JP5151898B2 - Curable resin composition, paint and paint - Google Patents

Description

  The present invention relates to a curable resin composition, a paint containing these, and a coated product obtained by coating the paint. More specifically, a curable resin composition that forms a cured product having a specific vinyl polymer, a titanosiloxane compound that is soluble in an organic solvent, and a curability that contains the organic solvent, as well as excellent corrosion resistance and a high refractive index. Further, the present invention relates to a paint containing the curable resin composition, and further to a coated article having a coating film having excellent corrosion resistance and high refractive index, which is obtained by coating and curing the paint on various substrates. .

  A curable composition comprising a vinyl polymer containing a hydrolyzable silyl group and a curing catalyst cures at room temperature, and forms cured products having excellent weather resistance and adhesion to various substrates. It is disclosed that it can be used for various uses, such as a coating material for base materials, an adhesive agent, and a sealing agent (for example, refer patent document 1). In the invention described in these patent documents, metal-containing compounds such as dialkyl tin dicarboxylate and alkoxy titanate, acids, amines and the like are used as a curing catalyst. Although the cured coating film obtained from such a composition is excellent in weather resistance and adhesion to various bases, it has a problem that it cannot be used for applications requiring high corrosion resistance because of insufficient corrosion resistance. On the other hand, the development of paints that form a coating film having a high refractive index as a coating agent used for various displays and the like is underway, but the paint films obtained from conventional paints are inferior in transparency, There is a problem such as coloring, and there is a demand for the development of a paint that can eliminate these drawbacks.

JP 57-172949 A

  The problem to be solved by the invention is to provide a cured product having excellent curability at room temperature and capable of imparting a high degree of corrosion resistance to various metals, and also to form a cured product having excellent transparency and low coloring and high refractive index. The object is to provide a resin composition, to provide a paint containing the curable resin composition, and to provide a coated product obtained by coating the paint.

As a result of intensive studies to solve the above problems, the present inventors have found that a vinyl polymer (A) containing a hydrolyzable silyl group, a titanosiloxane compound (B) soluble in an organic solvent, and A curable resin composition containing an organic solvent (C) , wherein a ratio of the vinyl polymer (A) to the titanosiloxane compound (B) is 100 parts by weight of the vinyl polymer (A). On the other hand, the curable resin composition in which the titanosiloxane compound (B) is 49 to 1,500 parts by weight is excellent in curability at room temperature, excellent in corrosion resistance, and forms a cured product having a high refractive index. In addition, when a paint containing the curable resin composition is applied to various substrates and cured, a coating film having a high refractive index is formed. When the paint is applied to a metal substrate and cured, it is extremely corrosion resistant. Forming an excellent coating film, Found has led to the completion of the present invention.

That is, the present invention is a curable resin composition containing a vinyl polymer containing a hydrolyzable silyl group, a titanosiloxane compound soluble in an organic solvent, and an organic solvent , the vinyl polymer ( Curing in which the ratio of A) to the titanosiloxane compound (B) is 49 to 1,500 parts by weight of the titanosiloxane compound (B) with respect to 100 parts by weight of the vinyl polymer (A). The present invention relates to a conductive resin composition . Moreover, it is also related with the coating material containing the said curable resin composition, and also is related with the coated material obtained by apply | coating the said coating material to a to-be-coated object.

  The curable resin composition according to the present invention is excellent in curability at room temperature and has a long pot life, and has a high degree of corrosion resistance when a coating containing the curable resin composition of the present invention is applied to a metal substrate. Since it forms a cured coating film, it is suitable as a curable resin composition for metal anticorrosive coatings. In addition, when a paint containing the curable resin composition of the present invention is applied to various substrates, it forms a low-colored and high-refractive-index coating film, so that it is cured for an anti-reflection coating agent for various displays. It is useful as a functional resin composition. Moreover, the curable resin composition of this invention can be effectively utilized also for various uses other than coating materials, such as a sealing agent and an adhesive agent.

  First, the vinyl polymer (A) containing a hydrolyzable silyl group used in the present invention will be described. Examples of the hydrolyzable silyl group contained in the vinyl polymer include atomic groups in which various hydrolyzable groups are bonded to silicon atoms as represented by the following general formula (I).

（ただし、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 (I) is an alkoxy group or a substituted alkoxy group from the viewpoint that the alcohol generated by hydrolysis easily evaporates from the cured product. Typical examples of the alkoxy group include lower alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group. Representative examples of the substituted alkoxy group include lower alkoxy groups such as 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-butoxyethoxy group, 3-methoxypropoxy group, 4-methoxybutoxy group. Examples thereof include substituted alkoxy groups having 2 to 4 carbon atoms.

  Representative examples of the vinyl polymer (A) containing a hydrolyzable silyl group include acrylic polymers, carboxylic acid vinyl ester polymers, aromatic vinyl polymers, fluoroolefin polymers, Although various polymers, such as a polyolefin-type polymer, are mentioned, since the freedom degree of design is high, an acrylic polymer is especially preferable.

  In order to prepare the vinyl polymer (A) containing such a hydrolyzable silyl group, for example, (1) a vinyl monomer containing a hydrolyzable silyl group is homopolymerized or the vinyl polymer (2) A method of adding a hydrosilane compound to a vinyl polymer containing a vinyl group prepared in advance by a hydrosilylation reaction, 3) A method of reacting a vinyl polymer containing an active hydrogen-containing group such as a previously prepared hydroxyl group with a silane compound having both an isocyanate group and a hydrolyzable silyl group, and (4) a previously prepared isocyanate group. A method of reacting a silane compound having both a hydrolyzable silyl group and an active hydrogen-containing group such as a hydroxyl group, an amino group or a mercapto group with a vinyl polymer containing A vinyl monomer in the presence of a silane compound having both a radical polymerization initiator or a mercapto group and a hydrolyzable silyl group having a silyl group can be applied a method of radical polymerization, an equal variety of ways.

  When the method (1), the method (5), or the method using both (1) and (5) is applied among the various methods described above, a vinyl polymer containing a hydrolyzable silyl group ( A) can be prepared easily and at low cost.

  A typical vinyl monomer containing a hydrolyzable silyl group used in preparing the vinyl polymer (A) by the method (1) is 3- (meth) acryloyloxy. Propyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyl-methyldimethoxysilane, 3- (meth) acryloyloxypropyl-methyldiethoxysilane, 3- (meth) acryloyl Oxypropyl-dimethylmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (meth) acryloyloxypropyl-dimethylhydroxysilane, trimethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl Ether and the like.

  A vinyl polymer (A) can be prepared by polymerizing one or more of vinyl monomers containing various hydrolyzable silyl groups as described above, and these vinyl monomers can be prepared. The vinyl polymer (A) can also be prepared by copolymerizing the monomer with other monomers copolymerizable therewith.

