JP2000129176A - Composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the reduction activity of titanium dioxide as a photocatalyst component to be blended, reduce the rate of removal of nitrogen oxides in the air as nitric acid, and have excellent storage stability and Provided is a coating composition excellent in general coating film performance including film appearance, weather resistance, heat resistance and the like. SOLUTION: The composition comprises (A) at least one component selected from a hydrolyzable organosilane represented by methotrimethoxysilane and the like, a hydrolyzate of the organosilane and a partial condensate of the organosilane, And (B) ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less contain fine particles of a composite oxide dispersed in a metal oxide other than titanium dioxide, or the components (A) and (B); (C) A polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal and / or a side chain of a polymer molecular chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition, and more particularly, to an organopolysiloxane containing fine particles of a composite oxide in which ultrafine titanium oxide particles having photocatalytic activity are dispersed in another metal oxide. The present invention relates to a silane-based coating composition.

[0002]

2. Description of the Related Art The development of organosilane-based coating materials as maintenance-free coating materials having excellent weather (light) resistance and stain resistance has been promoted, but there is a demand for such organosilane-based coating materials. Performance has become more and more severe, and recently
A coating material excellent in weather resistance, heat resistance, stain resistance, and the like is required. In recent years, various technologies have been proposed that focus on the germicidal, fungicidal, and antifouling properties of the photocatalytic component, as well as the action of removing nitrogen oxides from the air. Kaihei 7-331120
Publication), titanium dioxide, hydrolyzable silicon compound (alkyl silicate or silicon halide) hydrolyzate,
And a solvent (water or alcohol) and a titanium oxide coating film-forming composition for a photocatalyst (JP-A-8-164334) or titanium dioxide fine particles mixed with a binder such as a fluororesin to form a sheet or panel. A contaminant purifying material (Japanese Patent Application Laid-Open No. 6-315614) is known. In particular, the concentration of nitrogen oxides (NOx) is high due to the exhaust gas of automobiles around heavy traffic roads such as large cities. Since it has become a serious problem, attention has been paid to the action of the photocatalytic component for removing nitrogen oxides in the air. However, these conventional techniques basically use a photocatalytic component such as titanium dioxide in the form of a mixture, even if it is used in the form of a mixture.
By the way, titanium dioxide which is a typical photocatalytic component has the following properties. That is, when the surface of titanium dioxide particles as a semiconductor is irradiated with ultraviolet rays, electrons in the valence band are excited and move to the conduction band, and holes are generated in the valence band. Then, the electrons transferred to the conduction band reduce the oxygen present in the surroundings, and the superoxide anion (−
O ₂ ⁻ ) is generated, and the superoxide anion exhibits an oxidizing power by passing through hydrogen peroxide (H ₂ O ₂ ) or the like. Further, holes generated in the valence band are caused by surrounding water (H ₂
O) to oxidize it to produce a highly oxidative hydroxy radical (.
OH). Therefore, when the titanium dioxide irradiated with ultraviolet light comes into contact with the atmosphere containing nitrogen oxides, the nitrogen oxides are oxidized by hydroxy radicals and the like to become nitric acid, and the nitric acid is washed away from the surface of the titanium oxide particles by rainwater or the like, The photocatalytic activity of titanium dioxide will be regenerated. However, when nitric acid generated by the oxidation of nitrogen oxides is washed away by rainwater or the like, an aqueous solution having a high acidity flows out to the periphery,
Another problem of polluting the environment has arisen, and as a countermeasure, a process of neutralizing with alkali is necessary,
The above-mentioned conventional paint or purifying material containing a photocatalytic component has been inevitable.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art. The problem is that ultrafine titanium dioxide particles are dispersed as a photocatalytic component in another metal oxide. By using the fine particles composed of the composite oxide, the reduction activity of the photocatalyst component, that is, the performance of decomposing nitrogen oxides into nitrogen molecules (N ₂ ) and oxygen molecules (O ₂ ) is enhanced, and the rate of removal as nitric acid is improved. By combining this photocatalyst component with a specific organosilane component, the rate at which nitrogen oxides are removed as nitric acid can be reduced, and storage stability is excellent, and coating film appearance, weather resistance, An object of the present invention is to provide a coating composition excellent in general coating film performance including heat resistance and the like.

[0004]

The present invention firstly provides:
(A) The following general formula (1)

[0005]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
8 represents a monovalent organic group, R ² represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenyl group, and n is an integer of 0 to 2. ), At least one component selected from a hydrolyzate of the organosilane and a partial condensate of the organosilane, and (B) a composite oxide of titanium dioxide and a metal oxide other than titanium dioxide. A coating composition comprising fine particles of a composite oxide in which ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less are dispersed in a metal oxide other than titanium dioxide. Hereinafter, this will be referred to as “first invention”).

The present invention relates to (A) the following general formula (1)

[0008]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
8 represents a monovalent organic group, R ² represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenyl group, and n is an integer of 0 to 2. ), At least one component selected from a hydrolyzate of the organosilane and a partial condensate of the organosilane, (B) a composite oxide of titanium dioxide and a metal oxide other than titanium dioxide Particles having a crystallite diameter of 1
Ultrafine titanium dioxide particles having a particle size of 0 nm or less are dispersed in a metal oxide other than titanium dioxide, and are composed of composite oxide particles, and (C) a polymer molecule having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group. A coating composition containing a polymer having a chain terminal and / or a side chain (hereinafter, referred to as “second invention”).

Hereinafter, the first invention and the second invention will be described.
This will be described in detail. (A) Component The component (A) in the first invention and the second invention is an organosilane (hereinafter, referred to as “organosilane (1)”) represented by the general formula (1) or an organosilane (1). It comprises at least one component selected from a hydrolyzate and a partial condensate of organosilane (1), and acts as a main binder in a coating composition. In the first invention and the second invention, the hydrolyzate of the organosilane (1) does not need to have all of the ² to 4 OR ² groups contained in the organosilane (1) hydrolyzed. Component only hydrolyzed, 2
Any of a component in which at least one is hydrolyzed, or a mixture thereof may be used. The partial condensate of the organosilane (1) is a silanol group formed by hydrolyzing at least a part of ² to 4 OR ² groups contained in the organosilane (1) and condensing Si—O 2. -Means a component that forms a Si bond but has not yet been substantially completely cured, and includes a component in which only part of the silanol group is condensed, a mixture of components having different degrees of condensation of the silanol group, and the like. Is the concept of

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
Examples of the monovalent organic group of 8 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Alkyl groups such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclohexyl group, vinyl group, allyl group, acyl group, phenyl group, glycidyl group, glycidoxy group, 3 , 4-epoxycyclohexyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group and the like, and substituted derivatives of these groups. Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a ureido group, and an ammonium base. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. When a plurality of R ¹ are present in the general formula (1), they may be the same or different from each other.

