zirconosiloxane compound (C) include tetraalkoxysilanes, monoorganotrialkoxysilanes, diorganodialkoxysilanes, Examples include triorganomonoalkoxysilanes.

  Typical examples of the alkoxy group possessed by such alkoxysilanes include those exemplified as typical alkoxy groups possessed by the alkoxyzirconium compound (c-1). Of the various alkoxy groups, a C 1-4 alkoxy group having a C 1-4 unsubstituted alkoxy group, a methoxy group or an ethoxy group as a substituent is particularly preferable.

  Among the alkoxysilane compounds (c-3), representative examples of tetraalkoxylanes include tetramethoxysilane, tetraethoxysilane, tetra-n-butoxysilane, tetrakis (2-methoxyethoxy) silane, and the like. .

  Typical examples of monoorganotrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n- Alkyltrialkoxysilanes such as propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane: cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltri Cycloalkyltrialkoxysilanes such as ethoxysilane; arylates such as phenyltrimethoxysilane, phenyltriethoxysilane, 4-methylphenyltrimethoxysilane Alkoxysilanes: 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (2-methoxyethoxy) silane, allyl Examples thereof include silane compounds having a functional group generally called a silane coupling agent such as trimethoxysilane.

  Representative examples of diorganodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldiethoxysilane, di- Dialkyl dialkoxysilanes such as n-butyldimethoxysilane; dialkoxysilanes having a cycloalkyl group such as cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane; diphenyldimethoxysilane; Diphenyl diethoxysilane, diphenyldi-n-butoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane and the like having an aryl group Alkoxysilane compounds; vinyl methyl dimethoxysilane, 3- (meth) acryloyloxy propyl silane coupling agents having an alkoxy group such as a methyl dimethoxysilane and the like.

  Representative examples of triorganomonoalkoxysilanes include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, and the like.

  Of the various alkoxysilane compounds (c-3) described above, silane compounds preferable as the main component are tetraalkoxysilanes, monoorganotrialkoxysilanes, and diorganodialkoxysilanes. Among the monoorganotrialkoxysilanes and diorganodialkoxysilanes, particularly preferred silane compounds to be used as the main component are monoalkyltrialkoxysilane and dialkyldialkoxysilane, respectively.

  The various alkoxysilane compounds (c-3) described above are mainly used as monomers, but oligomers obtained by partially hydrolyzing and condensing them may be used in part.

  When preparing the zirconosiloxane compound (C) from the alkoxyzirconium compound (c-1) and / or its partially hydrolyzed condensate (c-2), the alkoxysilane compound (c-3) and water, the reaction Various methods can be applied as the method. Among them, a method of adding an alkoxyzirconium compound (c-1) and / or a partially hydrolyzed condensate thereof (c-2) and water to the initially charged component containing the alkoxysilane compound (c-3) is preferable. This method suppresses the formation of insoluble matter derived from the single hydrolysis condensate of the alkoxyzirconium compound (c-1) and / or its partial hydrolysis condensate (c-2), and is soluble in organic solvents. Since a conosiloxane compound (C) can be obtained, it is very effective. In carrying out such a reaction, an organic solvent can be further added to the alkoxysilane compound (c-3) initially charged. In performing this reaction, the alkoxysilane compound (c-3) may be initially charged in its entirety, or a part thereof may be initially charged, and the remainder may be added during the addition of the alkoxyzirconium compound and water. .

  Specific examples of the organic solvent used in the reaction by adding the organic solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, and ethylene glycol monomethyl. Ethers, alcohols such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether; esters of glycol ethers such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, dioxolane, Ethers such as tetrahydrofuran; dimethylformamide, N, N-dimethylacetamide, N-methyl Amide compounds such as pyrrolidone; dimethyl sulfoxide, sulfolane, N, polar solvents such N- dimethyl ethylene urea and various like. In the preparation of the zirconosiloxane compound (C), it is particularly preferable to use a water-soluble organic solvent because it is possible to suppress the formation of a hydrolytic condensate of only an alkoxyzirconium compound insoluble in the organic solvent.

  The alkoxyzirconium compound (c-1) and / or its partially hydrolyzed condensate (c-2) may be added without diluting with a solvent, but the viscosity decreases and it is easy to add. Since generation | occurrence | production of a melt can be suppressed, it is preferable to dilute and add with the organic solvent which was illustrated as a specific thing which can be added to an alkoxysilane compound (c-3). As an organic solvent used in that case, a water-soluble organic solvent is particularly preferable. The alkoxyzirconium compound (c-1) and / or the partial hydrolysis condensate (c-2) thereof may be added in its entirety to the reaction system containing the alkoxysilane compound (c-3). A part of the insoluble alkoxyzirconium compound can be initially charged as long as no hydrolytic condensate of the insoluble alkoxyzirconium compound alone is formed.

  Water may be dropped as it is without being dissolved in an organic solvent, but it can suppress the formation of a hydrolysis-condensation product of only an alkoxyzirconium compound that is insoluble in an organic solvent, so among the various organic solvents described above. It is particularly preferable to dilute water with a water-soluble organic solvent and add it as a solution.

  The addition method of the alkoxyzirconium compound (c-1) and / or its partially hydrolyzed condensate (c-2) and water in an organic solvent solution may be divided addition method, continuous dropping method, divided dropping method, divided addition and continuous. Various addition methods, such as a method combining a dropping method, can be employed. Among these methods, since a hydrolysis-condensation product of an insoluble alkoxyzirconium compound alone is unlikely to be generated, a method in which both are continuously dropped simultaneously is particularly preferable. In dropping, an alkoxysilane compound (c-3), an organic solvent added as necessary, an alkoxyzirconium compound (c-1) optionally added, and / or a partially hydrolyzed condensate thereof (c-2) It is preferable to gradually add dropwise a part of the mixture with sufficient stirring. If the stirring is insufficient or the dropping speed of both is too high, a hydrolysis condensation reaction of the alkoxyzirconium compound alone tends to occur, and an insoluble gel-like product is likely to be generated.

  In addition, in the process of preparing the zirconosiloxane compound (C), the formation of an insoluble gel is suppressed, and the process of preparing the organic-inorganic hybrid resin of the present invention is stably performed without causing gelation. Since the zirconosiloxane compound (C) soluble in an organic solvent useful for preparing the target organic-inorganic hybrid resin aqueous dispersion can be prepared, the alkoxyzirconium compound (c-1) and / or its partial hydrolysis By performing partial hydrolysis condensation by setting the use ratio of the condensate (c-2), alkoxysilane compound (c-3) and water so as to satisfy the following three conditions (a) to (c): It is preferable to prepare the zirconosiloxane compound (B), and in particular, it is set so as to satisfy the following four conditions (a) to (d), and the partial cohydrolysis condensation It is particularly preferred that zirconocene siloxane compound (C) is prepared by carrying out.

That is,
(I) Molar ratio of water and an alkoxy group (Zr-bonded alkoxy group) bonded to a zirconium atom contained in the alkoxyzirconium compound (c-1) and / or its partially hydrolyzed condensate (c-2) (water / Zr bond alkoxy group) is set to a range of 0.05 to 5.0, preferably 0.1 to 4.0, particularly preferably 0.3 to 3.0.
(B) The molar ratio of alkoxysilane compound (c-3) to water (alkoxysilane compound / water) is 0.3 to 5.0, preferably 0.3 to 4.0, particularly preferably 0.5 to 3. Set to a range of 0.
(C) The atomic ratio (Zr / Si) of zirconium atom to silicon atom is set to 0.01 to 5.0, preferably 0.03 to 4.0, particularly preferably 0.05 to 3.0. To do.
(D) molar ratio of water to the total of alkoxy groups bonded to zirconium atoms (Zr bonded alkoxy groups) and alkoxy groups bonded to silicon atoms (Si bonded alkoxy groups) (Zr bonded alkoxy groups + Si bonded alkoxy groups) [ Water / (Zr bond alkoxy group + Si bond alkoxy group)] is set in a range of 0.03 to 0.8, preferably 0.05 to 0.6, particularly preferably 0.1 to 0.45.

  In preparing the zirconosiloxane compound (C), the target product can be prepared without adding a catalyst that promotes hydrolysis and condensation, but various basic catalysts and acidic catalysts are added to promote the reaction. You can also When strong acids such as hydrochloric acid, sulfuric acid, and nitric acid are used as the acidic catalyst, these acids remain in the organic-inorganic hybrid resin aqueous dispersion of the present invention and can be obtained from the storage stability of the dispersion or the dispersion. Use of these strong acids requires caution as it may adversely affect the performance of the cured product. When an acid catalyst is used, it is preferable to use only an acid having a relatively low acidity such as phosphoric acid, acidic phosphoric acid ester, and carboxylic acid.

  To prepare a zirconosiloxane compound (C) by partially cohydrolyzing and condensing an alkoxyzirconium compound (c-1) and / or a partially hydrolyzed condensate thereof (c-2) and an alkoxysilane compound (c-3). Is generally about −30 to 120 ° C., preferably 0 to 100 ° C. for about 2 to 15 hours, preferably 4 to 10 hours.

  Thus, the zirconosiloxane compound (C) is obtained as a mixed solution of alcohols produced by the reaction and an organic solvent used as necessary, but this solution may be used as it is in the next step, You may use it, raising the content rate of a zirconosiloxane compound (C) by removing volatile components, such as alcohols and the organic solvent used as needed, by distillation.

  The zirconosiloxane compound (C) thus prepared contains an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom as a functional group for bonding to the composite resin (AB). In order to obtain an organic-inorganic hybrid resin aqueous dispersion having a more homogeneous and dense structure, it is particularly preferable that both have an alkoxy group.

  Next, preparation of the organic-inorganic hybrid resin aqueous dispersion from the composite resin (AB) and the zirconosiloxane compound (C) will be described.

  The organic-inorganic hybrid resin aqueous dispersion of the present invention is a neutralization obtained by modifying the composite resin (AB) with the zirconosiloxane compound (C) and then neutralizing or not neutralizing. The hydrolyzable group and / or silanol bonded to the silicon atom in the zirconosiloxane-modified composite resin (ABC) after the zirconosiloxane-modified composite resin (ABC) containing the generated acid group is dispersed in an aqueous medium It can be prepared by hydrolytic condensation of a group and an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom.