  Copolymerizable for use in preparing vinyl polymer (A) by copolymerizing hydrolyzable silyl group-containing vinyl monomers with other monomers copolymerizable therewith. Typical examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( Esters of (meth) acrylic acid with alkyl alcohols having 1 to 22 carbon atoms such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;

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 ( Tertiary amide group-containing monomers such as (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, N-vinylpyrrolidone;

  Ether bonds such as 2-methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and (meth) acrylates of ethylene oxide / propylene oxide copolymer having methoxy at one end And the like.

  Furthermore, vinyl monomers having various reactive functional groups such as a carboxyl group, a hydroxyl group, a cyclocarbonate group, a carbamate group, an amide group, and a tertiary amino group can be copolymerized.

  Among these reactive functional groups, typical vinyl monomers containing a carboxyl group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid, fumaric acid. Unsaturated carboxylic acids such as acids; saturated dicarboxylic acids such as monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate; Monoesters with saturated monohydric alcohols; Monovinyl esters of saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; Saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride and trimellitic anhydride Addition reaction between the anhydrides and vinyl monomers containing hydroxyl groups as described below Product; and a carboxyl group-containing monomers such as described above, and the like the monomers obtained by addition reaction of lactones.

  Among the reactive functional groups, representative vinyl monomers containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

  Among the reactive functional groups, typical vinyl monomers containing a cyclocarbonate group include 2,3-carbonate propyl (meth) acrylate and 2-methyl-2,3-carbonate propyl (meth) acrylate. 3,4-carbonate butyl (meth) acrylate and the like.

  Among the reactive functional groups, typical vinyl monomers containing an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl. Examples include vinyl ether.

Among the reactive functional groups, typical vinyl monomers containing a carbamate group include:
Examples include methyl N- (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate, ethyl N- [2- (meth) acryloyloxy] ethylcarbamate, 2-carbamoyloxyethyl (meth) acrylate, and the like.

  Among the reactive functional groups, typical vinyl monomers containing an amide group include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-butoxymethyl. (Meth) acrylamide etc. are mentioned.

Among the reactive functional groups, typical vinyl monomers containing a tertiary amino group include:
Examples include 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, and 2-di-n-propylaminoethyl (meth) acrylate.

  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, an α-olefin monomer, and a fluoroolefin monomer as essential components, An aromatic vinyl polymer, a carboxylic acid vinyl ester polymer, an α-olefin polymer, and a fluoroolefin polymer can be obtained, respectively.

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

  In preparing a vinyl polymer containing a hydrolyzable silyl 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. Tells; 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 such as Of these, alcohols are particularly preferably used as essential components.

  Various kinds of polymerization initiators are used for 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.

As the radical polymerization initiation used when preparing by the method (5), an azo polymerization initiator having a hydrolyzable silyl group as disclosed in JP-A-3-97702 should be used. Can do.

  Representative examples of the silane compound having both a mercapto group and a hydrolyzable silyl group used in the preparation of the method (5) include 3-mercaptopropyltrimethoxysilane and 3-mercapropropyltrimethyl. Examples include alkoxysilanes containing mercapto groups such as ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyldimethylmethoxysilane.

  In order to prepare the vinyl polymer (A) by the method (5), radical polymerization in an organic solvent solution is simple and preferable as in the method (1). As typical organic solvents and polymerization initiators used at that time, those exemplified as those used in the method (1) can be used.

  The vinyl polymer (A) prepared by the method (5) has a hydrolyzable silyl group at the polymer molecule end. The vinyl polymer (A) prepared by the method (1) has a hydrolyzable silyl group in a pendant form inside the polymer main chain. Therefore, by using the method (1) and the method (5) in combination, it is possible to obtain a vinyl polymer (A) having a hydrolyzable silyl group at both the polymer molecule end and the polymer main chain. it can.

  The amount of the hydrolyzable silyl group introduced into the vinyl polymer (A) containing the hydrolyzable silyl group prepared as described above depends on the curability, stability and the curable resin composition of the present invention. From the viewpoint of the flexibility of the cured product, a range of 0.02 to 3.0 mol per 1,000 g of the vinyl polymer (A) is preferable, and a range of 0.05 to 1.5 mol is more preferable. Especially preferably, it is the range of 0.1-1.0 mol.

  Further, the weight average molecular weight of the vinyl polymer described above is such that when blended with the titanosiloxane compound (B), the viscosity becomes high and the workability is not inferior or gelation occurs in a short time. From the viewpoint of properties, a range of 2,000 to 200,000 is preferable, a range of 3,000 to 100,000 is more preferable, and a range of 4,000 to 50,000 is particularly preferable.

The calculated value of the glass transition temperature (Tg) of the vinyl polymer (A) is preferably in the range of −80 to 70 ° C., more preferably −70 to 50 from the viewpoint of the transparency, hardness, and crack resistance of the cured product. It is the range of ° C, and particularly preferably is the range of -60 to 40 ° C. The calculated value (absolute temperature) of Tg here is calculated from the Tgi (absolute temperature) and weight fraction Wi of the homopolymer of each monomer constituting the vinyl polymer (A) by the following Fox formula. Indicates the value.
Tg ⁻¹ = ΣWiTgi ⁻¹

  If the transparency of the cured product is insufficient due to insufficient compatibility between the vinyl polymer (A) and the titanosiloxane compound (B), copolymerization of the carboxyl group-containing monomer described above The transparency of the cured product can be improved by introducing a carboxyl group into the vinyl polymer (A). In the case of introducing a carboxyl group, the amount introduced is 0.02 to 1.5 mol per 1,000 g of the vinyl polymer (A) from the viewpoint of the stability of the composition of the present invention and the transparency of the cured product. A range is preferable, More preferably, it is the range of 0.04-1.0 mol, Most preferably, it is the range of 0.07-0.7 mol.

Next, the titanosiloxane compound (B) soluble in the organic solvent used by blending with the vinyl polymer (A) will be described. In general, titanosiloxane is a generic term for compounds containing a Ti—O—Si bond in the molecule, and there are gel-like compounds that are insoluble in organic solvents and those that are soluble in organic solvents. In the present invention, a titanosiloxane compound that is soluble in an organic solvent is used from the viewpoint of forming a homogeneous and dense cured product. Of these titanosiloxane compounds (B) soluble in organic solvents, titanosiloxane compounds containing an alkoxy group bonded to a titanium atom and / or an alkoxy group bonded to a silicon atom are preferred from the viewpoint of curability. .

  Typical examples of the alkoxy group contained in the titanosiloxane compound (B) 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. Among these various alkoxy groups, a particularly preferable one is an unsubstituted alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 2 to 4 carbon atoms having a methoxy group or an ethoxy group as a substituent.

  The titanosiloxane compound (B), for example, partially cohydrolyzes and condenses an alkoxytitanium compound (b-1) and / or a partially hydrolyzed condensate thereof (b-2) and an alkoxysilane compound (b-3). It is prepared by.