The alkyl group having 1 to 5 carbon atoms for R ² includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and s.
ec-butyl group, t-butyl group, n-pentyl group and the like. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group and a caproyl group. Can be mentioned. When a plurality of R ² are present in the general formula (1), they may be the same or different from each other. As R ² in the general formula (1),
An alkyl group and an acyl group are preferred, and an alkyl group is more preferred, whereby a more excellent coating composition can be obtained.

Among the organosilanes (1), specific examples of the compound of the formula (1) wherein n is 0 include tetramethoxysilane, trimethoxyethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane,
Examples thereof include tetraalkoxysilanes such as tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane, as well as tetraacetyloxysilane and tetraphenoxysilane. Among these compounds, the tetraalkoxysilanes are particularly preferably tetramethoxysilane, trimethoxyethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetraethoxysilane and the like. The compounds of the formula (1) wherein n is 0 can be used alone or in combination of two or more.

Specific examples of the compound of the formula (1) wherein n is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane,
n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-
(Meth) acryloxypropyltrimethoxysilane,
3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, 3-chloropropyltrimethoxysilane,
-Chloropropyltriethoxysilane, 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane Methoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-
In addition to trialkoxysilanes such as mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane, Acetyloxysilane, methyltriphenoxysilane and the like can be mentioned. Among these compounds, the trialkoxysilanes are particularly preferably methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like.
The compounds of the formula (1) wherein n is 1 can be used alone or as a mixture of two or more.

Specific examples of the compound of the formula (1) wherein n is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, -N-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, n-pentylmethyldimethoxysilane, n-pentyl methyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, di-
n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane,
In addition to dialkoxysilanes such as di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldiacetyloxysilane, dimethyldisilane Phenoxysilane and the like can be mentioned. Among these compounds, dialkoxysilanes are particularly preferably dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane and the like. N in the general formula (1)
Can be used alone or in combination of two or more.

In the present invention, the organosilane (1)
Is a compound of the general formula (1) wherein n is 0,
Of the compound in which n is 1 and the compound of general formula (1) in which n is 2 or a mixture of any two or more of these three compounds May be. In the first invention and the second invention, when a hydrolyzate or a partial condensate of the organosilane (1) is used, the organosilane (1) may be used after being hydrolyzed or partially condensed. When preparing the composition by mixing the silane (1) with the remaining components,
By adding an appropriate amount of water, the organosilane (1)
Is preferably hydrolyzed or partially condensed. The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of the partial condensate of the organosilane (1) used in the first invention and the second invention is usually from 8,000 to.
It is in the range of 10,000, preferably 1,000 to 50,000. Commercially available products of the component (A) in the first and second inventions include MKC silicate manufactured by Mitsubishi Chemical Corporation, silicate manufactured by Tama Chemical Co., Ltd., silicone resin manufactured by Dow Corning Toray Co., Ltd., and Toshiba Silicone ( And silicone oligomers manufactured by Nippon Unica Co., Ltd., and these may be used. In the first invention and the second invention, the component (A) can be used alone or in combination of two or more.

Component (B) The component (B) in the first invention and the second invention is a composite oxide of titanium dioxide and a metal oxide other than titanium dioxide (hereinafter, referred to as “other metal oxide”). These are fine particles comprising a composite oxide in which ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less, preferably 8 nm or less, are dispersed in another metal oxide. here,
“Crystallite diameter” refers to Sheller data from X-ray diffraction data.
Means the basic particle diameter of the crystal calculated using the following equation.
Further, the lower limit of the crystallite diameter of the ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less is not particularly limited as long as the titanium dioxide can basically take the form of particles.

Other metal oxides include Al ₂ O ₃ , S
iO ₂ and composite oxides of these metals are preferable. The other metal oxides can be used alone or in combination of two or more.

The crystal form of the titanium dioxide ultrafine particles may be any of anatase type, rutile type and brookite type.
Preferably it is an anatase type. Particularly preferred titanium dioxide ultrafine particles are anatase type ultrafine particles having a crystallite diameter of 8 nm or less. The content of titanium dioxide in the component (B) is preferably from 1 to 80% by weight. The average particle diameter of the fine particles comprising the composite oxide constituting the component (B) is preferably smaller from the viewpoint of photocatalytic activity, and is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm or less.

Next, a preferred method for producing the component (B) will be described. Examples of the Ti source include titanium tetrachloride, titanium trichloride, titanyl sulfate, titanium sulfate and the like, and these can be used alone or in combination of two or more. Examples of the Al source include aluminum chloride, aluminum sulfate, sodium aluminate, and alumina sol. These can be used alone or in combination of two or more. Examples of the Si source include organic silicon compounds, sodium silicate, lithium silicate, silica sol, and the like. These can be used alone or in combination of two or more. Specifically, a preferred method for producing the component (B) is to hydrolyze a solution containing at least one selected from an Al source and a Si source and a Ti source,
The composite oxide is precipitated, and the pH of the obtained slurry of the composite oxide is usually adjusted to 3 to 10, and then washed and filtered. Thereafter, the obtained composite oxide is usually put in 100
After sintering at a temperature of ℃ 600 ° C., pulverization is performed as necessary. As the solvent used for the solution containing the Al source, the Si source and the Ti source, for example, water, a mixed solvent of water and a hydrophilic solvent (for example, lower alcohols) and the like can be used. Al source, Si source and Ti source
When preparing the solution containing the source, the respective components may be made into a solution in advance and then mixed, or the remaining components may be added and dissolved in a solution of one or two components. The hydrolysis temperature can be appropriately selected within the range of 20 to 120 ° C.,
The range of 105 ° C. is preferable in that the hydrolysis efficiency is high and more uniform composite oxide fine particles can be obtained. The alkalis and acids used for pH adjustment after hydrolysis can be appropriately selected. By producing the component (B) by such a method, it is possible to stably form ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less having excellent photocatalytic activity and extremely high nitrogen oxide reduction activity. Thus, the ultrafine particles can be uniformly dispersed in another metal oxide.