  In preparing the organic-inorganic hybrid resin aqueous dispersion of the present invention, the composite resin (AB) and the zirconosiloxane compound (C) are first mixed, and then about -10 to 120 ° C, preferably 0 to 80. An alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom contained in the zirconosiloxane compound (C) by stirring the mixture at a temperature of ° C for about 1 minute to 3 hours, preferably 3 minutes to 2 hours And at least a part of the acid group and / or neutralized acid group contained in the composite resin (AB) and one or more of a hydrolyzable group and / or silanol group bonded to a silicon atom. Forming a bond between the zirconosiloxane compound (C) and the composite resin (AB), and the zirconosiloxane compound of the composite resin (AB) C) to prepare a zirconocene siloxane-modified composite resin (ABC) is a modified product by. In mixing and reacting the composite resin (AB) and the zirconosiloxane compound (C), various apparatuses such as a batch-type mixing / reaction apparatus and a continuous mixing / reaction apparatus can be used.

  In preparing the zirconosiloxane-modified composite resin (ABC), it is preferable to perform the reaction in an organic solvent that dissolves both the composite resin (AB) and the zirconosiloxane compound (C). Representative examples of the organic solvent to be used include any of the various organic solvents described above as used when preparing the polymer (a) or the zirconosiloxane compound (C). Of these organic solvents, it is preferable to use a polar organic solvent as an essential component because of its high affinity for both the polymer (a) and the zirconosiloxane compound (C). Among these organic solvents having polarity, alcohols, ketones, and esters are more preferable, and alcohols are most preferably used as essential solvents.

  Next, the zirconosiloxane-modified composite resin (ABC) obtained as described above is dispersed in an aqueous medium to prepare a dispersion, and then bonded to silicon atoms contained in the zirconosiloxane-modified composite resin (ABC). An aqueous organic-inorganic hybrid resin dispersion can be obtained by hydrolyzing and further condensing the hydrolyzable group and / or silanol group, the alkoxy group bonded to the zirconium atom and the alkoxy group bonded to the silicon atom. However, in order to disperse the zirconosiloxane-modified composite resin (ABC) in water, the zirconosiloxane-modified composite resin (ABC) needs to be a modified resin having a neutralized acid group. Therefore, when the zirconosiloxane-modified composite resin (ABC) has only acid groups, at least a part of the acid groups is neutralized with a basic compound, and the zirconosiloxane-modified composite having neutralized acid groups. It is necessary to use resin (ABC). The addition amount of the basic compound at that time needs to be appropriately set according to the amount of acid groups contained in the polymer segment (A), the type of the zirconosiloxane compound (C), the modification amount, What is necessary is just to add about 0.2-6.0 mol with respect to 1 mol of acid groups, Preferably 0.3-5.0 mol, Especially preferably, 0.5-3.0 mol of basic compounds may be added.

  In addition, when a polymer having both acid groups and neutralized acid groups is used as the composite resin (AB), a sufficient amount of neutralized zirconosiloxane-modified polymer (ABC) is dispersed in water. When the acid group is contained, it is not necessary to neutralize the contained acid group. However, if the zirconosiloxane modified polymer (ABC) does not contain a sufficient amount of neutralized acid groups to be dispersed in water, at least a part of the acid groups contained by adding a basic compound It is necessary to impart water dispersibility by increasing the content of the neutralized acid group by neutralizing.

The use ratio of the composite resin (AB) to the zirconosiloxane compound (C) is 2 to 600 parts by weight, preferably 5 to 500 parts by weight of the zirconosiloxane compound (C) with respect to 100 parts by weight of the composite resin (AB). Part by weight, particularly preferably 10 to 400 parts by weight, and zirconium contained in the organic-inorganic hybrid resin is 0.5 to 50% by weight in terms of zirconium oxide (ZrO ₂ ), preferably 1 to 40%. It is preferable to set the weight%, particularly preferably 3 to 30% by weight. If the zirconium content is within the above range, a cured product having high corrosion resistance and excellent weather resistance and excellent mechanical properties can be obtained.

  In order to disperse the zirconosiloxane-modified composite resin (ABC) in the aqueous medium, for example, the zirconosiloxane-modified composite resin (ABC) having a neutralized acid group may be added to the aqueous medium, Conversely, a formulation may be adopted in which an aqueous medium is added to a zirconosiloxane-modified composite resin (ABC) having a neutralized acid group to perform phase inversion emulsification. Here, as the aqueous medium, water alone may be used, or a mixture of water and a water-soluble organic solvent may be used. In order to disperse the zirconosiloxane-modified polymer (AB) in the aqueous medium, various dispersing devices such as a batch type dispersing device and a continuous type dispersing device can be used.

  Next, hydrolyzable groups and / or silanol groups bonded to silicon atoms and alkoxy groups bonded to zirconium atoms or alkoxy bonded to silicon atoms contained in the aqueous dispersion of the zirconosiloxane-modified composite resin (ABC). In order to hydrolyze and condense the group, it may be left at room temperature of about 10 to 30 ° C., for example, for about 10 minutes to about 1 month, or at a temperature of about 40 to 90 ° C. for 1 minute to 24 hours. The reaction may be promoted by maintaining the degree.

  Thus, the organic-inorganic hybrid resin aqueous dispersion containing a zirconium atom and a silicon atom can be obtained. The obtained organic-inorganic hybrid resin aqueous dispersion contains an organic solvent used for dissolving the polymer (a) and an alcohol produced by hydrolysis condensation of a hydrolyzable group such as an alkoxy group. . These organic solvents and alcohols may remain in the aqueous dispersion, but it is preferable to remove at least a part of them by distillation to reduce their content.

  The organic-inorganic hybrid resin aqueous dispersion prepared as described above has an average particle size of about 10 to 1000 nm, preferably 10 to 800 nm. The solid content is determined based on the type of the polymer (a), the amount of acid groups and / or neutralized acid groups introduced into the polymer (a), the amount of zirconium atoms introduced, and the removal of the organic solvent. Although there is a difference depending on the amount and the like, it is generally as high as 15 to 50% by weight. Thus, the point which can make solid content rate high is one of the characteristics of the organic-inorganic hybrid resin aqueous dispersion of this invention. Moreover, the organic-inorganic hybrid resin aqueous dispersion of the present invention is excellent in storage stability and has a characteristic that no significant change in viscosity occurs even when stored at room temperature for several months.

  Next, utilization of the organic-inorganic hybrid resin aqueous dispersion prepared as described above will be described. The organic-inorganic hybrid resin in this aqueous dispersion contains a hydroxyl group (Zr) derived from an acid group such as a carboxyl group as a reactive functional group, a neutralized acid group such as a carboxylate group, and an alkoxy group bonded to a zirconium atom. -OH) group and a hydroxyl group (Si-OH) group derived from an alkoxy group bonded to a silicon atom. Therefore, when the organic-inorganic hybrid resin aqueous dispersion is applied to a substrate or the like and dried, bonds such as Zr-OC (O)-, Zr-O-Zr, Zr-O-Si, Si-O-Si are bonded. Formed, that is, self-crosslinked to form a cured product.

  Moreover, the organic-inorganic hybrid resin aqueous dispersion of the present invention has a more excellent curability by blending a curing agent (D) having a functional group that reacts with a functional group contained in the organic-inorganic hybrid resin. It can be set as the curable resin composition of invention. In addition, in advance, as the polymer (a), a functional group other than an acid group, a neutralized acid group, a hydrolyzable silyl group and a silanol group, such as a hydroxyl group, a carbonyl group, an alkoxymethylamide group, a hydroxymethylamide, By using a polymer having a functional group such as a ketone carbonyl group, various functional groups can be introduced into the organic-inorganic hybrid resin, and a curing agent having a functional group that reacts with these functional groups can be blended.

  Typical examples of the curing agent (D) used in preparing the curable resin composition of the present invention from the organic-inorganic hybrid resin aqueous dispersion and the curing agent (D) include a hydroxyl group bonded to a silicon atom. And / or a compound having a hydrolyzable group bonded to a silicon atom, a compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule, and a water having an epoxy group bonded to a silicon atom in one molecule Compound having both decomposable group, compound having both amino group and hydrolyzable group bonded to silicon atom in one molecule, polyisocyanate compound, block polyisocyanate compound, polyepoxy compound, polycyclocarbonate compound, amino resin, Primary or secondary amide group-containing compound, polyaziridine compound, polycarbodiimide compound, With a compound having two carboxylic acid anhydride groups, polyoxazoline compounds, polyhydrazide compounds such as these, these compounds may be a single use, or may be a combination of two or more thereof.

  As a typical example of the above-mentioned silicon compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, it is exemplified as a typical example of an alkoxysilane compound (c-3). Various compounds, their hydrolytic condensates, partial hydrolytic condensates, etc. are mentioned.

  Specific examples of the compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl-methyldimethoxysilane, 3- Examples thereof include silicon compounds such as isocyanate propyltriethoxysilane and 3-isocyanatopropyl-methyldiethoxysilane.

  Specific examples of the compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl-methyldimethoxysilane, Silicon compounds such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl-methyldiethoxysilane; partial hydrolysis condensates obtained by partial hydrolysis condensation of one of these silicon compounds; or these Examples thereof include partial cohydrolysis condensates obtained by two or more types of partial hydrolysis condensation of silicon compounds.

  Specific examples of the polyisocyanate compound include aromatic diisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane-4,4'-diisocyanate; , Α, α, α ′, α′-tetramethyl-metaxylylene diisocyanate and the like; hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diisocyanate, dicyclohexylmethane-4,4 ′ -Aliphatic or alicyclic diisocyanates such as diisocyanates; addition of various polyisocyanates as described above with polyhydric alcohols Various prepolymers having an isocyanate group obtained by reaction; various prepolymers having an isocyanurate ring obtained by cyclization and trimerization of various polyisocyanates as described above; And various polyisocyanates having a biuret structure obtained by reacting various polyisocyanates with water.