  Representative examples of the alkoxytitanium compound (b-1) used in this case include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrakis. Examples include tetraalkoxy titanium such as (2-ethylhexanoxy) titanium. Moreover, the partial hydrolysis-condensation product (b-2) of an alkoxytitanium compound is an oligomer in which the main chain obtained by partial hydrolysis-condensation of the above-described alkoxytitanium compound is connected by a Ti—O—Ti bond. Specifically, tetradecapropoxytitanium decamer A-10 and tetra-n-butoxytitanium dimer, tetramer, heptamer, and 10mer, respectively, B- 2, B-4, B-7, B-10 (all manufactured by Nippon Soda Co., Ltd.) and the like.

  Further, as the alkoxytitanium compound (b-1) or the partial hydrolysis condensate thereof (b-2), a part of the alkoxy groups in the various alkoxytitanium compounds or partial hydrolysis condensates thereof may be acetylacetone or acetoacetic acid. A compound substituted with a 1,3-dicarbonyl compound such as an ester, a monocarboxylic acid or a hydroxycarboxylic acid can also be used. Specific examples of such alkoxytitanium compounds include triisopropoxytitanium monoacetylacetonate, di-n-butoxytitanium bisacetylacetonate, triisopropoxytitanium monoethylacetoacetate, triisopropoxytitanium monoacetate, tri-n. -Butoxy titanium monoacetate etc. are mentioned.

  Among the various alkoxytitanium compounds (b-1) and partial hydrolysis condensates (b-2) thereof, tetraalkoxytitanium and partial hydrolysis condensates (oligomers) thereof are particularly preferable.

  The alkoxytitanium compound (b-1) and its partial hydrolysis-condensation product (b-2) may be used alone or in combination of two or more.

  Typical examples of the alkoxysilane compound (b-3) used in preparing the titanosiloxane compound (B) include tetraalkoxysilanes, monoorganotrialkoxysilanes, diorganodialkoxysilanes, And organomonoalkoxysilanes.

  As a typical thing of the alkoxy group which this alkoxysilane has, what was illustrated as a typical thing of the alkoxy group which an alkoxy titanium compound (b-1) has is mentioned. Of the various alkoxy groups, an alkoxy group having 2 to 4 carbon atoms having an unsubstituted alkoxy group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group as a substituent is particularly preferable.

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

  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) acrylate such as acryloyloxy propyl silane coupling agents having an alkoxy group such as a methyl dimethoxy silane.

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

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

  The various alkoxysilane compounds (b-3) described above are mainly used in the form of monomers, but an oligomer obtained by partially hydrolyzing and condensing them may be used in part.

  When preparing the titanosiloxane compound (B) from the above-described alkoxytitanium compound (b-1) and / or its partially hydrolyzed condensate (b-2), alkoxysilane compound (b-3) and water, the reaction Although various methods can be applied as the method, water is added dropwise to a mixture of the alkoxytitanium compound (b-1) and / or its partially hydrolyzed condensate (b-2) and the alkoxysilane compound (b-3). Is convenient and preferred. At that time, an organic solvent may be further added to the alkoxytitanium compound (b-1) and / or a mixture of the partially hydrolyzed condensate (b-2) and the alkoxysilane compound (b-3) for reaction.

  Examples of the organic solvent used in the reaction by adding an organic solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-octane, cyclohexane, and methylcyclohexane; toluene, xylene, and ethylbenzene. Aromatic hydrocarbons such as acetone; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and n-butyl acetate; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert- Alcohols such as butanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Esters of glycol ethers such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Diglycol ether esters; diethyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydrofuran, 1,3- Ethers such as dioxolane and tetrahydrofuran; amide compounds such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; aprotic polar solvents such as dimethylsulfoxide, sulfolane and N, N-dimethylethyleneurea Can be mentioned. Among these, it is particularly preferable to use a water-soluble organic solvent because the formation of a hydrolysis-condensation product of an alkoxytitanium compound that is insoluble in an organic solvent can be suppressed.

  The water-soluble organic solvent used for the preparation of the titanosiloxane compound (B) is not particularly limited as long as it has an appropriate miscibility with water, but among these, with respect to 100 parts by weight of water at 20 ° C. An organic solvent that dissolves 30 parts by weight or more is preferable. More preferred are organic solvents that are completely miscible with water.

  Among various organic solvents, typical water-soluble organic solvents include methanol, ethanol, n-propanol, isopropanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. Alcohols; glycol ethers such as ethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate or esters of diglycol ether; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, 1,3-dioxolane and tetrahydrofuran; dimethylformamide Amide compounds such as N, N-dimethylacetamide and N-methylpyrrolidone; Chill sulfoxide, sulfolane, N, include aprotic polar solvents such as N- dimethyl ethylene urea.

  Water may be dropped as it is without being dissolved in an organic solvent, but since it can suppress the formation of a hydrolysis-condensation product of an insoluble alkoxytitanium compound alone, it is particularly a water-soluble organic solvent among the various organic solvents described above. It is preferable to add dropwise as a solution diluted with water. In dropping a solution obtained by diluting water with a water-soluble organic solvent, an alkoxytitanium compound (b-1) and / or a partial hydrolysis-condensation product (b-2) thereof, an alkoxysilane compound (b-3) and, if necessary, It is preferable that the mixture of organic solvents added in the step is gradually added dropwise with sufficient stirring. If the stirring rate is insufficient or the dropping speed of a solution obtained by diluting water with a water-soluble organic solvent is too high, the hydrolysis and condensation reaction of the alkoxytitanium compound alone tends to occur, and the insoluble gel-like product Is easier to generate.

  Moreover, while suppressing the production | generation of an insoluble gel in the process of preparing a titanosiloxane compound (B), from the point of stability of the curable composition of this invention, an alkoxy titanium compound (b-1). And / or its partial hydrolysis-condensation product (b-2), alkoxysilane compound (b-3) and water are used in proportions such that the following two conditions (a) and (b) are satisfied. It is preferable to prepare the titanosiloxane compound (B) by performing hydrolytic condensation, and in particular, the partial co-hydrolytic condensation is set by satisfying the following three conditions (a) to (c). It is particularly preferable to prepare the titanosiloxane compound (B) by carrying out the process.

That is,
(I) The molar ratio (water / alkoxy group) of the alkoxy group bonded to the titanium atom contained in water and the alkoxytitanium compound (b-1) and / or the partial hydrolysis-condensation product (b-2) thereof is set to 0. It is set to a range of 2 to 1.3, preferably 0.4 to 1.1.
(B) The molar ratio [(b-3) / water] of the alkoxysilane compound (b-3) and water is set to a range of 0.3 to 5, preferably 0.5 to 3.
(C) The atomic ratio (Ti / Si) of titanium atoms to silicon atoms is set to a range of 0.1 to 4.0, preferably 0.3 to 3.0.