In the first invention and the second invention, (B)
The components can be used alone or in combination of two or more. The amount of the component (B) used in the first invention and the second invention is usually 1 to 500 parts by weight, preferably 5 to 400 parts by weight, based on 100 parts by weight of the organosilane (1).

The component (B) in the first and second inventions has a remarkably enhanced reduction activity of titanium dioxide as a photocatalytic component, and converts nitrogen oxides into nitrogen molecules (N ₂ ) and oxygen molecules (O ₂ ). Has the property that it can be decomposed effectively to reduce the rate of removal as nitric acid. Further, in the coating film obtained from the coating composition of the first and second inventions, the component (B) is co-condensed with the component (A) and the like,
The photocatalytic activity, hydrophilicity, stain resistance, bactericidal and fungicidal properties of the coating film are maintained for a long time.

Component (C) The component (C) in the second invention has a hydrolyzable group and / or
Alternatively, the polymer comprises a polymer having a silyl group having a silicon atom bonded to a hydroxyl group (hereinafter, referred to as “specific silyl group”) at the terminal and / or the side chain of the polymer molecular chain. When such a component (C) hardens a coating film obtained from the coating composition of the second invention, the hydrolyzable group and / or the hydroxyl group in the silyl group is changed to the component (A) and the component (B). ) A component that provides excellent coating performance by co-condensing with the component. The content of the specific silyl group in the component (C) is usually 0.001 to 2 with respect to the polymer before the introduction of the specific silyl group in terms of the amount of silicon atoms.
0% by weight, preferably 0.01 to 15% by weight. Preferred specific silyl groups are groups represented by the following general formula (2).

[0024]

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Wherein X is a hydrolyzable group such as a halogen atom, an alkoxyl group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxyl group, an amino group or a hydroxyl group; R ³ is a hydrogen atom; Represents an alkyl group having 10 to 10 or an aralkyl group having 1 to 10 carbon atoms, and i represents 1
-3. )

The component (C) includes, for example, (a) a hydrosilane compound corresponding to the general formula (2) (hereinafter referred to as “hydrosilane compound (a)”), a vinyl-based compound having a carbon-carbon double bond. A method of causing an addition reaction to the carbon-carbon double bond in a polymer (hereinafter, referred to as an “unsaturated vinyl polymer”), (b) the following general formula (3)

[0027]

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[0028] Table in (wherein, X, R ^3, i has the same meaning as X, R ^3, i, respectively, in formula (2), R ⁴ represents an organic group having a polymerizable double bond.) Silane compound (hereinafter referred to as "unsaturated silane compound (b)")
And another vinyl-based monomer.

Examples of the hydrosilane compound (a) used in the method (a) include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane Alkoxysilanes such as phenyldimethoxysilane, trimethoxysilane and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; methyldiaminoxysilane, triaminoxysilane, dimethyl Examples include aminoxysilanes such as aminoxysilane. These hydrosilane compounds (a) can be used alone or in combination of two or more.

The unsaturated vinyl polymer used in the above method (A) is not particularly limited as long as it is other than a polymer having a hydroxyl group. For example, the following (A-1) and (A)
It can be manufactured by the method 2) or a combination thereof. That is, the (a-1) functional group (hereinafter, referred to as
It is called "functional group (α)". )) Is (co) polymerized with a vinyl monomer having the functional group (α) in the (co) polymer.
Is reacted with a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (β)”) with an unsaturated compound having a carbon-carbon double bond to obtain a polymer molecular chain. A method for producing an unsaturated vinyl polymer having a carbon-carbon double bond in a side chain thereof. (A-2) A radical polymerization initiator having a functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid or the like) is used, or a functional group ( a) (for example, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid), and (co) polymerizing a vinyl monomer to form one end of the polymer molecular chain or After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at both ends, a functional group (β) is added to the functional group (α) in the (co) polymer. ) And an unsaturated compound having a carbon-carbon double bond to produce an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain. Examples of the reaction between the functional group (α) and the functional group (β) in the methods (a-1) and (a-2) include an esterification reaction between a carboxyl group and a hydroxyl group, a carboxylic anhydride group and a hydroxyl group. Ring-opening esterification reaction with carboxyl group and epoxy group, amidation reaction between carboxyl group and amino group, ring-opening amidation reaction between carboxylic anhydride group and amino group, epoxy group Ring-opening addition reaction between
A urethanization reaction between a hydroxyl group and an isocyanate group, a combination of these reactions, and the like can be given.

Examples of the vinyl monomer having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid;
Unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate;
Hydroxyl-containing vinyl monomers such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and 2-hydroxyethyl vinyl ether; 2-aminoethyl (meth) acrylate; Amino group-containing vinyl monomers such as 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-aminoethyl vinyl ether; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl -1-ethylamine (meth) acrylimide, 1,1-dimethyl-1-
(2-hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2 ′)
-Hydroxyethyl) amine (meth) acrylimide,
Amine-containing vinyl monomers such as 1,1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide; epoxy groups such as glycidyl (meth) acrylate and allyl glycidyl ether Vinyl monomers and the like. These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.

Other vinyl monomers to be copolymerized with a vinyl monomer having a functional group (α) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Cyclohexyl,
Trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, 3, (meth) acrylate
3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, heptafluoropropyl (meth) acrylate, 4,4,4-trifluoro (meth) acrylate Butyl, 3,3,4,4,4-pentafluorobutyl (meth) acrylate,
2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, nonafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 4- ( (Meth) acryloyloxy-
1,2,2,6,6-pentamethylpiperidine, (meth) acrylamide, crotonamide, maleic diamide, fumaric diamide, itaconic diamide, α-ethylacrylamide, N-butoxymethyl (meth) acrylamide, (meth ) Acrylonitrile, styrene, α
-Methylstyrene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, hexafluoropropylene, vinyl acetate, vinyl propionate, ethyl vinyl ether and the like. These other vinyl monomers can be used alone or in combination of two or more. Examples of the unsaturated compound having a functional group (β) and a carbon-carbon double bond include, for example, a vinyl monomer similar to the vinyl monomer having a functional group (α) and the hydroxyl group-containing vinyl compound. Examples include isocyanate group-containing unsaturated compounds obtained by reacting a monomer and a diisocyanate compound in equimolar amounts.

