KR100648563B1 - Coating Composition and Its Cured Product - Google Patents

Abstract

The present invention relates to a composition for organosilane coating containing a semiconductor component having ultraviolet absorbing ability. An object of the present invention is to provide a coating composition that is excellent in storage safety, excellent in appearance, adhesion, weather resistance, etc., having a high hardness, absorbing ultraviolet rays, and preventing deterioration of a substrate or a substrate. It is achieved by containing the organosilane component and the semiconductor component or organic compound which have a ultraviolet absorbing power in a composition for this purpose.

Coating composition, hydrolyzate of organosilane, ultraviolet absorbing ability, semiconductor component, silyl group-containing polymer, organometallic compound

Description

Coating composition and cured product {Coating Composition and Its Cured Product}

The present invention relates to a coating composition, and more particularly, to a composition for organosilane-based coating containing a semiconductor component having ultraviolet absorbing ability.

The organosilane-based coating material is a coating material having excellent weather resistance (light), fouling resistance, and the like, and is also excellent in heat resistance, alkali resistance, organic chemical resistance, moisture resistance, water resistance, insulation resistance, abrasion resistance, and scratch resistance. In recent years, there is a great demand for a coating material having long-term durability, and among them, more and more for the purpose of protecting the base and the substrate. However, the organosilane-based coating material is excellent in weatherability as described above. In other words, it is stable because there is no ultraviolet absorption. However, on the other hand, ultraviolet rays can transmit the substrate and the substrate, resulting in deterioration and peeling or cracking. In order to solve this problem, although a ultraviolet absorber is generally used, there exist many problems, such as coloring of a coating material, affinity with resin, film-forming property, transparency, and the like. In addition, when the amount added is large, there is a problem of bleeding out on the surface of the coating film, which adversely affects the physical properties of the film.

The present invention has been made on the background of the above-mentioned problems in the prior art, and has excellent storage safety, excellent coating appearance, adhesion, weather resistance, etc., high hardness, UV absorption ability, and a coating capable of preventing deterioration of a substrate or substrate. It is an object to provide a composition for.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that the composition for coating which has a desired physical property can be obtained by containing the specific organosilane component, the semiconductor component which has ultraviolet absorbing ability, or an organic compound. It was completed. That is, this invention provides the composition for coating of following [1]-[9], and its hardening body.

[1] (A) a hydrolyzate of organosilane represented by the following formula (1) and / or a partial condensate thereof,

(B) at least one ultraviolet absorbing component selected from the group consisting of semiconductor fine particles, sol and organic compounds having ultraviolet absorbing capacity, and

(C1) water and / or organic solvents

A coating composition (hereinafter referred to as "first composition") characterized in that it contains.

(R ¹ ) _n Si (OR ² ) _4-n

In formula, R <^1> represents a hydrogen atom or a C1-C8 monovalent organic group, R <^2> represents a C1-C5 alkyl group or a C1-C6 acyl group, n is an integer of 0-2.

[2] The coating composition according to [1], further comprising (D) at least one curing accelerator selected from acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds and partial hydrolyzates of organometallic compounds.

[3] The component (D) is an organometallic compound represented by the following formula (2),

(E) contains at least one compound selected from the group consisting of? -Diketones and / or? -Ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds represented by the following formula (3) Coating composition as described in [2].

M (OR ¹⁰ ) _p (R ¹¹ COCHCOR ¹² ) _q

In the formula, M represents zirconium, titanium or aluminum, and R ¹⁰ and R ¹¹ each independently represent an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n -pentyl, n- hexyl group, a cyclohexyl group, represents C 1 -C 61 monovalent hydrocarbon groups of the phenyl group, R ¹² is a methoxy group in addition to the monovalent hydrocarbon group of the same having 1 to 6 carbon atoms and R ¹⁰ and R ^11, Alkoxy groups having 1 to 16 carbon atoms, such as an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group and stearyloxy group, p and q are integers of 0 to 4, where (p + q) = (valence of M).

R ¹³ COCH ₂ COR ¹⁴

In the formula, R ¹³ to R ¹⁴ are the same as R ¹¹ to R ¹² in the formula (2).

[4] (A) a hydrolyzate of organosilane represented by the following formula (1) and / or a partial condensate thereof,

(B) at least one ultraviolet absorbing component selected from the group consisting of fine particles, sol and organic compounds of a semiconductor having ultraviolet absorbing capacity, and

(C2) polymers having silyl groups having silicon atoms bonded to hydrolyzable groups and / or hydroxyl groups at the terminal and / or side chains of the polymer molecular chain

A coating composition (hereinafter referred to as "second composition") characterized in that it contains.