  In preparing the titanosiloxane compound (B), 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 may remain in the cured product obtained from the curable resin composition of the present invention and adversely affect the performance of the cured product. Use of these strong acids requires care. 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 the titanosiloxane compound (B) by partially cohydrolyzing and condensing the alkoxytitanium compound (b-1) and / or its partial hydrolysis condensate (b-2) and the alkoxysilane compound (b-3). Is generally about −10 to 120 ° C., preferably 10 to 100 ° C., for about 2 to 15 hours, preferably 4 to 10 hours.

  Thus, the titanosiloxane compound (B) 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, Volatile components such as alcohols and organic solvents used as necessary may be removed by distillation to increase the content of the titanosiloxane compound (B).

  The titanosiloxane compound (B) thus prepared contains an alkoxy group bonded to a titanium atom and / or an alkoxy group bonded to a silicon atom as a functional group for reacting with the vinyl polymer (A). Since a cured product having a more homogeneous and dense cross-linked structure is obtained, those having both alkoxy groups are particularly preferred.

  Typical examples of the organic solvent (C) used in preparing the curable resin composition of the present invention include those used in preparing the titanosiloxane compound (B). As described above, various solvents can be used. Of these various solvents, it is preferable to use a solvent containing an alcohol as an essential component from the viewpoint of pot life of the curable resin composition of the present invention. The content of the alcohol is 20 to 100% by weight, preferably 30 to 100% by weight of the organic solvent.

Vinyl polymer (A), titanosiloxane compound (B) and organic solvent (C) described above
From the above, in preparing the curable resin composition of the present invention, the blending ratio of the vinyl polymer (A) and the titanosiloxane compound (B) is the resistance of the cured product obtained from the curable resin composition of the present invention. From the viewpoint of the effect of imparting cracking property, toughness and corrosion resistance, 49 to 1,500 parts by weight, preferably 49 to 1,200 parts by weight of the titanosiloxane compound (B) per 100 parts by weight of the vinyl polymer (A), Particularly preferably, it is 49 to 1,000 parts by weight, and 1 to 55 parts by weight, preferably 3 to 50 parts by weight, particularly preferably 5 to 5 parts by weight of titanium atoms in terms of titanium dioxide in 100 parts by weight of the resulting cured product. The ratio is such that 45 parts by weight is contained. In order to obtain a cured product having a high refractive index, vinyl is contained in a proportion such that titanium atoms are contained in an amount of 5 to 50 parts by weight, preferably 10 to 50 parts by weight in terms of titanium dioxide, in 100 parts by weight of the obtained cured product. A system polymer (A) and a titanosiloxane compound (B) may be used.

  The amount of the organic solvent (C) used may be appropriately set according to the stability of the curable resin composition of the present invention and the application application, but the vinyl polymer (A) and the titanosiloxane compound (B). The total amount is about 30 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and particularly preferably 100 to 2,000 parts by weight.

  In order to prepare the curable resin composition of the present invention from the vinyl polymer (A), the titanosiloxane compound (B) and the organic solvent (C), (i) the vinyl polymer (A), titano Mixing the siloxane compound (B) and the organic solvent (C), (b) mixing the organic solvent solution of the vinyl polymer (A), the titanosiloxane compound (B) and the organic solvent (C), (c) The organic solvent solution of the vinyl polymer (A) and the organic solvent solution of the titanosiloxane compound (B) are mixed. (D) The organic solvent solution of the vinyl polymer (A), the titanosiloxane compound (B) Various methods such as mixing an organic solvent solution and an organic solvent (C) can be employed. Among these, from the viewpoint of suppressing the formation of insoluble matter and the occurrence of gelation during the preparation of the curable resin composition, as in the methods (c) and (d), the vinyl polymer (A) and tita are used. A method of preparing each organic solvent solution of the nosiloxane compound (B) in advance and then mixing them is preferred.

  The curable resin composition of the present invention prepared as described above contains a hydrolyzable silyl group, an alkoxy group bonded to a titanium atom, and an alkoxy group bonded to a silicon atom as reactive functional groups. Moreover, when a vinyl polymer (A) contains functional groups, such as a carboxyl group, these functional groups are also contained. Therefore, when the composition is applied to a substrate or the like and dried at room temperature, a bond of Ti—O—Ti, Ti—O—Si, Si—O—Si, and Ti—O (CO) — is formed and cured. Form things. The bond between metal atoms via oxygen atoms such as Ti-O-Ti, Ti-O-Si, Si-O-Si, etc. is that the alkoxy group bonded to the Ti atom and the alkoxy group bonded to the Si atom are moisture in the air. It is formed by hydrolytic condensation in the presence of. And it is estimated that formation of the above-mentioned various bonds by this hydrolytic condensation is promoted by the catalytic action of titanosiloxane contained in the curable resin composition.

  The curable resin composition of the present invention prepared as described above can be used as a clear composition not containing a color pigment, and contains various organic or inorganic pigments. It can also be used as a coloring composition.

  Further, the curable resin composition of the present invention further includes various reactive diluents, flow modifiers, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers or water absorbing agents. It can be used for various purposes in a form that also contains additives.

  Specific examples of the reactive diluent described above include compounds having a hydrolyzable group or silanol group bonded to a silicon atom. Typical examples of these reactive diluents include a titanosiloxane compound (B). Examples include various compounds exemplified as representative alkoxysilanes used in the preparation, and polysiloxanes obtained by partial hydrolysis condensation or complete hydrolysis condensation of such alkoxysilanes.

  Since the curable resin composition of the present invention has moisture curability, when moisture in the air is mixed, it is hydrolyzed and condensed to increase the viscosity, and finally gelation occurs. Therefore, the addition of the water-absorbing agent described above is effective in order to suppress thickening and gelation due to mixed water. Representative examples of the water-absorbing agent include orthocarboxylic acid esters such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate and ethyl orthoacetate.

  Although the curable resin composition of the present invention can be used for various applications such as paints, adhesives, sealing agents, fiber treatment agents, optical materials, etc., it is a preferred application in which the characteristics of the curable resin composition of the present invention are exhibited. One is a paint application, and the paint of the present invention comprises the curable resin composition of the present invention.

  The coating material containing the curable resin composition of the present invention can be used for various applications in the same manner as various coating materials. However, when coated on a metal substrate, the coating material exhibits extremely excellent corrosion resistance. In addition, when a paint that forms a cured coating film with a high titanium content is applied to organic substrates such as various organic resins and inorganic substrates such as glass, a cured film with a high refractive index is formed. It can be used for applications where the characteristics can be utilized.

  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. Examples of such materials include various metal substrates, inorganic substrates, plastic substrates, paper, and 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 subjected to chemical conversion treatment such as the above.

  In addition, examples of the inorganic base material include those mainly composed of inorganic materials typified by cement-based, silicate-based, such as calcium silicate, gypsum-based, and ceramic-based materials. Wet) base materials include exposed concrete, cement mortar, gypsum plaster, dolomite plaster, plaster, etc. Also, factory-produced (dry) base materials include lightweight cellular concrete (ALC), glass fiber reinforced calcium silicate , Various types of materials such as a fired product of clay such as gypsum board and tile, and 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 base materials are used in various forms such as plate-like, spherical, film-like, sheet-like or large-sized structures, complex-shaped assemblies or molded products, 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, (1) the paint is directly applied to the base material, (2) the base coat is previously applied on the base, and then the paint is applied as the top coat. (3) the base coat is applied to the base. As described above, the coated product of the present invention can be obtained by a coating method such as coating the coating material of the present invention and then coating another top coating material to form a coating film.