As a specific example of the unsaturated silane compound ( _II ) used in the above method ( _II ), CH ₂ ＣＨCH
Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHSi (OCH
₃ ) ₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ ＣＨCH
SiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH
_{3) (OCH 3) 2,} CH 2 = CHCOO (CH 2) 2 Si
(OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (C
H ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si
(OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (C
H ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ SiCl
₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl
₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH ₂
ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ )
₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (OCH
₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH
₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃
Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ )
₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₂ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ )
₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₃ SiCl ₃ ,

[0034]

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[0035]

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[0036]

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[0037]

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And the like. These unsaturated silane compounds (b) can be used alone or in combination of two or more. Examples of other vinyl monomers to be copolymerized with the unsaturated silane compound (b) include, for example, vinyl monomers having the functional group (α) exemplified for the method (a-1) and other vinyl monomers. At least one vinyl monomer.

Other examples of the component (C) include a specific silyl group-containing epoxy resin, a specific silyl group-containing polyester resin, and a specific silyl group-containing fluororesin. The specific silyl group-containing epoxy resin is, for example, an epoxy group in an epoxy resin such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, an aliphatic polyglycidyl ether, and an aliphatic polyglycidyl ester. And aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes and the like. Further, the specific silyl group-containing polyester resin, for example, a carboxyl group or a hydroxyl group contained in the polyester resin, aminosilanes having a specific silyl group, carboxysilanes,
It can be produced by reacting glycidylsilanes and the like. Further, the specific silyl group-containing fluororesin includes, for example, aminosilanes, carboxysilanes, glycidylsilanes and the like having a specific silyl group in a carboxyl group or a hydroxyl group contained in a (co) polymer such as ethylene fluoride. Can be produced by reacting

The polystyrene-equivalent number average molecular weight (Mn) of the component (C) is preferably 2,000.
0-100,000, more preferably 4,000-5
It is 0000. In the second invention, the component (C) comprises:
They can be used alone or in combination of two or more. The amount of the component (C) used in the second invention is usually from 2 to 900 based on 100 parts by weight of the organosilane (I).
Parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 200 parts by weight. In this case, if the amount of component (C) used is less than 2 parts by weight, the effect of improving the alkali resistance of the resulting coating film tends to decrease, while if it exceeds 900 parts by weight, the weather resistance of the coating film decreases. Tend.

Furthermore, the following components (D) to (G) can be added to the coating compositions of the first and second inventions. Component (D) The component (D) comprises a catalyst for promoting the hydrolysis / condensation reaction of the component (A) and the like. By using such a component (D), the curing speed of the resulting coating film is increased, and when the coating film is formed, the Mn of the polysiloxane resin generated from the component (A) is increased, and the strength and long-term durability are increased. A coating film having excellent properties and the like can be obtained, and the coating film can be made thicker and the coating operation can be easily performed. As the component (D), an acidic compound, an alkaline compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter, the organometallic compound and / or a partial hydrolyzate thereof are collectively referred to as “organometallic compound or the like”). Is preferred. Among the components (D), examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, and phthalic acid, and acetic acid is preferred. Further, as the alkaline compound, for example, sodium hydroxide,
Potassium hydroxide and the like can be mentioned, and preferred is sodium hydroxide. Further, as the organometallic compound, for example, the following general formula

[0042]

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(Wherein M represents zirconium, titanium or aluminum, and R ⁵ and R ⁶ are each independently ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t- butyl, n- pentyl, n- hexyl group, a cyclohexyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a phenyl group, R ⁷ is
A monovalent hydrocarbon group having 1 to 6 carbon atoms similar to R ⁵ and R ⁶ (however, the hydrocarbon group of R ^{7 and} the hydrocarbon group of R ⁵ or R ⁶ may be the same or different). Other alkoxyl groups having 1 to 16 carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, lauryloxy and stearyloxy groups. And p and q are 0 to
An integer of 4, and (p + q) = (valence of M). ) Or partial hydrolysates of these compounds.

Specific examples of the organometallic compound include tetra-n-butoxyzirconium, tri-n-butoxy.
Ethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n
-Butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate)
Organic zirconium compounds such as zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxy. Organotitanium compounds such as bis (acetylacetate) titanium and di-i-propoxybis (acetylacetone) titanium; tri-i-propoxyaluminum, di-i-propoxyethylacetoacetatealuminum, di-i-propoxyacetylacetoacetate Aluminum nato, i-propoxybis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonato) aluminum, tris (ethylacetoacetate) Aluminum, tris (acetylacetonate) aluminum, organic aluminum compounds such as mono-acetylacetonate · bis (ethylacetoacetate) aluminum and can be given a partial hydrolysis products of these compounds. Of these,
n-butoxyethylacetoacetate zirconium,
Di-i-propoxybis (acetylacetonato) titanium, di-i-propoxyethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, or partial hydrolysates of these compounds are preferred.

The component (D) can be used alone or in combination of two or more. First invention and second invention
The amount of the component (D) used in the invention, other than the organometallic compound, is usually 0 to 100 parts by weight, preferably 0.01 to 8 parts by weight, per 100 parts by weight of the organosilane (1).
0 parts by weight, more preferably 0.1 to 50 parts by weight, and in the case of an organometallic compound or the like, the organosilane (1) 1
Usually, 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 00 parts by weight.
0 parts by weight. In this case, the amount of component (D) used is 10
If the amount exceeds 0 parts by weight, the storage stability of the composition tends to decrease, and the coating film tends to crack.