  Specific examples of the block polyisocyanate compound described above include cyclization of the block polyisocyanate compound and the isocyanate group obtained by blocking the various polyisocyanate compounds as described above with various blocking agents as described later. Examples thereof include compounds containing a uretdione structure obtained by dimerization.

  Specific examples of the blocking agent used in preparing the block polyisocyanate compound include carbinol group-containing compounds such as methanol, ethanol, benzyl alcohol, and lactic acid ester; phenolic compounds such as phenol, salicylic acid ester, and cresol. Hydroxyl-containing compounds; Amide compounds such as ε-caprolactam, 2-pyrrolidone and acetanilide; Oximes such as acetone oxime and methyl ethyl ketoxime; Active methylene compounds such as methyl acetoacetate, ethyl acetoacetate and acetylacetone.

  Specific examples of the polyepoxy compound described above include polyglycidyl ethers of aliphatic or alicyclic polyols such as ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, hydrogenated bisphenol A and the like. Polyglycidyl ethers of aromatic diols such as hydroquinone, catechol, resorcin, bisphenol A and bisphenol F; aromatic diol derivatives such as ethylene oxide and propylene oxide adducts of aromatic diols as described above Diglycidyl ethers; polyglycidyl ethers of polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol; adipic acid, butane tetraca Polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as boric acid, propanetricarboxylic acid, phthalic acid, terephthalic acid, trimellitic acid; bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexyl And alicyclic polyepoxy compounds such as methyl-3,4-epoxycyclohexylcarboxylate.

  Specific examples of the polycyclocarbonate compound are obtained by converting an epoxy group into a cyclocarbonate group by reacting various polyepoxy compounds as described above with, for example, carbon dioxide in the presence of a catalyst. Examples include polycyclocarbonate compounds having a 5-membered ring cyclocarbonate group.

  Specific examples of the polyoxazoline compound include 2,2′-p-phenylene-bis (1,3-oxazoline), 2,2′-tetramethylene-bis (1,3-oxazoline), 2,2′-octa A low molecular weight poly (1,3-oxazoline) compound such as methylene-bis (1,3-oxazoline); a homopolymer of an oxazoline group-containing vinyl monomer such as 2-isopropenyl-1,3-oxazoline; Examples thereof include a vinyl polymer containing a 1,3-oxazoline group obtained by copolymerizing this and a copolymerizable vinyl monomer.

  Specific examples of amino resins include alkylol groups obtained by reacting amino group-containing compounds such as melamine, benzoguanamine, acetoguanamine, urea and glycouril with aldehyde compounds (or aldehyde-supplying substances) such as formaldehyde and acetaldehyde. An amino resin having an alkoxyalkyl group obtained by reacting an amino resin having such an alkylol group with a lower alcohol such as methanol, ethanol, n-butanol or isobutanol.

  Specific examples of the polyhydrazide compound include dicarboxylic acid dihydrazides such as malonic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide.

  When the curing agent (D) is blended with the organic-inorganic hybrid resin aqueous dispersion, the curing agent (D) is organic-inorganic when the curing agent (D) is water-soluble or has a certain degree of hydrophilicity. A composition that is uniformly dissolved or uniformly dispersed in the aqueous hybrid resin dispersion can be obtained.

  However, when the hydrophilicity of the curing agent (D) is low, even when mixed with the organic-inorganic hybrid resin aqueous dispersion, a composition in which the curing agent (D) is uniformly dissolved or dispersed cannot be obtained. . In such a case, the hydrophilicity of the curing agent (D) can be improved by introducing a hydrophilic group into the curing agent (D) by various methods to obtain a more uniform composition. I can do it.

  When the curing agent (D) is a polymer, the curing agent can be used in any form of a solventless liquid, an organic solvent solution, an aqueous solution, or an aqueous dispersion. And when a hardening | curing agent (D) is a vinyl polymer especially, it is also suitable to use as an emulsion polymer.

  When the curable resin composition of the present invention is prepared from the organic-inorganic hybrid resin aqueous dispersion and the curing agent (D), the mixing ratio of the organic-inorganic hybrid resin aqueous dispersion and the curing agent (D) is as follows. It is necessary to set appropriately according to the kind of D).

  When the curing agent (D) is a compound having a hydrolyzable group and / or silanol group bonded to a silicon atom, the curing agent is used with respect to 100 parts by weight of the solid content of the organic-inorganic hybrid resin aqueous dispersion. The curing agent (D) is added so that the solid content of (D) is 0.1 to 200 parts by weight, preferably 0.5 to 150 parts by weight, more preferably 5 to 50 parts by weight. That's fine.

  When the curing agent (D) is a compound having both an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyisocyanate compound or a block polyisocyanate compound, an organic-inorganic hybrid resin aqueous dispersion The amount of the isocyanate group or blocked isocyanate group contained in the curing agent (D) is 0.1 to 10 equivalents relative to 1 equivalent of the functional group that reacts with the isocyanate group or blocked isocyanate group contained in the solid content of the body, What is necessary is just to mix | blend a hardening | curing agent (D) so that it may preferably become in the range which is 0.3-5 equivalent, More preferably, it is 0.5-2 equivalent.

  When the curing agent (D) is a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, a polyepoxy compound, a polycyclocarbonate compound, or a polyoxazoline compound, organic-inorganic Epoxy group contained in curing agent (D) with respect to 1 equivalent of functional group that reacts with epoxy group, cyclocarbonate group or oxazoline group, for example, carboxyl group, contained in solid content of aqueous hybrid resin dispersion Amount, cyclocarbonate group amount or oxazoline group amount in the range of 0.2 to 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents, more preferably in the range of 0.7 to 2 equivalents. What is necessary is just to mix | blend a hardening | curing agent (D) so that it may become.

  When the curing agent (D) is an amino resin, the solid content of the curing agent (D) is 1 to 200 parts by weight with respect to 100 parts by weight of the solid content of the organic-inorganic hybrid resin aqueous dispersion. The curing agent (D) may be blended so as to be in the range of preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight.

  When the curing agent (D) is a compound having a primary or secondary amide group, it is one of functional groups that react with the primary or secondary amide group contained in the organic-inorganic hybrid resin aqueous dispersion. The amount of primary or secondary amide group contained in the curing agent (D) with respect to the equivalent is within a range of 0.2 to 5.0 equivalents, preferably within a range of 0.5 to 3.0 equivalents, What is necessary is just to mix | blend a hardening | curing agent (D) so that it may become in the range of 0.7-2 equivalent more preferably.

  When the curing agent (D) is a polyhydrazide compound, the curing agent (D) is used for 1 equivalent of a carbonyl group derived from a ketone or an aldehyde contained in the solid content of the organic-inorganic hybrid resin aqueous dispersion. ) The amount of hydrazide groups contained therein is in the range of 0.2 to 5.0 equivalents, preferably in the range of 0.5 to 3.0 equivalents, more preferably in the range of 0.7 to 2 equivalents. What is necessary is just to mix | blend a hardening | curing agent (D) so that it may become.

  The organic-inorganic hybrid resin aqueous dispersion of the present invention prepared as described above or the curable resin composition of the present invention containing this aqueous dispersion and a curing agent (D) is a clear composition containing no color pigment. It can be used as a composition, and can also be used as a colored composition by blending various organic or inorganic pigments.

  The aqueous organic-inorganic hybrid resin dispersion or curable resin composition of the present invention further includes a curing catalyst, a flow regulator, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, or a plasticizer. In various forms such as various additives such as, can be used for various purposes.

  The organic-inorganic hybrid resin aqueous dispersion or curable resin composition of the present invention can be used for various applications such as paints, adhesives, fiber treatment agents, etc., but the organic-inorganic hybrid resin aqueous dispersion or curable of the present invention. One of the preferred applications in which the characteristics of the resin composition are exhibited is a paint application, and the paint of the present invention comprises the aqueous organic-inorganic hybrid resin dispersion or curable resin composition of the present invention. .

  The paint containing such an organic-inorganic hybrid resin aqueous dispersion or curable resin composition can be used for various purposes in the same manner as various paints, but when used for overcoating exterior materials, it is weather resistant. It exhibits extremely excellent characteristics, and when used for direct metal coating, it exhibits extremely excellent corrosion resistance.

  The curing conditions of such paints include the presence or absence of the curing agent (D) component, the type when it contains the curing agent (D), the presence or absence of a curing catalyst, the type and amount when it contains a curing catalyst, etc. Depending on the temperature, it can be dried for 1 to 14 days at room temperature or by baking for about 10 seconds to 3 hours, preferably about 20 seconds to 2 hours in a temperature range of about 60 ° C. to 250 ° C. A highly practical cured film can be obtained.

  The present invention also provides a coated product coated with the above-described coating material. In the present invention, there are various types of base materials used as an object to be coated. Typical examples include various metal substrates, inorganic substrates, plastic substrates, paper or wood-based substrates.

  Among these various substrates, specific examples of the metal substrate are obtained from simple metals such as iron, nickel, chromium, aluminum, magnesium, copper, and lead; from the aforementioned simple metals such as stainless steel and brass. Alloys: Metals plated with iron, etc. plated with metals such as zinc, nickel, chrome, etc .; Chromate treatment or phosphate treatment for the above-mentioned simple metals, alloys or plated metals, etc. Metals etc. which gave chemical conversion treatments etc. are mentioned.

  In addition, examples of the inorganic base material include cement-based materials, silicate-based materials such as calcium silicate, gypsum-based materials, asbestos-based materials, ceramic materials and the like, and specific examples thereof include: Examples of on-site construction (wet) base materials include exposed concrete, cement mortar, gypsum plaster, dolomite plaster, and plaster, and factory-produced (dry) base materials include lightweight cellular concrete (ALC) and glass fiber reinforcement. Calcium silicate, gypsum board, tiles and other various clay fired products or glass.

  Specific examples of plastic substrates include molded products of thermoplastic resins such as polystyrene, polycarbonate, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate, and polyethylene terephthalate; unsaturated Examples thereof include molded products of thermosetting resins such as polyester resins, phenol resins, cross-linked polyurethane, cross-linked acrylic resins, cross-linked saturated polyester resins, and the like.

  These various substrates are used in various forms such as plate-like, spherical, film-like, sheet-like or large-sized structures or complex-shaped assemblies or molded articles depending on applications. There is no particular limitation.