  In order to obtain a coated product according to the present invention by the direct coating method of (1) above, the paint of the present invention is applied to a substrate by brush coating, roller coating, spray coating, dip coating, flow coater coating, What is necessary is just to apply by coating methods, such as roll coater painting, electrodeposition painting, and spin coating. Then, the substrate coated with the uncured coating film is allowed to stand at room temperature for about 1 to 14 days, or is heated at 60 to 250 ° C. for about 10 seconds to 3 hours. A desired coated product coated with a film or a coating film excellent in corrosion resistance can be obtained.

  On the other hand, as the undercoat paint used when the coated product according to the present invention is obtained by the method (2), various paints can be used, and typical examples thereof include an aqueous solution type or a dispersion. Type paint; organic solvent-based solution-type or dispersion-type paint; powder paint, solvent-free liquid paint, and the like.

In order to apply such an undercoat paint and then apply and cure the paint of the present invention as an overcoat paint to obtain a coated product of the present invention, the above-described coating methods, various drying processes, etc. may be applied. When UV curable or electron beam curable paint is used as the undercoat,
It can be cured by irradiating with an active energy ray effective for curing acceleration.

  As the top coating used for obtaining the coated product according to the present invention by the method (3), various types can be used, and a typical one is an aqueous solution type or dispersion type coating. 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 (1). After coating and pre-curing under the curing conditions employed in (1) above, the above-mentioned top coating is applied and dried or cured under conditions suitable for drying or curing the top coating. A coated product having a film can be obtained. In addition, the coating material of the present invention is applied to the base material, and the coating film formed from the coating material of the present invention is uncured. By doing so, a coated product having a multilayer coating film can be obtained.

  As described above, a coated product according to the present invention coated with a cured coating film having excellent corrosion resistance or a cured coating film having a high refractive index can be obtained. More specific examples of such paints include automobiles, motorcycles, trains, and other transportation-related equipment that use a metal substrate as the substrate; use a metal substrate or plastic substrate as the substrate. TV, radio, refrigerator, washing machine, cooler, cooler outdoor unit, computer, other household appliances; various inorganic tiles and roofing materials, metal roofing materials, inorganic outer wall materials, solar cell Building materials such as protective materials, metal wall materials, metal window frames, glass, metal or wooden doors or interior wall materials; outdoor structures such as road signs, guardrails, bridges, tanks, chimneys, buildings; polyester resins Examples include coated films coated on various organic films such as films, acrylic resin films, and fluororesin films. In Applications, in which it can be effectively utilized.

  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, all parts and% are based on weight.

Synthesis Example 1 (Preparation of vinyl polymer containing hydrolyzable silyl group)
In a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas inlet, 37 parts of methyl methacrylate (MMA), 33 parts of n-butyl methacrylate (BMA), n-butyl acrylate (BA), 3-methacryloxypropyl 5 parts of trimethoxysilane (MPTMS), 1 part of methacrylic acid (MAA), 135 parts of n-butanol, 15 parts of methyl orthoformate and 7 parts of tert-butyl peroxybenzoate were charged. Next, the temperature was raised to 85 ° C. in a nitrogen gas atmosphere, and the mixture was heated and stirred at the same temperature for 20 hours.
A vinyl polymer solution containing a hydrolyzable silyl group having a weight average molecular weight (Mw) of 35,100 and a calculated Tg value of 20.3 ° C. was obtained. Hereinafter, this is abbreviated as a polymer solution (A-1).

Synthesis Examples 2 to 5 [Preparation of vinyl polymer containing hydrolyzable silyl group]
Polymerization was carried out in the same manner as in Synthesis Example 1 except that those described in Tables 1 and 2 were used as vinyl monomers to obtain a vinyl polymer solution having a hydrolyzable silyl group. Hereinafter, these are abbreviated as polymer solutions (A-2) to (A-5). Tables 1 and 2 show calculated values of NV, Mw and Tg.

Table 1

Table 2

Footnotes in Table 1 and Table 2 Calculated Tg values for the copolymers using the following values as the Tg values for the homopolymers obtained from the respective monomers.
Styrene 373 ° K
MMA 378 ° K
BMA 293 ° K
MPTMS 293 ° K
MAA 417 ° K

Synthesis Example 6 [Preparation of titanosiloxane compound (B)]
In a reaction vessel equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen gas inlet, 1,090 parts of methyltrimethoxysilane (MTMS), B-7 [Tetra-n-butoxy titanium manufactured by Nippon Soda Co., Ltd. Partially hydrolyzed condensate (average heptamer)] of 1,601 parts and IPA of 2,190 parts were charged and heated to 70 ° C. While stirring at the same temperature in a nitrogen atmosphere, a mixture of 144 parts of deionized water and 500 parts of IPA was added dropwise over 2 hours, and the mixture was further heated and stirred at the same temperature for 5 hours. Thereafter, IPA and methanol and n-butanol produced by the reaction were distilled off under reduced pressure to obtain 1,983 parts of a yellow transparent liquid product. The product is a titanosiloxane compound containing an alkoxy group bonded to a titanium atom as well as an alkoxy group bonded to a silicon atom. Hereinafter, this is abbreviated as a titanosiloxane compound (B-1). The titanium atom and silicon atom contained in the titanosiloxane compound (B-1) are 27.1% and 27.1%, respectively, in terms of TiO ₂ and CH ₃ SiO _1.5 . In this synthesis example, the molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is 0.50, the molar ratio of alkoxysilane compound to water (alkoxysilane / water) is 1.00, titanium The atomic ratio (Ti / Si) of atoms and silicon atoms was 0.88.

Synthesis Example 7 [Preparation of titanosiloxane compound (B)]
A reaction vessel similar to Synthesis Example 6 was charged with 1,635 parts of MTMS, 1,601 parts of B-7 and 2,480 parts of IPA, and comprised of 216 parts of deionized water and 756 parts of IPA under air cooling while stirring in a nitrogen atmosphere. The mixture was added dropwise over 2 hours. During this time, the temperature of the mixture rose from 22 ° C. to 37 ° C. due to heat generation. Next, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 5 hours. Thereafter, IPA and methanol and n-butanol produced by the reaction were distilled off under reduced pressure to obtain 2,446 parts of a pale yellow transparent liquid product. This liquid product is a titanosiloxane compound containing an alkoxy group bonded to a titanium atom and an alkoxy group bonded to a silicon atom. Hereinafter, this is abbreviated as a titanosiloxane compound (B-2). The titanium atom and silicon atom contained in this titanosiloxane compound (B-2) are 21.9% and 33.0%, respectively, in terms of TiO ₂ and CH ₃ SiO _1.5 . In this synthesis example, the molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is 0.75, the molar ratio of alkoxysilane compound to water (alkoxysilane / water) is 1.0, titanium The atomic ratio (Ti / Si) of atoms and silicon atoms was 0.58.