<Formula 1>

(R ¹ ) _n Si (OR ² ) _4-n

In formula, R <^1> represents a hydrogen atom or a C1-C8 monovalent organic group, R <^2> represents a C1-C5 alkyl group or a C1-C6 acyl group, n is an integer of 0-2.

[5] The coating composition according to [4], which contains at least one curing accelerator selected from (D) an acidic compound, an alkaline compound, a salt compound, an amine compound, an organometallic compound and a partial hydrolyzate of an organometallic compound.

[6] The component (D) is an organometallic compound represented by the following formula (2),

(E) contains at least one compound selected from the group consisting of? -Diketones and / or? -Ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds represented by the following formula (3) The coating composition as described in [4].

<Formula 2>

M (OR ¹⁰ ) _p (R ¹¹ COCHCOR ¹² ) _q

In the formula, M represents zirconium, titanium or aluminum, and R ¹⁰ and R ¹¹ each independently represent an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n -pentyl, n- hexyl group, a cyclohexyl group, represents C 1 -C 61 monovalent hydrocarbon groups of the phenyl group, R ¹² is a methoxy group in addition to the monovalent hydrocarbon group of the same having 1 to 6 carbon atoms and R ¹⁰ and R ^11, Alkoxy groups having 1 to 16 carbon atoms, such as an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group and stearyloxy group, p and q are integers from 0 to 4 where (p + q) = (valence of M).

<Formula 3>

R ¹³ COCH ₂ COR ¹⁴

In the formula, R ¹³ to R ¹⁴ are the same as R ¹¹ to R ¹² in the formula (2).

[7] The coating composition according to [4], wherein the ultraviolet absorbing component (B) is co-condensed with a polymer having a component (C2).

[8] A cured product obtained by applying the coating composition described in [1] or [4] to a substrate and drying it.

[9] A cured product obtained by applying a primer to a substrate, and applying and drying the coating composition described in [1] or [4] on the primer.

Hereinafter, each component which comprises the composition of this invention is demonstrated in order.

(A) component

Component (A) in the composition of the present invention consists of a hydrolyzate of organosilane represented by Chemical Formula 1 (hereinafter referred to as "organosilane") and / or a partial condensate thereof, and is a main bond in the composition of the present invention. It works zero.

A monovalent organic group of R ¹ is 1 to 8 carbon atoms in the formula (1) include methyl group, ethyl group, n- propyl, i- propyl, n- butyl, sec- butyl, t- butyl, n- hexyl group, Alkyl groups, such as n-heptyl group, n-octyl group, and 2-ethylhexyl group, and a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an acyl group, glycidyl group, a (meth) acryloxy group, a ureido group, an amido group In addition to the fluoroacetoamido group, isocyanato group, and the like, substituted derivatives of these groups may be mentioned.

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 isocyanato group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryl jade. A timing, a ureido group, ammonium base, etc. are mentioned. However, carbon number of R <^1> which consists of these substituted derivatives is 8 or less including carbon atom in a substituent.

When there are a plurality of R ^{1 in} Formula 1, they may be the same or different.

Moreover, as a C1-C5 alkyl group which is R <^{2> in} General formula (1), a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n- A pentyl group etc. are mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, butyryl group, valeryl group, a caproyl group, etc. are mentioned, for example.

^Two or more R <^2> in Formula 1 may mutually be same or different.

In the general formula (1), n is an integer of 0 to 2, and if n is 3 or more, it is not suitable as the component (A) of the present invention because it cannot be high molecular weight.

Here, as a specific example of the organosilane whose n is 0 in (A) component, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n- Butoxysilane, tetraacetyloxysilane, tetraphenoxysilane, etc. are mentioned.

These organosilanes can be used individually or in mixture of 2 or more types.

In the formula (1), specific examples of the organosilane where n is 1 are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n -Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyl Triethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) Krilloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltri Methoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltri Ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysil In addition trialkoxy silanes such as methyltrimethoxysilane, and the like acetyloxy-silane, methyltriethoxysilane phenoxy silanes.

Among these organosilanes, trialkoxysilanes are preferable, and methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane are more preferable.