  By applying and curing the coating material of the present invention on various substrates as described above, the coated product according to the present invention can be obtained. At that time, (I) the paint is directly applied to the base material, (II) an undercoat paint is applied on the base material in advance, and then the paint is applied as an overcoat, (III) the base material is applied. The coated product of the present invention can be obtained by a coating method such as applying the paint of the present invention as an undercoat and then applying another topcoat to form a coating film.

  In order to obtain a coated product according to the present invention by the direct coating method as in (I) above, the paint of the present invention is applied to the above-mentioned various substrates by brush coating, roller coating, spray coating. After coating by a coating method such as dip coating, flow coater coating, roll coater coating, electrodeposition coating, etc., it may be cured.

  And the base material coat | covered with the uncured top coat film is left to stand at normal temperature for about 1 to 14 days, or is heated at 60 to 250 ° C. for about 10 seconds to 3 hours, thereby weather resistance and corrosion resistance. It is possible to obtain a desired coated product coated with a coating film excellent in the above.

  On the other hand, various coating materials can be used as the undercoat used in obtaining the coated product according to the present invention by the method (II), and typical examples thereof include an aqueous solution. Examples include mold-type or dispersion-type paints; organic solvent-based solution-type or dispersion-type paints; powder paints, solvent-free liquid paints, and the like.

  In order to obtain such a coated product of the present invention by coating such a base coating on various substrates and then applying and curing the coating of the present invention as a top coating, after drying or curing the base coating in advance, the above (I The coating material provided with a multilayer coating film by applying the coating material of the present invention as a top coating material and curing under the curing conditions employed in the above (I) by various coating methods applied by the method of Can be obtained. In addition, the base coating is applied to the base material, the coating of the present invention is applied as a top coating while the coating formed from the base coating is undried or uncured, and the top coating is applied simultaneously with drying or curing of the base coating. A cured product having a multilayer coating film can be obtained by curing the film.

  On the other hand, various coating materials can be used as the top coating used in obtaining the coated product according to the present invention by the method (III), and typical examples thereof include an aqueous solution. Examples include mold-type or dispersion-type paints; organic solvent-based solution-type or dispersion-type paints; powder paints, solvent-free liquid paints, and the like.

  In order to obtain a coated product according to the present invention using such a top coating material, first, the coating material of the present invention is used as an undercoating material on various substrates by various coating methods applied by the method (I). After coating and pre-curing under the curing conditions as employed in (I) above, the above-mentioned top coating can be applied and dried or cured to obtain a coated product having a multilayer coating film. . In addition, after applying the coating material of the present invention to the base material and applying the above coating material as a top coating material while the coating film formed from the coating material of the present invention is uncured, the undercoating film is simultaneously dried or cured with the top coating film. A cured product having a multilayer coating film can be obtained by curing.

  As described above, a coated product according to the present invention coated with a cured coating film having excellent weather resistance and corrosion resistance can be obtained. As a more specific example of such a coated product, a metal as a substrate is used. Automobiles, motorcycles, trains, and other transportation-related equipment that use base materials; TVs, radios, refrigerators, washing machines, coolers, cooler outdoor units that use metal or plastic base materials as base materials , Computers, other household appliances; various inorganic tiles and roofing materials, metal roofing materials, inorganic outer wall materials, metal wall materials, solar cell protection materials, metal window frames, glass, Building materials such as metal or wooden doors or inner wall materials; outdoor structures such as road signs, guardrails, bridges, tanks, chimneys, buildings; polyester resin films, acrylic resin films, hooks While various coating films various painted in an organic film such as a resin film and the like, coated article according to the present invention, in such applications, as it can be utilized effectively.

  Next, the present invention will be described more specifically by reference examples, examples and comparative examples, but the present invention is not limited to these examples. In the following, parts and% are all based on weight except for the neutralization rate and gloss retention of carboxyl groups.

Synthesis Example 1 [Preparation of Composite Resin (AB)]
In a reaction vessel equipped with a stirrer, a thermometer, a condenser, a dropping funnel and a nitrogen gas inlet, 18.0 parts of propylene glycol mono-n-propyl ether (PNP), 73.0 parts of isopropyl alcohol (IPA), phenyltri 26.8 parts of methoxysilane (PTMS) and 16.2 parts of dimethyldimethoxysilane (DMDMS) were charged, and the temperature was raised to 85 ° C. with stirring in a nitrogen gas atmosphere. Next, at the same temperature, 56.4 parts of methyl methacrylate (MMA), 46.2 parts of n-butyl methacrylate (BMA), 26.2 parts of n-butyl acrylate (BA), 8.0 parts of acrylic acid (AA), A mixture consisting of 4.2 parts of 3-methacryloyloxypropyltrimethoxysilane (MPTMS), 9.9 parts of tert-butylperoxy-2-ethylhexanoate (TBPO) and 7.0 parts of PNP was added dropwise over 4 hours. . The mixture was heated and stirred at the same temperature for 2 hours to obtain an acrylic polymer solution containing a carboxyl group having a weight average molecular weight of 15,400 and a hydrolyzable silyl group. Next, a mixture of 0.04 part of “Fossrex A-3” [Isopropyl acid phosphate manufactured by Sakai Chemical Industry Co., Ltd.] and 12.2 parts of deionized water was added, and the temperature was lowered to 80 ° C. Carboxylic group-containing acrylic system in which alkoxysilane is hydrolyzed by continuing heating and stirring for 16 hours, and further condensed with an acrylic polymer to have a nonvolatile content (NV) of 55.7% and a solution acid value of 21.4 mgKOH / g A solution of a composite resin having a polymer segment and a polysiloxane segment was obtained. Hereinafter, this solution is abbreviated as a composite resin solution (AB-1).

Synthesis Example 2 [Preparation of composite resin (AB)]
In a reaction vessel similar to Synthesis Example 1, 251.2 parts of PNP, 199.5 parts of PTMS and 120.9 parts of DMDMS were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen gas atmosphere. Next, at the same temperature, a mixture consisting of 52.5 parts of MMA, 49.5 parts of BMA, 35.0 parts of BA, 32.9 parts of AA, 5.3 parts of MPTMS, 13.0 parts of TBPO and 8.8 parts of PNP was added dropwise over 4 hours. . Thereafter, the mixture was heated and stirred at the same temperature for 2.5 hours to obtain an acrylic polymer solution containing a carboxyl group having a weight average molecular weight of 14,900 and a hydrolyzable silyl group. Next, a mixture of 0.03 part of “Fossrex A-3” and 90.7 parts of deionized water was added at the same temperature, and the alkoxysilane was hydrolyzed by continuing heating and stirring for 16 hours. To obtain a solution of a composite resin having a carboxyl group-containing acrylic polymer segment and a polysiloxane segment having an NV of 41.3% and a solution acid value of 30.8 mgKOH / g. Hereinafter, this solution is abbreviated as a composite resin (AB-2) solution.

Synthesis Example 3 [Preparation of Composite Resin (AB)]
In a reaction vessel similar to that of Synthesis Example 1, in a nitrogen gas atmosphere, “PTMG-650” [Mitsubishi Chemical Co., Ltd. polytetramethylene glycol, hydroxyl group equivalent 325 g / equivalent] 500 parts, 2,2-dimethylolpropionic acid 51 Part, 307 parts isophorone diisocyanate and 572 parts ethyl acetate. Next, the mixture was heated to 75 ° C. while stirring and heated and stirred at the same temperature for 10 hours to obtain a urethane prepolymer solution having isocyanate groups at both ends. After completion of the reaction, the solution was cooled to 40 ° C.

  In a reactor similar to Synthesis Example 1, 92 parts of 3-aminopropyltriethoxysilane and 853 parts of IPA were charged, and the entire amount of the urethane prepolymer solution was added dropwise over 1 hour while stirring at 35 ° C. in a nitrogen atmosphere. Next, the temperature was raised to 50 ° C., and the mixture was heated and stirred at the same temperature for 2 hours to react the isocyanate group of the urethane prepolymer with 3-aminopropyltriethoxysilane, so that NV was 40.3% and the solution acid value was 9 A solution of a polyurethane polymer having a carboxyl group of 2 mg KOH / g and Mw of 11,300 and a hydrolyzable silyl group was obtained. Hereinafter, this solution is abbreviated as a polymer solution (a-3).

In a reaction vessel similar to Synthesis Example 1, 173.7 parts of the polymer solution (a-3) was charged, the temperature was raised to 50 ° C. with stirring, the solvent was removed under reduced pressure, and 57.0 parts of the solvent was added. Distilled off. At that time, the temperature of the contents decreased from 50 ° C to 21 ° C. The temperature was raised again to 50 ° C., and 7.0 parts of triethylamine was added at the same temperature to neutralize 100 mol% of the carboxyl group. Next, 14.3 parts of methyltrimethoxysilane (MTMS) partially hydrolyzed condensate (CH ₃ SiO _1.5 content: 70.0%) and 3.6 parts of deionized water were added and the temperature was raised to 60 ° C. The mixture is heated and stirred at the same temperature for 2 hours to co-hydrolyze and condense the triethoxysilyl group and the partial hydrolysis-condensation product of methyltrimethoxysilane contained in the polyurethane-based polymer. A solution of a composite resin having 56.5% neutralized carboxyl group-containing polyurethane polymer segment and polysiloxane segment was obtained. Hereinafter, this solution is abbreviated as a composite resin (AB-3) solution.

Synthesis Example 4 [Preparation of Zirconosiloxane Compound (C)]
MTMS (749.1 parts) was charged into the same reactor as in Synthesis Example 1, and ORGATIX ZA-60 [Zirconium tetra-n-butoxide and n-butanol manufactured by Matsumoto Fine Chemical Co., Ltd.] was vigorously stirred under air cooling in a nitrogen atmosphere. A mixture of zirconium tetra-n-butoxide 85.6%], a mixture of 448.2 parts and 100.0 parts of IPA, and a mixture of 99.0 parts of deionized water and 297.0 parts of IPA were simultaneously added dropwise over 2 hours. . During this time, the temperature of the reaction mixture rose from 26 ° C to 37 ° C. Next, the temperature was raised to 70 ° C., and the mixture was heated and stirred at the same temperature for 4.5 hours to prepare a pale yellow transparent solution of a zirconosiloxane compound containing an alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom. Obtained. From this solution, volatile components such as the solvent and the produced alcohol were distilled off under reduced pressure to obtain 778.4 parts of a pale yellow transparent liquid zirconosiloxane compound. Hereinafter, this is abbreviated as a zirconosiloxane compound (C-1).