Synthesis Example 8 [Preparation of titanosiloxane compound (B)]
In a reaction vessel similar to Synthesis Example 6, 2,179 parts of MTMS, 1,601 parts of B-7 and 2,780 parts of IPA were charged, and 288 parts of deionized water and 1,000 parts of IPA were stirred under a nitrogen atmosphere under air cooling. The mixture consisting of was added dropwise over 2 hours. During this time, the temperature of the mixture rose from 20 ° C. to 35 ° C. due to heat generation. Next, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 4.5 hours. Thereafter, IPA and methanol and n-butanol produced by the reaction were distilled off under reduced pressure to obtain 2,749 parts of a pale yellow transparent liquid product. This liquid product is a titanosiloxane compound containing an alkoxy group bonded to a titanium atom and an alkoxy group bonded to a silicon atom. Hereinafter, this is abbreviated as a titanosiloxane compound (B-3). The titanium atom and silicon atom contained in the titanosiloxane compound (B-3) are 19.5% and 39.1% in terms of TiO ₂ and CH ₃ SiO _1.5 , respectively. In this synthesis example, the molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is 1.0, the molar ratio of alkoxysilane compound to water (alkoxysilane / water) is 1.0, titanium The atomic ratio (Ti / Si) of atoms and silicon atoms was 0.43.

Synthesis Example 9 [Preparation of titanosiloxane compound (B)]
A reaction vessel similar to Synthesis Example 6 was charged with 1,667 parts of tetraethoxysilane, 1,601 parts of B-7 and 2,768 parts of IPA, and 144 parts of deionized water and IPA500 under air cooling while stirring in a nitrogen atmosphere. The mixture consisting of parts was added dropwise over 2 hours. During this time, the temperature of the mixture rose from 20 ° C. to 35 ° C. due to heat generation. Next, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 4.5 hours. Thereafter, IPA and ethanol and n-butanol produced by the reaction were distilled off under reduced pressure to obtain 2,428 parts of a pale yellow transparent liquid product. This liquid product is a titanosiloxane compound containing an alkoxy group bonded to a titanium atom and an alkoxy group bonded to a silicon atom. Hereinafter, this is abbreviated as a titanosiloxane compound (B-4). The titanium atom and silicon atom contained in the titanosiloxane compound (B-4) are 22.1% and 19.8%, respectively, in terms of TiO ₂ and SiO ₂ . In this synthesis example, the molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is 0.5, the molar ratio of alkoxysilane compound to water (alkoxysilane / water) is 1.0, and titanium. The atomic ratio (Ti / Si) of atoms and silicon atoms was 0.87.

Synthesis Example 10 [Preparation of titanosiloxane compound (B)]
In a reaction vessel similar to Synthesis Example 6, 272.4 parts of MTMS, 340.3 parts of tetra-n-butoxytitanium and 432 parts of IPA were charged, and from 36 parts of deionized water and 180 parts of IPA under air cooling while stirring in a nitrogen atmosphere. The resulting mixture was added dropwise over 2 hours. During this time, the temperature of the mixture rose from 27 ° C. to 34 ° C. due to heat generation. Next, the temperature was raised to 80 ° C., and the mixture was heated and stirred at the same temperature for 5 hours to obtain a pale yellow transparent solution of a titanosiloxane compound containing an alkoxy group bonded to a titanium atom and an alkoxy group bonded to a silicon atom. . Hereinafter, this solution is abbreviated as a titanosiloxane solution (B-5). The titanium atom and silicon atom contained in the titanosiloxane solution (B-5) are 6.4% and 10.6%, respectively, in terms of TiO ₂ and CH ₃ SiO _1.5 . In this synthesis example, the molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is 0.5, the molar ratio of alkoxysilane compound to water (alkoxysilane / water) is 1.0, and titanium. The atomic ratio (Ti / Si) of atoms and silicon atoms was 0.5.

Synthesis Example 11 [Preparation of titanosiloxane compound (B)]
In a reaction vessel similar to Synthesis Example 6, MTMS681 parts, B-4 [partial hydrolysis condensate of tetra-n-butoxytitanium (average tetramer) manufactured by Nippon Soda Co., Ltd.] 1,011 parts and IPA1,182 A mixture consisting of 90.1 parts deionized water and 313 parts IPA was added dropwise over 2 hours under air cooling while stirring under a nitrogen atmosphere. During this time, the temperature of the mixture rose from 20 ° C. to 28 ° C. due to heat generation. Next, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 4.5 hours. Thereafter, IPA and methanol and n-butanol produced by the reaction were distilled off under reduced pressure to obtain 256.8 parts of a yellow transparent liquid product. This liquid product is a titanosiloxane compound containing an alkoxy group bonded to a titanium atom and an alkoxy group bonded to a silicon atom. Hereinafter, this is abbreviated as a titanosiloxane compound (B-6). The titanium atom and silicon atom contained in this titanosiloxane compound (B-6) are 24.8% and 26.2% in terms of TiO ₂ and CH ₃ SiO _1.5 , respectively. In this synthesis example, the molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is 0.5, the molar ratio of an alkoxysilane compound to water (alkoxysilane / water) is 0.5, and titanium. The atomic ratio (Ti / Si) of atoms and silicon atoms was 0.80.

Example 1
A mixed solvent consisting of 129.2 parts of titanosiloxane compound (B-1), propylene glycol monomethyl ether acetate (PGMAC) and IPA (weight ratio: PGMAC / IPA = 50/50, hereinafter abbreviated as solvent (S)) 132 0.02 parts of the polymer solution (A-1) 72.1 parts was added and mixed well to prepare a curable resin composition having an active ingredient of 30.0%. Hereinafter, this curable resin composition is abbreviated as a composition (S-1). In this example and the following examples and comparative examples, the active ingredient refers to a cured product that is generated when it is assumed that the curing reaction of the curable composition has progressed 100%.

  Subsequently, the prepared composition (S-1) was used as a paint as it was, and a coated product was prepared as follows.