The organosilanes in which n is 1 in Formula 1 may be used alone or in combination of two or more thereof.

In addition, specific examples of the organosilane in which n is 2 in Formula 1 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, and di- n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, n-pentylmethyldimethoxy Silane, n-pentyl methyldiethoxysilane, cyclohexyl methyldimethoxysilane, cyclohexyl methyl diethoxysilane, phenyl methyldimethoxysilane, phenyl methyl diethoxysilane, di-n-pentyldimethoxysilane, Di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyl Dimethoxysilane, di-n-octyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyl diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy In addition to di-alkoxy silanes, such as is, and the like can be mentioned acetyloxy dimethyl silane, dimethyl silane diphenoxylate during recording.

The organosilane whose n is 2 in these general formula (1) can be used individually or in mixture of 2 or more types.

The organosilane may be previously hydrolyzed and partially condensed to be used as the component (A). However, when preparing the composition by mixing the organosilane with the remaining components as described below, an appropriate amount of water [(C1) component] is added. It is preferable to hydrolyze and partially condense organosilane to make (A) component by doing so.

When component (A) is used as partial condensate, the polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of this partial condensate is usually in the range of 800 to 100,000, preferably 1,000 to 50,000. The Mw of (A) component which consists of partial condensates is suitably selected according to the film-forming property of a composition, the hardness, flexibility, etc. of a coating film.

As a commercial item of (A) component, MKC silicate by Mitsubishi Chemical Corporation, silicate by Tama Chemical Corporation, silicone resin by Toray Dow Corning Corporation, silicone resin by Toshiba Silicone Corporation And silicone oligomers manufactured by Nippon Unicar Co., Ltd., and the like may be used.

In the composition of this invention, (A) component can be used individually or in mixture of 2 or more types.

(B) component

In the composition of the present invention, the component (B) is referred to as semiconductor fine particles, sol (hereinafter referred to as "(B1) inorganic ultraviolet absorbing component") and organic compound (hereinafter referred to as "(B2) organic ultraviolet absorbing component" having ultraviolet absorbing ability. At least one ultraviolet absorbing component selected from the group consisting of

In the composition of this invention, the ultraviolet absorbing ability of (B) component can obtain the ultraviolet absorbing property of a coating film substantially without damaging a coating film performance, and can prevent the base and substrate deterioration by an ultraviolet-ray.

(B1) Examples of the semiconductor having ultraviolet absorbing ability as the inorganic ultraviolet absorbing component include rutile crystals TiO ₂ , ZnO, CeO ₂ , and the like, and preferably ZnO.

The presence of component (B1) includes three types of powder consisting of fine particles, aqueous sol in which fine particles are dispersed in water, and solvent sol in which fine particles are dispersed in polar solvent such as isopropyl alcohol or nonpolar solvent such as toluene. In the case of a solvent-based sol, depending on the dispersibility of the semiconductor fine particles, it may be diluted with water or a solvent again. In these present forms, the average particle diameter of the semiconductor fine particles is preferably smaller from the viewpoint of ultraviolet absorbing ability, and is usually 1 m or less, preferably 0.5 m or less, and particularly preferably 0.1 m or less. By atomizing the component (B), it is possible to make a UV absorber that can be used semi-permanently without transparency and deterioration at the same time. These microparticles | fine-particles and a sol are used suitably either surfactant, a dispersing agent, a coupling agent, etc., or surface-treating them for the purpose of improving dispersibility, storage stability, and preventing photocatalytic activity.

The solid content concentration when the component (B1) is an aqueous sol or a solvent sol is preferably 60% by weight or less, more preferably 50% by weight or less.

As a method of mix | blending (B1) component in the composition of this invention, the composition which consists of said (A) component and (C1) component mentioned later, or the composition which consists of said (A) component and later-mentioned (C2) component etc. May be added after preparation of the composition, or may be added during preparation of the composition of the present invention to hydrolyze and partially condense the organosilane constituting the component (A) in the presence of the component (B1). When (B1) component is added at the time of preparation of a composition, the semiconductor compound in (B1) component can be cocondensed with (A) component etc., and the dispersibility of (B1) component can be improved. Moreover, when (B1) component is an aqueous sol, it is preferable to add at the time of preparation of a composition, and when (V1) component is added at the time of preparation of a composition even if the viscosity in system rises by mix | blending (F) component mentioned later. It is preferable.