Component (E) The component (E) is represented by the following general formula:

[0047]

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(Wherein, R ⁸ and R ⁹ are the same as R ⁶ and R ⁷ in each of the general formulas in the metal chelate compound)
Is synonymous with )) And / or β-ketoesters. Such a component (E) is preferably used together when an organometallic compound or the like among the components (D) is used. The component (E) functions as a stability improver of the composition. That is,
By coordinating the component (E) to a metal atom such as an organometallic compound, by appropriately controlling the action of the component (D) to promote the co-condensation reaction between the component (A) and the component (B). It is considered that the composition acts to further improve the storage stability of the obtained composition. Specific examples of the component (E) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, and acetoacetic acid. -T-butyl,
Hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methylhexane-
2,4-dione and the like can be mentioned. Of these, acetylacetone and ethyl acetoacetate are preferred.
The component (E) can be used alone or in combination of two or more. The amount of the component (E) used in the first invention and the second invention is usually 2 mol or more, preferably 3 to 20 mol, per 1 mol of the organometallic compound in the organometallic compound or the like. In this case, if the amount of the component (E) is less than 2 mol, the effect of improving the storage stability of the obtained composition tends to be insufficient.

Component (F) The component (F) is composed of fine particles and / or sol or colloid of an inorganic compound other than the component (B), and is blended according to the desired properties of the coating film. Specific examples of the compound constituting the component (F) include Al (OH) ₃ , Sb ₂ O ₅ ,
_{Si 3 N 4, Sn-In} 2 O 3, Sb-In 2 O 3, M
gF, CeF ₃ , ZnO, CeO ₂ , SiO ₂ , Al _{2
O 3, 3Al 2 O 3 ·} 2SiO 2, BeO, SiC, A
1N, Fe ₄ N, Ba ferrite, SmCO ₅ , YCO
_{5, CeCO 5, PrCO 5,} Sm 2 CO 17, Nd 2 F
e ₁₄ B, ZrO ₂ , Al ₄ O ₃ , AlN, SiC, Be
O and the like can be mentioned. The component (F) may be present in the form of fine particles, an aqueous sol or colloid in which the fine particles are dispersed in water, or a solvent in which the fine particles are dispersed in a polar solvent such as isopropyl alcohol or a non-polar solvent such as toluene. There are sols or colloids in the system. In the case of a solvent-based sol or colloid, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor fine particles. (F)
When the components are an aqueous sol or colloid and a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less. The component (F) may be used alone or
A mixture of more than one species can be used. The amount of the component (F) used in the first invention and the second invention is usually 0% in solid content with respect to 100 parts by weight of the organosilane (1).
To 500 parts by weight, preferably 0.1 to 400 parts by weight.

Component (G) The component (G) comprises a curing accelerator other than the component (D). By using such a component (G), the first
In order to increase the curing rate of a coating film formed from the coating composition of the invention and the second invention and to cure at a relatively low temperature, it is more effective to further add (G). As the component (G), for example, alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine,
Tetraethylenepentamine, piperidine, piperazine,
Metaphenylenediamine, ethanolamine, triethylamine, 3-aminopropyltriethoxysilane, 3
-(2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropylmethyldimethoxysilane, 3-anilinopropyltrimethoxysilane, and various modified amines used as curing agents for epoxy resins Amine compounds such as (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOO) (C ₄ H ₉ )
₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOO (C ₄ H) ₉ )
₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC _{8
H 17) 2, Sn (OCOCC} 8 H 17) carboxylic acid type organic tin compounds such as _{2; (C 4 H 9)} 2 Sn (SCH 2 COOC 8 H 17) 2, (C 4 H 9) 2 Sn (SCH _{2 CH 2 COOC 8 H 17)} 2, (C 8 H 17) 2 Sn (SCH 2 COOC 8 H 17) 2, (C 8 H 17) 2 Sn (SCH 2 CH 2 COOC 8 H 17) 2, (C _{8 H 17) 2 Sn (SCH} 2 COOC 12 H 25) 2, (C 8 H 17) 2 Sn (SCH 2 CH 2 COOC 12 H 25) 2,

[0051]

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Mercaptide-type organotin compounds such as (C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

[0053]

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Sulfide type organotin compounds such as (C ₄ H
_{9) 2} SnO, (or organic tin oxide C ₈ H _{17) 2} SnO or the like, these organic tin oxide and ethyl silicate, dimethyl maleate, diethyl maleate, reaction products of the ester compounds such as dioctyl phthalate Can be mentioned. The component (G) can be used alone or in combination of two or more. First invention and second invention
The amount of the component (G) used in the invention is usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the organosilane (I). Department.

Other Components In the coating composition of the present invention, a filler may be separately added for coloring and thickening the obtained coating film. Such fillers include, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, particulate, fibrous or flaky ceramics, metals or alloys,
And oxides, hydroxides, carbides, nitrides, sulfides and the like of these metals. Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc,
Ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide,
Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, carbonate Magnesium, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth,
Manganese green, Pigment green, Ultramarine blue, Navy blue, Pigment green, Rock ultramarine, Cobalt blue, Cerulean blue, Copper borate, Molybdenum blue, Copper sulfide, Cobalt purple, Mars purple, Manganese purple, Pigment violet, Lead suboxide, Lead acid Calcium, zinc yellow, lead sulfide, chrome yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, bengala, zinc white, antimony white, basic Lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, lead sulfate,
Graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like can be given. The amount of the filler used in the first invention and the second invention is 1% of the total solid content of the composition.
It is usually 300 parts by weight or less based on 00 parts by weight.
Further, the coating compositions of the first and second inventions may optionally contain a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, a surfactant, a silane coupling agent, a titanium cup. Other additives such as a ring agent, a dye, a dispersant, a thickener, a leveling agent and the like can also be blended.

Further, it is preferable to add water and an organic solvent to the coating compositions of the first and second inventions as described below. Water Water is the time of preparing the coating composition, organosilane (1) is hydrolyzed, or a hydrolyzate of organosilane (1) is partially condensed reaction and act to satisfactorily disperse the particulate components Is shown. First invention and second invention
The amount of water used in the invention is usually 0.5 to 3 mol, preferably 0.7 mol, per 1 mol of the organosilane (1).
About 2 mol.

Organic Solvent The organic solvent mainly mixes the components (A) to (G) uniformly to adjust the total solid content of the composition,
It has an effect of being applicable to various coating methods and further improving the dispersion stability and storage stability of the composition. Such an organic solvent is not particularly limited as long as the components can be uniformly mixed.
One or more of alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be mentioned.
Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol,
sec-butyl alcohol, t-butyl alcohol, n
-Hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether,
Examples include ethylene glycol monoethyl ether acetate. Further, specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. , Diisobutyl ketone and the like, and specific examples of the esters include ethyl acetate, n-propyl acetate, n-butyl acetate, propylene carbonate and the like.