In preparing the coated product, the following hot-dip galvanized steel sheet, polyethylene terephthalate (PET) film, and polypropylene resin (PP) molded plate were used as substrates.
Hot-dip galvanized steel sheet: Hot-dip galvanized steel sheet treated with chromate (size 70 x 150 x 0.8 mm)
PET film: PET film subjected to corona discharge treatment (film thickness: 25 μm)
PP resin molded plate: Untreated PP resin plate (size 70 x 150 x 2 mm)

The composition (S-1) was applied to the hot-dip galvanized steel sheet, PET film and PP resin molded plate using a bar coater so that the dry film thicknesses were 2 μm, 10 μm and 30 μm, respectively, and room temperature (25 ) For 7 days and cured, and coated plate (1) of hot dip galvanized steel sheet with clear coating containing acrylic resin, titanium atom and silicon atom, coated film (2) on PET film and PP A resin-plated plate (3) was obtained. The obtained film had excellent transparency and was slightly colored yellow. The calculated values of the content ratio (weight ratio) of titanium and silicon in terms of the acrylic resin and oxide in the clear coating film obtained are as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 30.0: 35.0: 35.0

Using these coated plates and coated films, the performance was evaluated as follows.
Corrosion resistance: A coating on the hot-dip galvanized steel sheet (1) was cut using a cutter knife and set in a salt spray tester to perform a salt spray test for 480 hours (JIS K-5400). Test according to 9.1). After completion of the test, the coated plate 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. The smaller this value, the better the corrosion resistance.
Curability: Judged by gel fraction value. The gel fraction was obtained by peeling the cured coating film on the coated plate (3) of the PP resin molded plate and immersing it in acetone at room temperature (25 ° C.) for 1 day and drying the residual coating film at 110 ° C. for 1 hour. The value obtained by dividing the weight of the gel content by the coating weight before immersion was multiplied by 100 and determined. The higher this value, the better the curability.
Refractive index: Refractive index measuring device (METRCON) for coated film (2) on PET film
The refractive index of the cured coating film was obtained by measuring the refractive index using a model 2010 prism coupler).

The performance of the cured coating film obtained from the paint of this example was as follows.
Corrosion resistance: Maximum width of rust 0.2mm
Refractive index: 1.589
Gel fraction: 91.7%

  When the composition (S-1) was allowed to stand at 25 ° C. in a sealed state, it did not gel after 2 months and was stable.

Example 2
Add 74.3 parts of the polymer solution (A-3) to a mixture of 129.9 parts of the titanosiloxane compound (B-1) and 129.8 parts of the solvent (S) and mix well. % Curable resin composition was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (S-2).

Next, the prepared composition (S-2) was used as a coating as it was, and painted and cured in the same manner as in Example 1 except that the composition (S-2) was used instead of the composition (S-1). A hot-dip galvanized steel plate coated with a clear coating containing acrylic resin, titanium atoms and silicon atoms (1), a coating film on a PET film (2) and a PP resin molded plate (3 ) The obtained film had excellent transparency and was slightly colored yellow. The calculated value of the content ratio (weight ratio) of titanium and silicon in terms of polyurethane resin and oxide in the clear coating film obtained is as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 30.0: 35.0: 35.0

The cured coating film obtained from the coating material of this example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 0.4mm
Refractive index: 1.601
Gel fraction: 92.9%

  When the composition (S-2) was allowed to stand at 25 ° C. in a sealed state, it did not gel after 2 months and was stable.

Example 3
The polymer solution (A-4) 74.6 is added to a mixture of the titanosiloxane compound (B-2) 126.8 parts and the solvent (S) 131.9 and mixed well, and the active ingredient is 30.0%. A curable resin composition was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (S-3).

Next, the prepared composition (S-3) was used as it was as a paint, and painted and cured in the same manner as in Example 1 except that the composition (S-3) was used instead of the composition (S-1). A coating plate (1) of a hot-dip galvanized steel plate provided with a clear coating film containing polyurethane resin, titanium atom and silicon atom, a coating film (2) on a PET film, and a coating plate of a PP resin molding plate (3 ) The obtained film had excellent transparency and was slightly colored yellow. The calculated values of the content ratio (weight ratio) of titanium and silicon in terms of polyurethane resin and oxide in the clear coating film obtained are as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 30.0: 27.8: 42.8

The cured coating film obtained from the coating material of this example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 0.7mm
Refractive index: 1.579
Gel fraction: 90.5%

  When the composition (S-3) was allowed to stand at 25 ° C. in a sealed state, it did not gel after 2 months and was stable.

Example 4
100.5 parts of the polymer solution (A-4) is added to a mixture composed of 58.8 parts of the titanosiloxane compound (B-3) and 130.5 parts of the solvent (S) and mixed well. A 0% curable resin composition was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (S-4).

Next, the prepared composition (S-4) was used as it was as a paint, and painted and cured in the same manner as in Example 1 except that the composition (S-4) was used instead of the composition (S-1). A coating plate (1) of a hot-dip galvanized steel plate provided with a clear coating film containing polyurethane resin, titanium atom and silicon atom, a coating film (2) on a PET film, and a coating plate of a PP resin molding plate (3 ) The obtained film had excellent transparency and was slightly colored yellow. The calculated values of the content ratio (weight ratio) of titanium and silicon in terms of polyurethane resin and oxide in the clear coating film obtained are as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 40.0: 20.0: 40.0

The cured coating film obtained from the coating material of this example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 0.7mm
Refractive index: 1.565
Gel fraction: 91.5%

When the composition (S-4) was allowed to stand at 25 ° C. in a sealed state, it did not gel after 2 months and was stable.

Example 5
To a mixture comprising 190.9 parts of the titanosiloxane compound (B-4) and 158.8 parts of the solvent (S), 50.3 parts of the polymer solution (A-4) is added and mixed well, and the active ingredient is 25. A 0% curable resin composition was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (S-5).

Next, the prepared composition (S-5) was used as a coating as it was, and painted and cured in the same manner as in Example 1 except that the composition (S-5) was used instead of the composition (S-1). A coating plate (1) of a hot-dip galvanized steel plate provided with a clear coating film containing polyurethane resin, titanium atom and silicon atom, a coating film (2) on a PET film, and a coating plate of a PP resin molding plate (3 ) The obtained film had excellent transparency and was slightly colored yellow. The calculated content ratio (weight ratio) of titanium and silicon in terms of acrylic resin and oxide in the clear coating film obtained is as follows.
Acrylic resin: TiO ₂ : SiO ₂ = 20.0: 42.2: 37.8

The cured coating film obtained from the coating material of this example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 0.2mm
Refractive index: 1.595
Gel fraction: 90.1%

  When the composition (S-5) was allowed to stand at 25 ° C. in a sealed state, it did not gel after 2 months and was stable.

Example 6
Add 171.6 parts of polymer solution (A-5) to a mixture of titanosiloxane solution (B-5) and 106.4 parts of solvent (S), mix well, and cure 22.0% active ingredient A functional resin composition was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (S-6).

Next, the prepared composition (S-6) was used as it was as a paint, and was coated and cured in the same manner as in Example 1 except that the composition (S-6) was used instead of the composition (S-1). A coating plate (1) of a hot-dip galvanized steel plate provided with a clear coating film containing polyurethane resin, titanium atom and silicon atom, a coating film (2) on a PET film, and a coating plate of a PP resin molding plate (3 ) The obtained film had excellent transparency and was slightly colored yellow. The calculated values of the content ratio (weight ratio) of titanium and silicon in terms of polyurethane resin and oxide in the clear coating film obtained are as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 70.0: 11.3: 18.7

The cured coating film obtained from the coating material of this example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 1.1mm
Refractive index: 1.556
Gel fraction: 90.1%

When the composition (S-6) was allowed to stand at 25 ° C. in a sealed state, it did not gel after 2 months and was stable.