The zirconium atom and silicon atom contained in this zirconosiloxane compound (C-1) are respectively 15.8% and 47.4% in terms of ZrO ₂ and CH ₃ SiO _1.5 . In this synthesis example, the molar ratio of water and an alkoxy group bonded to a zirconium atom (water / Zr bonded alkoxy group) is 1.38, and the molar ratio of the alkoxysilane compound to water (alkoxysilane compound / water) is 1. 00, the number ratio of zirconium atom to silicon atom (Zr / Si) is 0.18, the sum of water, alkoxy group bonded to zirconium atom and alkoxy group bonded to silicon atom (Zr bonded alkoxy group + Si bonded alkoxy group) The molar ratio [water / (Zr bonded alkoxy group + Si bonded alkoxy group)] was 0.27.

Synthesis Example 5 [Preparation of Zirconosiloxane Compound (C)]
A reactor similar to Synthesis Example 1 was charged with 61.8 parts of MTMS and 300.0 parts of IPA, and 448.2 parts of Orgatics ZA-60 and 100.0 parts of IPA were stirred vigorously under a nitrogen atmosphere under air cooling. The mixture and a mixture of 18.0 parts deionized water and 90.0 parts IPA were added dropwise simultaneously over 2 hours. During this time, the temperature of the reaction mixture rose from 16 ° C to 23 ° C. Next, the temperature was raised to 70 ° C., and the mixture was heated and stirred at the same temperature for 4.5 hours to prepare a pale yellow transparent solution of a zirconosiloxane compound containing an alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom. Obtained. From the resulting solution, volatile components such as the solvent and the generated alcohol were distilled off under reduced pressure to obtain 308.0 parts of a pale yellow, highly viscous liquid zirconosiloxane compound. Hereinafter, this is abbreviated as a zirconosiloxane compound (C-2).

The zirconium atom and silicon atom contained in this zirconosiloxane compound (C-2) are 40.0% and 10.9% in terms of ZrO ₂ and CH ₃ SiO _1.5 , respectively. In this synthesis example, the molar ratio of water and an alkoxy group bonded to a zirconium atom (water / Zr bonded alkoxy group) is 0.25, and the molar ratio of the alkoxysilane compound to water (alkoxysilane compound / water) is 0. 50, the atomic ratio (Zr / Si) of zirconium atom to silicon atom is 2.00, the sum of water, the alkoxy group bonded to the zirconium atom and the alkoxy group bonded to the silicon atom (Zr bonded alkoxy group + Si bonded alkoxy group) The molar ratio [water / (Zr bond alkoxy group + Si bond alkoxy group)] was 0.18.

Synthesis Example 6 [Preparation of Zirconosiloxane Compound (C)]
In a reactor similar to Synthesis Example 1, 136.2 parts of MTMS and 200.0 parts of IPA were charged, and while the mixture was vigorously stirred under air cooling under nitrogen atmosphere, ORGATIZ ZA-40 [Zirconium tetra- produced by Matsumoto Fine Chemical Co., Ltd.] n-propoxide and n-propanol mixture, zirconium tetra-n-propoxide content 74.5%] simultaneously 439.7 parts IPA 100 parts mixture and deionized water 36.0 parts IPA 180.0 parts It was dripped in 1 hour. During this time, the temperature of the reaction mixture increased from 20 ° C to 31 ° C. Next, the temperature was raised to 70 ° C. and heated and stirred at the same temperature for 4 hours to obtain a yellow transparent solution of a zirconosiloxane compound containing an alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom. From the obtained solution, a part of volatile components such as the solvent and the generated alcohol was distilled off under reduced pressure, 125.0 parts of n-butanol was added and mixed well, and 488.0 parts of yellowish brown and transparent A solution of the zirconosiloxane compound was obtained. Hereinafter, this solution is abbreviated as a zirconosiloxane solution (C-3).

Zirconium atoms and silicon atoms contained in this zirconosiloxane solution (C-3) are 25.2% and 13.8% in terms of ZrO ₂ and CH ₃ SiO _1.5 , respectively. In this synthesis example, the molar ratio of water and an alkoxy group bonded to a zirconium atom (water / Zr-bonded alkoxy group) is 0.50, and the molar ratio of alkoxysilane compound to water (alkoxysilane compound / water) is 0.00. 50, the atomic ratio (Zr / Si) of zirconium atom to silicon atom is 1.00, the sum of water, alkoxy group bonded to zirconium atom and alkoxy group bonded to silicon atom (Zr bonded alkoxy group + Si bonded alkoxy group) The molar ratio [water / (Zr bonded alkoxy group + Si bonded alkoxy group)] was 0.29.

Synthesis Example 7 [Preparation of Zirconosiloxane Compound (C)]
In a reactor similar to Synthesis Example 1, 408.6 parts of MTMS, 198.3 parts of phenyltrimethoxysilane, and 300.0 parts of IPA were charged, and the mixture was vigorously stirred under air cooling under a nitrogen atmosphere while ORGATIXX ZA-60 448 was added. A mixture of 2 parts and 100.0 parts of IPA and 72.0 parts of deionized water and 216.0 parts of IPA were added dropwise simultaneously over 2 hours. During this time, the temperature of the reaction mixture increased from 10 ° C to 22 ° C. Next, the temperature was raised to 70 ° C. and heated and stirred at the same temperature for 4 hours to obtain a pale yellow transparent solution of a zirconosiloxane compound containing an alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom. . From the obtained solution, volatile components such as the solvent and the generated alcohol were distilled off under reduced pressure to obtain 715.8 parts of a pale yellow transparent liquid zirconosiloxane compound. Hereinafter, this is abbreviated as a zirconosiloxane compound (C-4).

The zirconium atom and silicon atom contained in this zirconosiloxane compound (C-4) are 17.2% in terms of ZrO ₂ , CH ₃ SiO _1.5 and C ₆ H ₅ SiO _1.5 , respectively. , 28.1% and 18.1%. In this synthesis example, the molar ratio of water and an alkoxy group bonded to a zirconium atom (water / Zr-bonded alkoxy group) is 1.00, and the molar ratio of alkoxysilane compound to water (alkoxysilane compound / water) is 1. 00, the number ratio of zirconium atom to silicon atom (Zr / Si) is 0.25, the sum of water, the alkoxy group bonded to the zirconium atom and the alkoxy group bonded to the silicon atom (Zr bonded alkoxy group + Si bonded alkoxy group) The molar ratio [water / (Zr bonded alkoxy group + Si bonded alkoxy group)] was 0.25.

Synthesis Example 8 [Preparation of Zirconosiloxane Compound (C)]
A reactor similar to Synthesis Example 1 was charged with 937.4 parts of tetraethoxysilane and 250.0 parts of dioxane, and 448.2 parts of ORGATIZ ZA-60 and dioxane were stirred vigorously under a nitrogen atmosphere under air cooling. 100.0 parts of the mixture and 81.0 parts of deionized water and 243.0 parts of dioxane were added dropwise simultaneously over 2 hours. During this time, the temperature of the reaction mixture rose from 21 ° C to 27 ° C. Next, the temperature is raised to 70 ° C., and the mixture is heated and stirred at the same temperature for 3.5 hours to contain a zirconosiloxane compound having an alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom. Got. From the resulting solution, volatile components such as tetraalkoxysilane having a structure in which a part of ethoxy group of tetraethoxysilane as a by-product is substituted with methoxy group and n-butoxy group are reduced under reduced pressure. To obtain 666.0 parts of a pale yellow transparent liquid zirconosiloxane compound. Hereinafter, this is abbreviated as a zirconosiloxane compound (C-5).

The zirconosiloxane compound (C-5) was diluted with IPA and then dried in a hot air dryer at 110 ° C. for 2 hours to obtain a flaky solid of the hydrolytic condensate of the zirconosiloxane. When the flaky solid was analyzed with an energy dispersive X-ray analyzer (SEM / EDS), the atomic ratio (Zr / Si) of zirconium atoms to silicon atoms contained was 1 / 2.7. . Therefore, the zirconium atom and silicon atom contained in this zirconosiloxane (C-5) are respectively 18.5% and 24.4% in terms of ZrO ₂ and SiO ₂ . In this synthesis example, the molar ratio of water and an alkoxy group bonded to a zirconium atom (water / Zr-bonded alkoxy group) is 1.13, and the molar ratio of alkoxysilane compound to water (alkoxysilane compound / water) is 1. 00, the atomic ratio of zirconium atom to silicon atom (Zr / Si) is 0.22, the sum of water, the alkoxy group bonded to the zirconium atom and the alkoxy group bonded to the silicon atom (Zr bonded alkoxy group + Si bonded alkoxy group) The molar ratio [water / (Zr bonded alkoxy group + Si bonded alkoxy group)] was 0.38.

Example 1 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In the same reactor as in Synthesis Example 1, 311.9 parts of the composite resin solution (AB-1) was charged and heated to 40 ° C. while stirring in a nitrogen atmosphere. Next, while stirring at the same temperature, 14.3 parts of triethylamine was added and stirred for 10 minutes. Thereby, 100 mol% of the carboxyl groups contained in the composite resin solution (AB-1) were neutralized to obtain a composite resin solution having neutralized carboxyl groups (carboxylate groups). Next, a mixture consisting of 69.3 parts of zirconosiloxane (C-1) and 70.0 parts of IPA was added while stirring at the same temperature, followed by stirring at the same temperature for 20 minutes. Furthermore, 504.0 parts of deionized water was added dropwise at the same temperature while stirring for 10 minutes to carry out phase inversion emulsification, and then stirred for 20 minutes at the same temperature to hydrolyze and condense the zirconosiloxane part. . Then, over 1 hour at an internal temperature of 45 to 60 ° C., a part of water was distilled off under reduced pressure together with methanol, IPA and n-butanol, and zirconium having an NV of 34.9% and an average particle diameter of 97 nm was obtained. An organic-inorganic hybrid resin aqueous dispersion containing atoms and silicon atoms was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-1). The calculated value of the solid content acid value of the organic-inorganic hybrid resin is 30.5 mgKOH / g, and the weight ratio of the contained components is as follows.
Acrylic polymer: ZrO ₂ : C ₆ H ₅ SiO _1.5 : (CH ₃ ) ₂ SiO: CH ₃ SiO _1.5 = 66.5: 5.1: 8.2: 4.7: 15.5

  The viscosity immediately after preparation of the dispersion (Ds-1) was 27 mPa · s, and the viscosity after storage for 3 months at 30 ° C. was 31 mPa · s, which was excellent in storage stability.