Method for Preparing the Coating Composition When preparing the coating composition of the first invention, when the organometallic compound and the like in the component (D) and the component (E) are not used, a method of mixing the components is used. Is not particularly limited, but when an organometallic compound or the like and the component (E) are used, preferably, (E) of the components (A) to (E) is used.
After obtaining a mixture from which the components have been removed, a method of adding the component (E) thereto, specifically, the following methods (1) to (4) are employed. Organosilane (1), component (B), component (D),
A method in which water and an organic solvent are mixed to carry out a hydrolysis reaction or a partial condensation reaction, and then the component (E) is added later. The organosilane (1), the component (B), water and an organic solvent are mixed to perform a hydrolysis reaction or a partial condensation reaction, and then the component (D) is added and mixed, and then a partial condensation reaction is performed. (E) A method of post-adding the component. Alternatively, a hydrolysis reaction or a partial condensation reaction is performed using each component except the component (B), and then the components (B) and (E) are added later. In the first invention, the components other than the components (A) to (E) can be added at an appropriate stage of preparing the composition.

In preparing the coating composition of the second invention, if the organometallic compound and the like in the component (D) and the component (E) are not used, the method of mixing the components is not particularly limited. , Organometallic compounds and (E)
When using a component, preferably (A) to (E)
After obtaining a mixture obtained by removing the component (E) from the components, a method of adding the component (E) to the mixture, specifically, the following methods (1) to (4) are employed. Organosilane (1), component (B), component (C),
A method in which the component (D), water and an organic solvent are mixed to carry out a hydrolysis reaction or a partial condensation reaction, and then the component (E) is added later. The organosilane (1), the component (B), water and an organic solvent are mixed to carry out a hydrolysis reaction or a partial condensation reaction, and then the components (C) and (D) are added, followed by a partial condensation reaction. Thereafter, a method of post-adding the component (E). Organosilane (1), component (B), component (D),
Water and an organic solvent are mixed to perform a hydrolysis reaction or a partial condensation reaction, and then the component (C) is added and mixed.
Further, after a partial condensation reaction is performed, the component (E) is added later. After performing a hydrolysis reaction or a partial condensation reaction using each component except the component (B) according to the methods of the above,
A method of post-adding the component (B) and the component (E). In addition,
In the second invention, components other than the components (A) to (E) can be added at an appropriate stage of preparing the composition.

The total solid content of the coating compositions of the first and second inventions is preferably 50% by weight or less, and is appropriately adjusted depending on the purpose of use. For example, when the purpose is to impregnate a thin film forming substrate, usually 5 to 3
0% by weight, and when it is used for forming a thick film, it is usually 20 to 50% by weight, preferably 30 to 45% by weight. In this case, when the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease.

When the coating compositions of the first and second inventions are applied to a substrate, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater Using a coating method such as dipping, flowing coating, spraying, screen process, electrodeposition, vapor deposition, etc .; 2-80μ
m can be formed. Then, dry at room temperature, or at a temperature of about 30 to 200 ° C for 10 minutes.
By heating and drying for about 60 minutes, a coating film can be formed on various substrates. Examples of the substrate to which the coating composition of the first invention and the second invention can be applied include:
For example, metals such as iron, aluminum, and stainless steel; cement, concrete, ALC, flexible boards, mortar, slates, gypsum, ceramics, bricks; and other inorganic ceramic materials; phenolic resins, epoxy resins, Plastic molded products such as polyester, polycarbonate, polyethylene, polypropylene, ABS resin (acrylonitrile-butadiene-styrene resin); polyethylene,
Examples include plastic films such as polypropylene, polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, and polyimide; wood, paper, and glass. Further, the first invention and the second invention
The coating composition of the invention is also useful for repainting a deteriorated coating film. These substrates may be subjected to a surface treatment in advance for the purpose of adjusting the base, improving the adhesion, filling the porous substrate, smoothing, and patterning. For example, examples of the surface treatment for a metal-based substrate include polishing, degreasing, plating, chromate treatment, flame treatment, and coupling treatment. Examples of the surface treatment for a plastic-based substrate include, for example, , Blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and the like.Examples of surface treatment for inorganic ceramics-based substrates include, for example, Polishing, filling, patterning and the like can be mentioned. Examples of the surface treatment on the wood substrate include polishing, filling, insect repellent treatment, and the like. Examples of the surface treatment on the paper substrate include, for example, , Sealing, insect repellent treatment, and the like, and the surface treatment for the deteriorated coating film includes, for example, kerosene.

The application operation using the coating compositions of the first and second inventions differs depending on the type and condition of the substrate and the application method. For example, in the case of a metal-based substrate, if rust prevention is necessary, use a primer.In the case of an inorganic ceramic-based substrate,
Primers are usually used because the hiding power of the coating film varies depending on the characteristics (surface roughness, impregnation, alkalinity, etc.) of the substrate. In the case of repainting a deteriorated coating film, a primer is used when the old coating film is significantly deteriorated. In the case of other substrates, for example, plastic, wood, paper, glass, etc., a primer may or may not be used depending on the application. Second
In the coating composition of the present invention, when no primer is used, the component (C) contains at least 0.5% by weight of at least one of a carboxyl group, an acid anhydride group, a hydroxyl group, a carbonyl group and a glycidyl group. Preferably, the surface treatment is performed on the substrate.
The type of the primer is not particularly limited as long as it has an effect of improving the adhesion between the substrate and the coating composition, and is appropriately selected depending on the type of the substrate and the purpose of use. . The primers can be used alone or in combination of two or more, and may be an enamel containing a coloring component such as a pigment or a clear containing the coloring component.
Examples of the type of primer include, for example, alkyd resin, aminoalkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluorine resin, acrylic silicone resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, and the like. it can. In addition, these primers can be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required. Examples of such a functional group include a hydroxyl group, a carboxyl group,
Examples include a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, an ester bond and the like. For the purpose of further increasing the abrasion resistance and gloss of the coating film, for example, U.S. Pat. No. 3,986,997 is provided on the surface of the coating film formed from the coating composition of the first invention and the second invention. A clear layer composed of a siloxane resin-based coating material such as a stable dispersion of colloidal silica and a siloxane resin described in US Pat. No. 4,027,073 and the like can also be formed.