Commercially available products of the component (B1) include Taipek TTO manufactured by Ishihara Sangyo Co., Ltd., ZW-143, ZW-513C, ZS-300, ZS-303, ZnO-100, ZnO- 200, Z-NOUVE made by Mitsui Ginjoku Kogyo Co., Ltd., neural made by Taki Kagaku Co., Ltd., CERIGUARD made by Nippon Muki Kagaku Kogyo Co., Ltd., high-seller super K29, Sakai Kagaku high school ) FINEX etc. are mentioned.

In the composition of this invention, (B1) component can be used individually or in mixture of 2 or more types.

The usage-amount of (B1) component is 0.1-500 weight part normally in solid content with respect to 100 weight part (organosilane conversion) of (A) component in 1st composition, Preferably it is 0.5-200 weight part, and in 2nd composition ( The solid content is usually 1 to 1,000 parts by weight, preferably 2 to 600 parts by weight based on 100 parts by weight of the component A) (organosilane equivalent). When the amount of the component (B1) used in the composition of the present invention is too small, the effect of the present invention is hardly expressed because of insufficient ultraviolet absorbing ability. When the amount of the component (B1) is too small, the film forming property of the coating material obtained is poor and cracks and peeling may occur.

(B2) The organic ultraviolet absorbing component is an organic compound having ultraviolet absorbing ability. It is preferable that such (B2) component is soluble in organic solvents, such as alcohol.

Specifically, salicylic acid type ultraviolet absorbers, such as phenyl salicylate, p-t- butylphenyl salicylate, and p-octylphenyl salicylate;

2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxy-benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2, 2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl Benzophenone ultraviolet absorbers such as methane and 2,2 ', 4,4'-tetrahydroxybenzophenone;

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy Oxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole, 2 -{2'-hydroxy-3 '-(3' ', 4' ', 5' ', 6' '-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, 2,2'-methylene Bis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, 2- (2'-hydroxy-5'-octylpropionate Benzotriazole-based ultraviolet absorbers such as benzotriazole;

Cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate;

Triazine type ultraviolet absorbers, such as 2-hydroxyphenyl benzotriazine, etc. are mentioned.

Especially, the salicylic acid type, benzophenone type, and triazine type ultraviolet absorber which absorbs the ultraviolet-ray (UV-B) of wavelength 320 nm or less efficiently are preferable.

In the composition of the present invention, the component (B2) may be used alone or in combination of two or more thereof, or may be used in combination with the component (B1). It is particularly preferable to use a mixture of a) component and a component (B2) which efficiently absorbs ultraviolet rays (UV-A) having a wavelength longer than 320 nm. As a (B2) component which absorbs UV-A efficiently, a benzotriazole type and a cyanoacrylate type ultraviolet absorber are mentioned.

The method similar to the method of mix | blending the said (B1) component is mentioned as a method of mix | blending (B2) component in the composition of this invention. Moreover, you may co-condense with the (C2) component which comprises the composition of this invention using the monomer which has an ultraviolet absorbing power as (B2) component.

Specific examples of such a component (B2) include 2- (meth) acryloyloxy-4-methoxybenzophenone, 2- (meth) acryloyloxy-2'-hydroxy-4-methoxybenzophenone, 2,2'-di (meth) acryloyloxy-4-methoxybenzophenone, 2,2'-di (meth) acryloyloxy-4,4'-dimethoxybenzophenone, 2- (meth) Acryloyloxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2,2'- Benzophenone compounds such as dihydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone; 2- [2 '-(meth) acryloyloxy-5'-methylphenyl] benzotriazole, 2- [2'-(meth) acryloyloxy-5'-t-octylphenyl] benzotriazole, 2 Benzotriazole compounds such as-[2 '-(meth) acryloyloxy-3', 5'-di-t-butylphenyl] benzotriazole; 2-ethylhexyl-2-cyano-3,3-diphenyl (meth) acrylate, 1,3-bis (4-benzoyl-3-hydroxyphenoxy) -2-propyl (meth) acrylate, ethyl 2-cyano-3,3-diphenyl (meth) acrylate etc. are mentioned. These monomers may be used individually by 1 type, or may mix and use 2 or more types.

The usage-amount of (B2) component in the composition of this invention is 0.1-10 weight part normally with respect to 100 weight part of (A) component, Preferably it is 0.5-8 weight part. If it is less than 0.1 weight part, the ultraviolet absorbing power of the coating film obtained may be inadequate, and when it exceeds 10 weight part, the weather resistance of the coating film obtained may worsen.