Example 2 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In the same reactor as in Synthesis Example 1, 51.5 parts of the composite resin solution (AB-2) was charged, and 5.5 parts of triethylamine was added with stirring at 30 ° C. in a nitrogen atmosphere, followed by stirring for 10 minutes. . Thereby, 100 mol% of the carboxyl groups contained in the composite resin solution (AB-2) were neutralized to obtain a composite resin solution having neutralized carboxyl groups (carboxylate groups). Next, a mixture of 19.3 parts of zirconosiloxane (C-1) and 15.0 parts of IPA was added while stirring at the same temperature, and then stirred at the same temperature for 5 minutes. Further, 70.0 parts of deionized water was added dropwise with stirring for 5 minutes at the same temperature to effect phase inversion emulsification, then the temperature was raised to 50 ° C., and stirring was performed for 20 minutes at the same temperature. Hydrolytic condensation was performed. Then, methanol, IPA, n-butanol and a part of water were distilled off under reduced pressure over an hour at an internal temperature of 45 to 60 ° C., and zirconium having an NV of 37.0% and an average particle diameter of 450 nm was obtained. An organic-inorganic hybrid resin aqueous dispersion containing atoms and silicon atoms was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-2). The calculated value of the solid content acid value of the organic-inorganic hybrid resin is 48.6 mgKOH / g, and the weight ratios of the components contained are as follows.
Acrylic polymer: ZrO ₂ : C ₆ H ₅ SiO _1.5 : (CH ₃ ) ₂ SiO: CH ₃ SiO _1.5 = 30.0: 8.7: 22.3: 12.8: 26.2

  The viscosity immediately after preparation of the dispersion (Ds-2) was 360 mPa · s, the viscosity after storage at 30 ° C. for 3 months was 375 mPa · s, and was excellent in storage stability.

Example 3 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In a reactor similar to Synthesis Example 1, 311.9 parts of the composite resin solution (AB-1) was charged, and 24.0 parts of triethylamine was added while stirring at 30 ° C. in a nitrogen atmosphere, followed by stirring for 10 minutes. . Thereby, 100 mol% of the carboxyl groups contained in the composite resin solution (AB-1) were neutralized to obtain a composite resin solution having neutralized carboxyl groups (carboxylate groups). Next, a mixture consisting of 64.6 parts of zirconosiloxane (C-2) and 70.0 parts of IPA was added while stirring at the same temperature, followed by stirring at the same temperature for 5 minutes. Further, 480.0 parts of deionized water was added dropwise at the same temperature while stirring for 10 minutes, and after phase inversion emulsification, the temperature was raised to 50 ° C., and the mixture was stirred at the same temperature for 30 minutes. Hydrolytic condensation was performed. Then, methanol, IPA, n-butanol and a part of water are distilled off under reduced pressure at an internal temperature of 45-60 ° C. over 1.5 hours, NV is 35.0%, and average particle size is 120 nm. An aqueous organic-inorganic hybrid resin dispersion containing zirconium atoms and silicon atoms was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-3). The calculated value of the solid content acid value of the organic-inorganic hybrid resin is 32.1 mgKOH / g, and the weight ratios of the contained components are as follows.
Acrylic polymer: ZrO ₂ : C ₆ H ₅ SiO _1.5 : (CH ₃ ) ₂ SiO: CH ₃ SiO _1.5 = 70.0: 12.8: 8.7: 5.0: 3.5

  In addition, the viscosity immediately after preparation of the dispersion (Ds-3) was 145 mPa · s, the viscosity after storage at 30 ° C. for 3 months was 140 mPa · s, and the storage stability was excellent.

Example 4 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In a reactor similar to Synthesis Example 1, 311.9 parts of the composite resin solution (AB-1) was charged, and 30.0 parts of triethylamine was added while stirring at 30 ° C. in a nitrogen atmosphere, followed by stirring for 10 minutes. . Thereby, 100 mol% of the carboxyl groups contained in the composite resin solution (AB-1) were neutralized to obtain a composite resin solution having neutralized carboxyl groups (carboxylate groups). Next, after stirring at the same temperature, a mixture consisting of 84.8 parts of the zirconosiloxane solution (C-3) and 50.0 parts of IPA was added, followed by stirring at the same temperature for 5 minutes. Further, 470.0 parts of deionized water was added dropwise at the same temperature while stirring for 10 minutes, and after phase inversion emulsification, the temperature was raised to 50 ° C., and the mixture was stirred at the same temperature for 20 minutes. Hydrolytic condensation was performed. Then, methanol, IPA, n-propanol, n-butanol and a part of water were distilled off under reduced pressure at an internal temperature of 40 to 60 ° C. for 1.5 hours, so that NV was 36.1% and average An organic-inorganic hybrid resin aqueous dispersion containing zirconium atoms and silicon atoms having a particle diameter of 135 nm was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-4). The calculated value of the solid content acid value of the organic-inorganic hybrid resin is 32.1 mgKOH / g, and the weight ratios of the contained components are as follows.
Acrylic polymer: ZrO ₂ : C ₆ H ₅ SiO _1.5 : (CH ₃ ) ₂ SiO: CH ₃ SiO _1.5 = 70.0: 10.5: 8.7: 5.0: 5.8

  The viscosity immediately after preparation of the dispersion (Ds-4) was 160 mPa · s, the viscosity after storage at 30 ° C. for 3 months was 175 mPa · s, and the storage stability was excellent.

Example 5 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In the same reactor as in Synthesis Example 1, 51.5 parts of the composite resin solution (AB-2) was charged, and 5.5 parts of triethylamine was added with stirring at 30 ° C. in a nitrogen atmosphere, followed by stirring for 10 minutes. . Thereby, 100 mol% of the carboxyl groups contained in the composite resin solution (AB-2) were neutralized to obtain a composite resin solution having a neutralized carboxyl group (carboxylate group). Next, a mixture consisting of 19.3 parts of zirconosiloxane (C-4) and 15.0 parts of IPA was added while stirring at the same temperature, followed by stirring at the same temperature for 10 minutes. Further, 70.0 parts of deionized water was added dropwise with stirring for 5 minutes at the same temperature to effect phase inversion emulsification, then the temperature was raised to 50 ° C., and stirring was performed for 20 minutes at the same temperature. Hydrolytic condensation was performed. Then, methanol, IPA, n-butanol and a part of water are distilled off under reduced pressure over an hour at an internal temperature of 40 to 60 ° C., and zirconium having an NV of 35.5% and an average particle diameter of 175 nm is obtained. An organic-inorganic hybrid resin aqueous dispersion containing atoms and silicon atoms was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-5). The calculated value of the solid content acid value of the organic-inorganic hybrid resin is 48.6 mgKOH / g, and the weight ratios of the components contained are as follows.
Acrylic polymer: ZrO ₂ : C ₆ H ₅ SiO _1.5 : (CH ₃ ) ₂ SiO: CH ₃ SiO _1.5 = 30.0: 9.5: 32.2: 12.8: 15.5

  The viscosity immediately after preparation of the dispersion (Ds-5) was 180 mPa · s, and the viscosity after storage at 30 ° C. for 3 months was 195 mPa · s, which was excellent in storage stability.

Comparative Example 1 [Preparation of Comparative Acrylic Polymer-Polysiloxane Hybrid Resin Aqueous Dispersion]
As in Example 3, 100 mol% of the carboxyl groups contained in the composite resin solution (AB-1) was neutralized to obtain a composite resin solution containing neutralized carboxyl groups (carboxylate groups). It was. Subsequently, 47.0 parts of MTMS partial hydrolysis condensate (CH ₃ SiO _1.5 content: 70.0%) was added while stirring at the same temperature, and the mixture was stirred at the same temperature for 20 minutes. After adding 470.0 parts of deionized water dropwise over 15 minutes with stirring, phase inversion emulsification was carried out, and then the temperature was raised to 60 ° C. and stirring was performed for 2 hours to obtain a partial hydrolysis condensate of methyltrimethoxysilane. The hydrolysis condensation of was carried out. Then, over 1.5 hours at an internal temperature of 40 to 55 ° C., methanol, IPA and a part of water were distilled off under reduced pressure to obtain an acrylic polymer having an NV of 38.5% and an average particle size of 110 nm. A polysiloxane hybrid resin aqueous dispersion was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (RDs-1). The calculated solid content acid value of the acrylic polymer-polysiloxane hybrid resin in the dispersion (RDs-1) is 30.9 mgKOH / g, and the weight ratios of the components contained are as follows.
Acrylic polymer: C ₆ H ₅ SiO _1.5 : (CH ₃ ) ₂ SiO: CH ₃ SiO _1.5 = 70.0: 8.7: 5.0: 16.3

  The viscosity immediately after preparation of the dispersion (RDs-1) was 80 mPa · s, the viscosity after storage at 30 ° C. for 3 months was 90 mPa · s, and the storage stability was excellent.

Comparative Example 2 [Preparation of Comparative Acrylic Polymer-Polysiloxane Hybrid Resin Aqueous Dispersion]
470 parts of IPA was charged into the same reaction vessel as in Synthesis Example 1, and the temperature was raised to 80 ° C. while stirring under a nitrogen gas flow. Next, at the same temperature, a mixture of 100 parts of styrene, 300 parts of MMA, 334 parts of BMA, 186 parts of BA, 30 parts of MPTMS, 50 parts of AA, 450 parts of IPA and 50 parts of TBPO was added dropwise over 4 hours. Thereafter, the mixture was heated and stirred at the same temperature for 16 hours to obtain an acrylic polymer solution containing a carboxyl group and a trimethoxysilyl group having NV of 53.5% and a number average molecular weight of 12,800. Hereinafter, this polymer solution is abbreviated as a polymer solution (R-2).