There are the following forms in which the coating compositions of the first and second inventions are applied to a substrate. (A) substrate / coating composition (clear, enamel) (b) substrate / coating composition (enamel) / coating composition (clear) (c) substrate / coating composition (clear) −, Enamel) / other organic paint / coating composition (clear) (Note) Clear is a composition containing no coloring component, and enamel is a composition containing a coloring component. In the cases (a) to (c), as described above, a primer layer may be provided on the base material in advance as necessary.

[0064]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described by way of examples.
Embodiments will be described more specifically. However, the present invention
The embodiment is not limited in any way. Example
Parts and% in Comparative Examples and Comparative Examples are based on weight unless otherwise specified.
It is. Various measurements and evaluations in Examples and Comparative Examples
Was performed by the following method. Mn Gel permeation chromatography under the following conditions
-(GPC) method. Sample: 1 g of a partial condensate of organosilane or a vinyl resin containing a silyl group was used, using tetrahydrofuran as a solvent. 1 g was prepared by dissolving each in 100 cc of tetrahydrofuran. Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Co. was used. Apparatus; High-temperature high-speed gel permeation chromatograph (Waters, USA) (Model 150-C ALC / GPC) Column: SHOdex A-80M (50 cm in length) manufactured by Showa Denko KK Measurement temperature: 40 ° C. Flow rate: 1 cc / MinStorage stability A composition without a curing accelerator was added to a polyethylene bottle.
Inside, keep sealed for 3 months at room temperature and visually check for gelation
It was determined by What does not cause gelation
Measures viscosity with a BM viscometer manufactured by Tokyo Keiki Co., Ltd.
If the rate of change is within 20%,
Was.Weatherability According to JIS K5400, sunshine
Conduct an irradiation test for 3,000 hours with an Ether meter,
Visually observe the appearance of the coating (with or without cracks, peeling, etc.)
Was.Heat-resistant The specimen was kept in an electric furnace at 300 ° C. × 240 hours.
Visual observation of the state of the coating film when allowed to cool naturally
did.Alkali resistance Hydroxide whose concentration is gradually changed in the range of 1 to 40% on the coating film
1 cc of sodium chloride solution is dropped into a Petri dish with a lid
After standing for 6 hours and washing with water, the state of the coating film is visually observed.
Observe, sodium hydroxide aqueous solution that does not cause abnormality in the coating film
Evaluation was made based on the maximum concentration of the solution. The higher the maximum concentration, the more resistant
Indicates good alkalinity.

The total nitrogen oxide removal (Rt) composition was applied to a commercially available lightweight foam concrete panel (plane size: 300 mm × 500 mm) and dried to prepare a test piece, which was provided with a gas inlet and a gas outlet. The test piece was placed in a closed reaction cell having an upper wall made of a transparent quartz glass plate so that the coating surface was turned up, and the measurement was carried out at normal temperature and normal pressure as follows. A conditioned air and a standard gas of nitric oxide are mixed, and a test gas adjusted to a relative humidity of 50% and a nitric oxide concentration of 1.0 ppm is continuously reacted at a rate of 4 liters per minute. The test gas supplied to the cell and having undergone the reaction was discharged from the reaction cell at the same rate. At the same time, using a black light fluorescent lamp, the UV irradiation intensity on the coating film surface from the upper surface of the transparent quartz glass plate of the reaction cell was 1 mW / cm.
^The coating film was irradiated with ultraviolet rays so as to obtain ^2, and the oxidation and reduction reaction of nitric oxide was performed by the photocatalytic action of titanium dioxide ultrafine particles contained in the coating film. Measuring the concentration of nitric oxide in the test gas supplied to the reaction cell and the total concentration of nitric oxide and nitrogen dioxide in the test gas discharged from the reaction cell over 4 hours;
Total removal of nitrogen oxides (Rt) (unit NO ₂ -mg / m ²
/ 4 hr) in terms of nitrogen dioxide. This total nitrogen oxide removal amount (Rt) corresponds to the total amount of nitric acid (HNO ₃ ) generated by the oxidation reaction and nitrogen (N ₂ ) generated by the reduction reaction. Nitrogen oxide decomposition removal rate (Rd) The nitrogen oxide decomposition removal rate (Rd) was measured as follows. Take out the test piece after the measurement from the reaction cell,
It was immersed in 1 liter of ion-exchanged water placed in a measuring cylinder protected from light for 15 hours to elute nitric acid generated by the oxidation reaction of nitric oxide, and the amount was quantified by an ion chromatograph to remove nitric acid Amount (unit NO ₂ −
mg / a m ² / 4hr), it was calculated in terms of the amount of nitrogen dioxide. The value obtained by subtracting the nitric acid removal amount from the total nitrogen oxide removal amount (Rt) is calculated as the nitrogen oxide decomposition removal amount (unit NO ₂ -mg / m
² / 4hr) and then, the decomposition of nitrogen oxides removal amount by dividing the nitrogen oxides total removal amount, the nitrogen oxide decomposing removal rate (Rd)
(%) Was calculated.

[0066]

EXAMPLES Production Example 1 (Production of fine particles of composite oxide) Commercial silica sol (SiO ₂ = 20% by weight, pH = 3;
Trade name: Silica Doll 20A, manufactured by Nippon Chemical Industry Co., Ltd.)
After 3000 g was diluted with 3200 g of water, the pH was adjusted to 1 by adding sulfuric acid. Then, while stirring at 85 ° C., 14.3 liters of an aqueous solution of titanium tetrachloride having a TiO ₂ conversion concentration of 168 g / l was added, and ammonia water was gradually added to adjust the pH to 7, thereby obtaining a precipitate. Was. The precipitate is then washed, filtered and
, And then calcined at 450 ° C and pulverized to obtain fine particles of the composite oxide of the present invention. These fine particles were ultrafine titanium dioxide particles having a crystallite diameter of 7 nm which were uniformly dispersed in silicon dioxide. These microparticles are (B-
1).