Example 7
Add 199.0 parts of polymer solution (A-2) to a mixture of 39.2 parts of titanosiloxane solution (B-6) and 95.1 parts of solvent (S) and mix well. A 0% curable resin composition was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (S-6).

Next, the prepared composition (S-6) was used as it was as a paint, and was coated and cured in the same manner as in Example 1 except that the composition (S-6) was used instead of the composition (S-1). A coating plate (1) of a hot-dip galvanized steel plate provided with a clear coating film containing polyurethane resin, titanium atom and silicon atom, a coating film (2) on a PET film, and a coating plate of a PP resin molding plate (3 ) The obtained film had excellent transparency and was slightly colored yellow. The calculated values of the content ratio (weight ratio) of titanium and silicon in terms of polyurethane resin and oxide in the clear coating film obtained are as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 80.0: 9.7: 10.3

The cured coating film obtained from the coating material of this example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 1.5mm
Refractive index: 1.530
Gel fraction: 91.1%

When the composition (S-6) was allowed to stand at 25 ° C. in a sealed state, it gelled after 4 days and had good stability.

Comparative Example 1
240.3 parts of polymer solution (A-1), 2.0 parts of dibutyltin diacetate (DBTDA) as a curing catalyst and 91.0 parts of solvent (S) were mixed to form a titano having an NV of 30.0%. A comparative curable composition containing no siloxane compound was prepared. Hereinafter, this curable resin composition is abbreviated as a composition (RS-1). Then, the prepared composition (RS-1) was used as a coating as it was, and painted and cured in the same manner as in Example 1 except that the composition (RS-1) was used instead of the composition (S-1). Thus, a hot-dip galvanized steel plate coated plate (1), a PET film coated film (2) and a PP resin molded plate coated plate (3) provided with a clear coating film from an acrylic resin were obtained.

The cured coating film obtained from the paint of this comparative example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Maximum width of rust 6.5mm
Refractive index: 1.510
Gel fraction: 89.1%

  When the composition (RS-1) was left at 25 ° C. in a sealed state, it gelled after 4 hours and was inferior in stability.

Comparative Examples 2-5
Each polymer fat solution, DBTDA and solvent (S) were blended in the ratios shown in Table 3, and comparative compositions (RS-2) to (RS-) containing no titanosiloxane having an NV of 30% 5) was prepared. Next, the prepared compositions (RS-2) to (RS-5) were used as they were as paints, and Example 1 was used except that each composition for comparison was used instead of the composition (S-1). Painted and cured in the same way, painted plate of hot-dip galvanized steel sheet with clear coating from acrylic resin (1), painted film on PET film (2) and painted plate of PP resin molded plate (3) Got.

  The cured coating film obtained from the coating material of this comparative example was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 6
B-4 (oligomer of titanium tetra-n-butoxide used in Synthesis Example 11) 192.3 parts, MTMS partial hydrolysis condensate (CH ₃ SiO _1.5 content: 70.0%) 14.7 Part of the solvent and 96.9 parts of the solvent (S) and 192.3 parts of the polymer solution (A-1) were mixed, and the comparative curability containing 30.0% titanium and silicon atoms in NV. A composition was prepared. Hereinafter, this curable composition is abbreviated as a composition (RS-3). Next, the prepared composition (RS-3) was used as a coating as it was, and painted and cured in the same manner as in Example 1 except that the composition (RS-3) was used instead of the composition (S-1). Thus, a hot-dip galvanized steel plate coated plate (1), a PET film coated film (2) and a PP resin molded plate coated plate (3) provided with a clear coating film from an acrylic resin were obtained. The obtained coating film was considerably clouded. The calculated values of the content ratio (weight ratio) of titanium and silicon in terms of polyurethane resin and oxide in the clear coating film obtained are as follows.
Acrylic resin: TiO ₂ : CH ₃ SiO _1.5 = 80.0: 9.7: 10.3

The cured coating film obtained from the paint of this comparative example was evaluated in the same manner as in Example 1 and the following results were obtained.
Corrosion resistance: Rust is generated on the entire coating surface. Refractive index: 1.530
Gel fraction: 88.1%

  When the composition (RS-3) was left in a sealed state at 25 ° C., it gelled in 8 hours and was inferior in stability.

Claims (9)

A curable resin composition comprising a vinyl polymer (A) containing a hydrolyzable silyl group, a titanosiloxane compound (B) soluble in an organic solvent, and an organic solvent (C) , wherein the vinyl polymer The ratio of the polymer (A) to the titanosiloxane compound (B) is 49 to 1,500 parts by weight of the titanosiloxane compound (B) with respect to 100 parts by weight of the vinyl polymer (A). A curable resin composition .   The curable resin composition according to claim 1, wherein the titanosiloxane compound (B) soluble in the organic solvent contains an alkoxy group bonded to a titanium atom and / or an alkoxy group bonded to a silicon atom. .   A titanosiloxane compound (B) soluble in the organic solvent partially comprises an alkoxytitanium compound (b-1) and / or a partial hydrolysis-condensation product (b-2) thereof and an alkoxysilane compound (b-3). The curable resin composition according to claim 1 or 2, which is obtained by cohydrolysis condensation.   The titanosiloxane compound (B) soluble in the organic solvent has a molar ratio (water / alkoxy group) of alkoxy groups bonded to water and titanium atoms of 0.2 to 1.3, and an alkoxysilane compound Alkoxytitanium compound (b-1) and / or its partial hydrolysis at a ratio satisfying the molar ratio of (b-3) to water [(b-3) / water] of 0.3 to 5 The curable resin composition according to claim 1 or 2, which is obtained by performing partial cohydrolysis condensation using the condensate (b-2), the alkoxysilane compound (b-3) and water. .   In the organic solvent-soluble titanosiloxane compound (B), a molar ratio of water and an alkoxy group bonded to a titanium atom (water / alkoxy group) is in the range of 0.2 to 1.3, an alkoxysilane compound (b -3) and water molar ratio [(b-3) / water] is 0.3 to 5, and the atomic ratio (Ti / Si) of titanium atoms to silicon atoms is 0.1 to 4.0. In a ratio satisfying all of the above, partially co-hydrolyzed using an alkoxy titanium compound (b-1) and / or a partially hydrolyzed condensate thereof (b-2), an alkoxysilane compound (b-3) and water. The curable resin composition according to claim 1 or 2, which is obtained by performing condensation.   The curable resin composition according to claim 1 or 2, wherein the vinyl polymer contains a carboxyl group. The curable resin composition according to claim 1, 2 or 6 wherein the vinyl polymer is an acrylic resin. A paint comprising the curable resin composition according to any one of claims 1 to 7 . A coated article obtained by painting the paint according to claim 8 .