  In a reaction vessel equipped with a stirrer, a thermometer, a condenser and a dropping funnel, 354 parts of PTMS and 365 parts of IPA were charged and heated to 80 ° C. while stirring. Next, a mixture of 2.9 parts of “Fossrex A-3” and 96 parts of deionized water was added dropwise at the same temperature over 5 minutes, and the mixture was heated and stirred at the same temperature for 4 hours to obtain a hydrolysis condensate of PTMS. Prepared. Thereafter, 1,480 parts of the previously prepared polymer solution (R-2) was added to the PTMS hydrolysis condensate, and the mixture was stirred at 80 ° C. for 4 hours to obtain a PTMS hydrolysis condensate and an acrylic polymer. A polymer condensate was prepared.

Next, a mixture of 55 parts of triethylamine and 1,485 parts of deionized water was added dropwise at the same temperature over 30 minutes, and then methanol and IPA were distilled off by distillation under reduced pressure, so that NV was 44.9% and the average particle diameter was A 160 nm acrylic polymer-polysiloxane hybrid resin aqueous dispersion was obtained. Hereinafter, this acrylic polymer-polysiloxane hybrid resin aqueous dispersion is abbreviated as a dispersion (RDs-2). The calculated solid content acid value of the acrylic polymer-polysiloxane hybrid resin in the dispersion (RDs-2) is 30.1 mgKOH / g, and the weight ratios of the components contained are as follows.
Acrylic polymer: C ₆ H ₅ SiO _1.5 = 77.4: 22.6

Example 6
100 parts of the dispersion (Ds-1) prepared in Example 1, 6.7 parts of 3-glycidoxypropyltrimethoxysilane (GPTMS) as a curing agent, tripropylene glycol mono n-butyl ether as a film-forming aid (TPNB) 7.0 parts and 12.3 parts deionized water were mixed to prepare a curable resin composition having an NV of 33.0%. Hereinafter, this composition is abbreviated as composition (KS-1).

  Subsequently, the prepared composition (KS-1) was used as it was as a coating material to prepare a coated product as follows.

The following hot-dip galvanized steel plate and aluminum plate were used as the base material when preparing the coated product.
Hot-dip galvanized steel sheet: Hot-dip galvanized steel sheet treated with chromate (size 70 x 150 x 0.8 mm)
Aluminum plate: Chromate-treated aluminum plate (size 70 x 150 x 0.8 mm)

  The composition (KS-1) was applied to each of the hot-dip galvanized steel plate and the aluminum plate using a bar coater so that the dry film thickness was 2 μm. Next, these coated plates were allowed to stand at room temperature (25 ° C.) for 10 days to cure the coating film, thereby preparing a coated plate (1) of a hot dip galvanized steel plate and a coated plate (2) of an aluminum plate. These were evaluated for corrosion resistance and weather resistance as described below. The evaluation results are shown in Table 1.

  Corrosion resistance: A coating plate on which a cross cut was applied using a cutter knife to the coating film on the hot-dip galvanized steel plate (1) was set in a salt spray tester and subjected to a salt spray test for 480 hours. (Test based on JIS K-5400 9.1). After completion of the test, the paint plate taken out was washed with water and dried, and then the maximum width (single width) of rust generated from the cut portion was measured and used as a measure of corrosion resistance. It shows that it is excellent in corrosion resistance, so that this value is small.

Weather resistance: 20 ° gloss value when the coating film on the aluminum plate (2) was exposed for 4,000 hours under the following test conditions using the following test machine was started. The value obtained by dividing the previous 20 ° gloss value by 100 (gloss retention) was used as a measure of weather resistance. The larger this value, the better the weather resistance.
(A) Tester: Suga Test Instruments Co., Ltd. Deyupanel light control weather meter (b) Test conditions: UV exposure (60 ° C-4 hours) and wetting (40 ° C-4 hours) are repeatedly exposed as one cycle.

Examples 7-10
Compositions (KS-2) to (KS-5) were prepared by blending the respective components at the ratios described in Table 1 or Table 2. Subsequently, each composition was coated on each of the hot-dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that each of the compositions (KS-2) to (KS-5) was used. The coating film was cured under the conditions described in Table 2 to prepare a coated plate. The obtained coated plates were evaluated for corrosion resistance and weather resistance in the same manner as in Example 6. The evaluation results are shown in Tables 1 and 2.

Comparative Example 3
Composition having NV of 33.0% from 100 parts of dispersion (RDs-1) prepared in Comparative Example 1, 7.8 parts of GPTMS, 7.7 parts of PNP as a film-forming aid, and 24.8 parts of deionized water ( RKS-1) was prepared. Next, the composition (RKS-1) was applied to each of the hot dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (RKS-1) was used. The film was cured to produce a painted plate. The obtained coated plates were evaluated in the same manner as in Example 6. The evaluation results are shown in Table 3.

Comparative Example 4
Composition having NV of 35.0% from 100 parts of dispersion (RDs-2) prepared in Comparative Example 2, 8.5 parts of GPTMS, 9.0 parts of TPNB as a film-forming aid and 35.1 parts of deionized water ( RKS-2) was prepared. Next, the composition (RKS-2) was applied to each of the hot dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (RKS-2) was used. The film was cured to produce a painted plate. The obtained coated plates were evaluated in the same manner as in Example 6. The evaluation results are shown in Table 3.

Footnote “GPTMS” in Tables 1 to 3 above: 3-glycidoxypropyltrimethoxysilane “EX-614B”: Denacol EX-614B manufactured by Nagase ChemteX Corp. [sorbitol polyglycidyl ether (epoxy equivalent 174 g / eq)]
“PNP”: propylene glycol mono n-propyl ether “TPNB”: tripropylene glycol mono n-butyl ether “WS-500”: Epocros WS-500 manufactured by Nippon Shokubai Co., Ltd. [oxazoline group-containing water-soluble resin (oxazoline equivalent: resin) (Solid content: 220 g / eq, nonvolatile content: 40%)

Example 11 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In a reaction vessel similar to that in Synthesis Example 1, 141.6 parts of the composite resin (AB-3) solution was charged, and 31.6 parts of zirconosiloxane compound (C-1) and IPA50. After adding 0 part of the mixture, the mixture was stirred at the same temperature for 5 minutes. Furthermore, 280.0 parts of deionized water was added dropwise at the same temperature over 10 minutes to phase-invert and emulsify, and then stirred at the same temperature for 30 minutes to obtain zirconium in the zirconosiloxane compound (C-1). Hydrolytic condensation of an alkoxy group bonded to an atom and an alkoxy group bonded to a silicon atom was performed. Then, over 1 hour at an internal temperature of 40 to 60 ° C., methanol, IPA, n-butanol and a part of water were distilled off under reduced pressure to obtain a zirconium atom having an NV of 33.9% and an average particle diameter of 80 nm. An organic-inorganic hybrid resin aqueous dispersion containing silicon atoms was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-6). The calculated solid acid value of the organic-inorganic hybrid resin in the dispersion (Ds-6) was 16.0 mgKOH / g, and the weight ratios of the components contained were as follows.
Polyurethane polymer: ZrO ₂ : CH ₃ SiO _1.5 = 70.0: 5.0: 25.0

  The viscosity immediately after preparation of the dispersion (Ds-6) was 86 mPa · s, and the viscosity after storage at 30 ° C. for 3 months was 90 mPa · s, which was excellent in storage stability.

Example 12 [Preparation of aqueous organic-inorganic hybrid resin dispersion]
In a reaction vessel similar to Synthesis Example 1, 141.6 parts of the composite resin (AB-3) solution was charged, and 17.5 parts of the zirconosiloxane compound (C-5) and IPA20. After adding 0 part of the mixture, the mixture was stirred at the same temperature for 5 minutes. Further, 210.0 parts of deionized water was added dropwise at the same temperature over 10 minutes to effect phase inversion emulsification, followed by stirring at the same temperature for 30 minutes to obtain zirconium in the zirconosiloxane compound (C-5). Hydrolytic condensation of an alkoxy group bonded to an atom and an alkoxy group bonded to a silicon atom was performed. A portion of methanol, ethanol, IPA, n-butanol and water was distilled off under reduced pressure over 1 hour at an internal temperature of 40-60 ° C., and the zirconium having an NV of 35.0% and an average particle size of 110 nm An organic-inorganic hybrid resin aqueous dispersion containing atoms and silicon atoms was obtained. This organic-inorganic hybrid resin aqueous dispersion is abbreviated as dispersion (Ds-7). The calculated solid acid value of the organic-inorganic hybrid resin in the dispersion (Ds-7) was 18.3 mgKOH / g, and the weight ratios of the components contained were as follows.
Polyurethane polymer: ZrO ₂ : CH ₃ SiO _1.5 : SiO ₂ = 80.0: 3.7: 11.4: 4.9

  The viscosity immediately after preparation of the dispersion (Ds-7) was 90 mPa · s, the viscosity after storage at 30 ° C. for 3 months was 95 mPa · s, and the storage stability was excellent.