Example 1 In a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane, 20 parts of a polyfunctional dimethylpolysiloxane (manufactured by Nippon Yunika KK), and di-i-propoxy.
Ethyl acetoacetate aluminum (10 parts), ion-exchanged water (40 parts) and i-propyl alcohol (200 parts) were added and mixed. The mixture was reacted at 60 ° C. for 4 hours with stirring, and then cooled to room temperature. Next, (B-1) 10 obtained in Production Example 1
0 parts, 6 parts of acetylacetone, 20 parts of di-n-butyltin dilaurate and 310 parts of i-butyl alcohol were added later to prepare a composition (Ia) having a solid concentration of 20%. Next, the coating operation of applying the composition (Ia) to a soda glass plate by a dipping method (pulling speed of the glass plate = 40 mm / sec) and drying by heating at 150 ° C. for 20 minutes is repeated twice to obtain a test piece. Obtained. Table 1 shows the evaluation results of the storage stability of the composition (Ia) and various evaluation results of the test pieces.

Examples 2 to 4 The compositions (Ib) to (Ib) having a solid content of 20% were carried out in the same manner as in Example 1 except that the composition was as shown in Table 1.
Preparation of -d) and preparation of each test piece were performed. Table 1 shows the evaluation results of the storage stability of each composition and the various evaluation results of each test piece.

Comparative Examples 1 to 8 Compositions (ia) to (i) having a solid concentration of 20% were prepared in the same manner as in Example 1 except that the formulation was as shown in Table 2.
Preparation of -h) and preparation of each test piece were performed. Table 2 shows the evaluation results of the storage stability of each composition and the various evaluation results of each test piece.

[0070]

[Table 1] (* 1) Toshiba Silicone Co., Ltd. (* 2) Nippon Yunika Co., Ltd.

[0071]

[Table 2] (* 1) Toshiba Silicone Co., Ltd. (* 2) Nihon Yunika Co., Ltd. (* 3) Furukawa Machine Metal Co., Ltd.

Production Example 2 (Production of Component (C)) In a reactor equipped with a reflux condenser and a stirrer, 90 parts of methyl methacrylate, 40 parts of n-butyl acrylate, γ-methacryloxypropyltrimethoxysilane 20 After adding and mixing 130 parts of xylene, the mixture was heated to 80 ° C. with stirring, and a solution obtained by dissolving 4 parts of azobisisovaleronitrile in 10 parts of xylene was added dropwise to the mixture over 30 minutes. The reaction was carried out at 80 ° C. for 5 hours, and the solid content
% Of the component (C) was obtained. M of the obtained component (C)
n is 12,000, and an average of 6 per polymer molecule.
Contained two silyl groups. This component (C) is referred to as (C
-1).

Production Examples 3 to 5 (Production of Component (C)) A solution of each component (C) shown in Table 3 was obtained in the same manner as in Example 1 except that the reaction components were as shown in Table 3. . These components (C) are sequentially converted into (C-2), (C-3), (C
-4).

Example 5 In a reactor equipped with a stirrer and a reflux condenser, 73 parts of methyltrimethoxysilane, 39 parts of dimethyldimethoxysilane,
64 parts of (C-1) obtained in Production Example 2, 10 parts of di-i-propoxyethyl acetoacetate aluminum, 40 parts of ion-exchanged water, and 200 parts of i-propyl alcohol were added and mixed, followed by stirring at 60 ° C. For 4 hours, and then cooled to room temperature. Next, (B-1) 1 obtained in Production Example 1
50 parts, 6 parts of acetylacetone, 20 parts of di-n-butyltin dilaurate and 600 parts of i-butyl alcohol were added later to prepare a composition (II-a) having a solid concentration of 20%. Next, an aluminum plate (JIS H4000, A1050P) obtained by alkali-degreasing the composition (II-a)
Was applied by a spray method so as to have a dry film thickness of 20 μm, and dried by heating at 150 ° C. for 10 minutes to prepare a test piece. Table 4 shows the evaluation results of the storage stability of the composition (II-a) and various evaluation results of the test pieces.

Examples 6 to 8 In the same manner as in Example 5 except that the formulation was as shown in Table 4, the compositions (II-b) to (II-b) having a solid concentration of 20% were prepared.
Preparation of -d) and preparation of each test piece were performed. Table 4 shows the evaluation results of the storage stability of each composition and the various evaluation results of each test piece.

Comparative Examples 9 to 16 Compositions (ii-a) to (ii) having a solid content of 20% were prepared in the same manner as in Example 5 except that the formulation was as shown in Table 5.
Preparation of -h) and preparation of each test piece were performed. Table 5 shows the evaluation results of the storage stability of each composition and various evaluation results of each test piece.

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5] (* 3) Furukawa Machinery & Metal Co., Ltd.

[0080]

The coating composition of the present invention has a photocatalytic component reducing activity, that is, nitrogen oxides are converted to nitrogen molecules (N
₂ ) and the ability to decompose into oxygen molecules (O ₂ ) is remarkably high, the rate of removal of nitrogen oxides in the air as nitric acid can be reduced, pollution of the surrounding environment can be suppressed, and storage stability is excellent, and Excellent general coating performance including coating appearance, weather resistance, heat resistance, etc.

Claims (2)

[Claims] (A) The following general formula (1): (Wherein, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenyl group; n is 0-2
Is an integer. ), At least one component selected from a hydrolyzate of the organosilane and a partial condensate of the organosilane, and (B) a composite oxide of titanium dioxide and a metal oxide other than titanium dioxide. A coating composition comprising fine particles of a composite oxide, in which ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less are dispersed in a metal oxide other than titanium dioxide. (A) The following general formula (1): (Wherein, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenyl group; n is 0-2
Is an integer. ), At least one component selected from a hydrolyzate of the organosilane and a partial condensate of the organosilane, (B) a composite oxide of titanium dioxide and a metal oxide other than titanium dioxide And ultrafine titanium dioxide particles having a crystallite diameter of 10 nm or less bonded to fine particles composed of a composite oxide dispersed in a metal oxide other than titanium dioxide, and (C) a hydrolyzable group and / or a hydroxyl group. A coating composition comprising a polymer having a silyl group having a silicon atom at a terminal and / or a side chain of a polymer molecular chain.