Comparative Example 5 [Preparation of aqueous polyurethane-polysiloxane hybrid resin dispersion for comparison]
In a reaction vessel similar to Synthesis Example 1, 198.5 parts of the polymer solution (a-3) obtained in Synthesis Example 3 was charged, and the temperature was raised to 60 ° C. with stirring, and then 30.0 parts of solvent under reduced pressure. Was distilled off. Next, 3.9 parts of triethylamine was added with stirring at 50 ° C., and the mixture was stirred for 10 minutes. Thereby, 100 mol% of the carboxyl group contained in the polymer solution (a-3) is neutralized to neutralize the neutralized carboxyl group (carboxylate group) and a polymer solution having both hydrolyzable silyl groups. was gotten. Next, 28.6 parts of MTMS partially hydrolyzed condensate (CH ₃ SiO _1.5 content: 70.0%) and 11.0 parts of deionized water were added while stirring at the same temperature, and the mixture was then heated to 70 ° C. The temperature was raised and the mixture was heated and stirred at the same temperature for 3.5 hours to carry out hydrolytic condensation of hydrolyzable silyl groups. Next, 240.0 parts of deionized water was added dropwise with stirring over 10 minutes at the same temperature to effect phase inversion emulsification, and then over 1.0 hour at an internal temperature of 50 to 60 ° C, methanol, IPA and water A portion of was distilled off under reduced pressure to obtain a polyurethane polymer-polysiloxane hybrid resin aqueous dispersion having an NV of 32.7% and an average particle size of 75 nm. This aqueous polyurethane polymer-polysiloxane hybrid resin dispersion is abbreviated as a dispersion (RDs-3). The calculated value of the solid content acid value of the polyurethane-based polymer-polysiloxane hybrid resin is 18.3 mgKOH / g, and the weight ratio of the contained components is as follows.
Polyurethane polymer: CH ₃ SiO _1.5 = 80.0: 20.0

  The viscosity immediately after preparation of the dispersion (RDs-3) was 145 mPa · s, the viscosity after storage at 30 ° C. for 3 months was 155 mPa · s, and the storage stability was excellent.

Example 13
100 parts of the dispersion (Ds-6) prepared in Example 11 and 6.8 parts of PNP as a film-forming aid were mixed to prepare a curable composition having an NV of 31.7%. Hereinafter, this composition is abbreviated as composition (KS-6).

  Next, the composition (KS-6) was applied to each of the hot-dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (KS-6) was used, and was allowed to stand at room temperature (25 ° C.) for 10 days. A coating plate was prepared by allowing to stand and curing. The obtained coated plate was evaluated in the same manner as in Example 6 except that the test time of the salt spray test was changed to 600 hours and the exposure time of the weather resistance test was changed to 250 hours. The evaluation results are shown in Table 4.

Example 14
100 parts of the dispersion (Ds-6) prepared in Example 11, 3.4 parts of GPTMS as a curing agent, 6.8 parts of PNP as a film-forming aid, and 2.8 parts of deionized water were mixed to obtain an NV of 33. A 0.0% curable composition was prepared. Hereinafter, this composition is abbreviated as composition (KS-7).

Next, the composition (KS-7) was coated on each of the hot-dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (KS-7) was used, and was allowed to stand at room temperature (25 ° C.) for 10 days. A coating plate was prepared by allowing to stand and curing. The obtained coated plate was evaluated in the same manner as in Example 6 except that the test time of the salt spray test was changed to 600 hours and the exposure time of the weather resistance test was changed to 250 hours. The evaluation results are shown in Table 4.
Example 15
Mixing 100 parts of the dispersion (Ds-7) prepared in Example 12, 4.0 parts of GPTMS as a curing agent, 7.0 parts of PNP as a film-forming aid, and 7.2 parts of deionized water, the NV was 33 A 0.0% curable composition was prepared. Hereinafter, this composition is abbreviated as composition (KS-8).

  Next, the composition (KS-8) was applied to each of the hot-dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (KS-8) was used, and the composition was subjected to normal temperature (25 ° C.) for 10 days. A coating plate was prepared by allowing to stand and curing. The obtained coated plate was evaluated in the same manner as in Example 6 except that the test time of the salt spray test was changed to 600 hours and the exposure time of the weather resistance test was changed to 250 hours. The evaluation results are shown in Table 4.

Comparative Example 6
A curable composition having an NV of 30.7% was prepared by mixing 100 parts of the dispersion (RDs-3) prepared in Comparative Example 5 and 6.5 parts of PNP as a film forming aid. Hereinafter, this composition is abbreviated as a composition (RKS-3).

  Next, the composition (RKS-3) was applied to each of the hot-dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (RKS-3) was used, and was allowed to stand at room temperature (25 ° C.) for 10 days. A coating plate was prepared by allowing to stand and curing. The obtained coated plate was evaluated in the same manner as in Example 6 except that the test time of the salt spray test was changed to 600 hours and the exposure time of the weather resistance test was changed to 250 hours. The evaluation results are shown in Table 5.

Comparative Example 7
100 parts of the dispersion (RDs-3) prepared in Comparative Example 5, 3.8 parts of GPTMS as a curing agent, 6.5 parts of PNP as a film-forming aid, and 0.3 part of deionized water were mixed to obtain an NV of 33. A 0.0% curable composition was prepared. Hereinafter, this composition is abbreviated as a composition (RKS-4).

  Next, the composition (RKS-4) was applied to each of the hot-dip galvanized steel sheet and the aluminum sheet in the same manner as in Example 6 except that the composition (RKS-4) was used, and was allowed to stand at room temperature (25 ° C) for 10 days. A coating plate was prepared by allowing to stand and curing. The obtained coated plate was evaluated in the same manner as in Example 6 except that the test time of the salt spray test was changed to 600 hours and the exposure time of the weather resistance test was changed to 250 hours. The evaluation results are shown in Table 5.

Claims (13)

A composite comprising a polymer segment (A) containing acid groups and / or neutralized acid groups and a polysiloxane segment (B) containing hydrolyzable groups and / or silanol groups bonded to silicon atoms. The resin (AB) is modified with a zirconosiloxane compound (C) containing an alkoxy group bonded to a zirconium atom and / or an alkoxy group bonded to a silicon atom, and then neutralized or not neutralized. A zirconosiloxane-modified composite resin (ABC) containing neutralized acid groups obtained in this manner is dispersed in an aqueous medium, and then bonded to hydrolyzable groups and / or silanol groups bonded to silicon atoms and zirconium atoms. obtained by performing hydrolytic condensation of alkoxy groups bonded to the alkoxy group and / or a silicon atom organic - No A hybrid resin aqueous dispersion, wherein the polymer segment (A), characterized in that a vinyl polymer segment or polyurethane polymer segment organic - inorganic hybrid resin aqueous dispersion. In the composite resin (AB), the polymer segment (A) and the polysiloxane segment (B) are represented by the following structural formula (S-1).

[However, the carbon atom in the structural formula (S-1) constitutes a part of the polymer segment (A), and the silicon atom and the oxygen atom constitute a part of the polysiloxane segment (B). ]
The organic-inorganic hybrid resin aqueous dispersion according to claim 1, which is bonded via a bond represented by the formula:   The composite resin (AB) comprises a polymer (a) containing an acid group and / or a neutralized acid group and a hydrolyzable silyl group and / or silanol group, a hydrolyzable group bonded to a silicon atom, and // A composite resin obtained by hydrolytic condensation or condensation of a polysiloxane (b) containing a silanol group, or a silane compound having a hydrolyzable group bonded to a silicon atom in the presence of the polymer (a) The organic-inorganic hybrid resin aqueous dispersion according to claim 1, which is a composite resin obtained by hydrolytic condensation of.   The organic-inorganic hybrid resin aqueous dispersion according to claim 1, wherein the zirconosiloxane compound (C) contains an alkoxy group bonded to a zirconium atom and an alkoxy group bonded to a silicon atom.   The zirconosiloxane compound (C) is obtained by subjecting an alkoxyzirconium compound (c-1) and / or a partial hydrolysis condensate thereof (c-2) and an alkoxysilane compound (c-3) to partial cohydrolysis condensation. The organic-inorganic hybrid resin aqueous dispersion according to claim 1, 2 or 3, which is obtained. A range in which the molar ratio (water / Zr-bonded alkoxy group) of the alkoxy group (Zr-bonded alkoxy group) in which the zirconosiloxane compound (C) is bonded to water and a zirconium atom is 0.05 to 5.0, an alkoxysilane compound The range of ( c- 3) to water molar ratio (alkoxysilane compound / water) is 0.3 to 5.0, and the atomic ratio of zirconium atom to silicon atom (Zr / Si) is 0.01 to 5 0.0 using an alkoxyzirconium compound ( c- 1) and / or a partially hydrolyzed condensate thereof ( c- 2), an alkoxysilane compound ( c- 3) and water at a ratio satisfying any of the ranges of 0.0, The organic-inorganic hybrid resin aqueous dispersion according to claim 1, 2 or 3, which is obtained by performing partial cohydrolysis condensation. A range in which the zirconosiloxane compound ( C ) has a molar ratio of water and an alkoxy group bonded to a zirconium atom (Zr bonded alkoxy group) (water / Zr bonded alkoxy group) of 0.05 to 5.0, an alkoxysilane compound ( c- 3) and the molar ratio of water (alkoxysilane compound / water) in the range of 0.3 to 5.0, and the atomic ratio of zirconium atoms to silicon atoms (Zr / Si) in the range of 0.01 to 5.0. Range and molar ratio of water to the sum of alkoxy groups bonded to zirconium atoms (Zr bonded alkoxy groups) and alkoxy groups bonded to silicon atoms (Si bonded alkoxy groups) (Zr bonded alkoxy groups + Si bonded alkoxy groups) The ratio of [water / (Zr bond alkoxy group + Si bond alkoxy group)] in the range of 0.03 to 0.8 satisfies Shi zirconium compound (c -1) and / or its partially hydrolyzed condensate (c -2), using an alkoxysilane compound (c -3) and water, those obtained by performing the partial cohydrolysis condensation The organic-inorganic hybrid resin aqueous dispersion according to claim 1, 2 or 3.

  The ratio of the composite resin (AB) to the zirconosiloxane compound (C) is 2 to 600 parts by weight of the zirconosiloxane compound (C) with respect to 100 parts by weight of the composite resin (AB). 2. The organic-inorganic hybrid resin aqueous dispersion according to 2 or 3. The organic-inorganic hybrid resin aqueous dispersion according to claim 1, 2, 3, or 8, wherein the acid group is a carboxyl group. Organic according to any one of claims 1 to 9 - inorganic hybrid resin aqueous dispersion and the curing agent (D) The curable resin composition characterized by containing a. Organic according to any one of claims 1 to 9 - paint containing inorganic hybrid resin aqueous dispersion. Paint characterized by containing a curable resin composition according to claim 1 0. Coated article, characterized in that is obtained by coating a coating composition according to claim 1 1 or 1 2.