(C1) ingredient

In the first composition, the component (C1) consists of water and / or an organic solvent.

Although the 1st composition makes the said (A) component and (B) component essential, and contains the (D)-(F) component etc. which are mentioned later as needed, Usually, when preparing a composition, the organosilane is hydrolyzed, Water is added to partially condense or disperse the particulate components.

The amount of water used in the first composition is usually 0.5 to 3 mol, preferably 0.7 to 2 mol, based on 1 mol of the total organosilane constituting the component (A).

Moreover, although a 2nd composition requires the said (A) component, (B) component, and the (C2) component mentioned later, and contains the (D)-(F) component etc. which are mentioned later in some cases, Usually, a composition is prepared. In doing so, it is preferable to add water in order to hydrolyze, partially condense or disperse the organosilane and the component (C2).

The amount of water used in the second composition is usually 0.5 to 3 mol, preferably about 0.7 to 2 mol, per 1 mol of the organosilane constituting the component (A).

On the other hand, in the first composition, the organic solvent uniformly mixes the main (A) component, the (B) component and the (D) to (F) components used as necessary, and simultaneously adjusts the total solid concentration of the composition. It can be applied to the eggplant coating method, and is used to further improve the dispersion stability and the storage stability of the composition.

The organic solvent is not particularly limited as long as the above components can be uniformly mixed, but examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones and esters.

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 and n-octyl alcohol. Ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, and the like. Can be mentioned.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers, tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone and methyl isobutyl ketone. And diisobutyl ketone and the like, and specific examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate and the like.

The total solid concentration of the first composition is preferably 50% by weight or less, and is appropriately adjusted according to the purpose of use. For example, when it is for the purpose of impregnation with a thin film formation base material, it is 5-30 weight% normally, and when it is used for the purpose of thick film formation, it is 10-50 weight% normally, Preferably it is 20-40 weight%. If the total solid concentration of the composition exceeds 50% by weight, the storage stability tends to be lowered.

Moreover, also about a 2nd composition, the said organic solvent is made to mix uniformly the main (A) component, (B) component, (C2) component, and (D)-(F) component used as needed, and It can be used to adjust the total solid concentration of the composition and at the same time can be applied to various coating methods, to further improve the dispersion stability and storage stability of the composition.

The total solid concentration of the second composition is preferably 50% by weight or less, and is appropriately adjusted according to the purpose of use. For example, when it is for the purpose of impregnation with a thin film formation base material, it is 5-30 weight% normally, and when it is used for the purpose of thick film formation, it is 10-50 weight% normally, Preferably it is 20-40 weight%. When the total solid concentration of the composition exceeds 50% by weight, the storage stability tends to be lowered.

Component (C2) in the second composition has a silyl group (hereinafter referred to as a "specific silyl group") having a silicon atom bonded to a hydrolyzable group and / or hydroxyl group at the terminal and / or side chain of the polymer molecular chain. It consists of a polymer.

When the (C2) component cures the coating film obtained from the second composition, the hydrolyzable group and / or hydroxyl group in the silyl group are condensed with the component (A) and the component (B) to make the coating film excellent. Ingredient.

The content of the specific silyl group in the component (C2) is usually 0.001 to 20% by weight relative to the polymer before introducing the specific silyl group in terms of the amount of silicon atoms.

Here, the specific silyl group is preferably represented by the following formula (4).

In the formula, X represents a hydrolyzable group or hydroxyl group such as a halogen atom, an alkoxy group, an acyloxy group, an amineoxy group, a phenoxy group, a thioalkoxy group, an amino group, and R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An aralkyl group having 1 to 10 carbon atoms and i is an integer of 1 to 3;

As the component (C2), for example,

(A) The hydrosilane compound (hereinafter referred to as "hydrosilane compound (A)") corresponding to the formula (4) in the vinyl polymer having a carbon-carbon double bond (hereinafter referred to as "unsaturated vinyl polymer") Addition reaction to a carbon-carbon double bond,

(B) What is manufactured by the method of copolymerizing the silane compound represented by following formula (5) (Hereinafter, it is called "unsaturated silane compound (B)"), and another vinylic monomer.

In the formula, X, R ^3, i is equal to the respective X, R ^3, i in the formula (4), and, R ⁴ represents an organic group having a polymerizable double bond.

As a hydrosilane compound (A) used for the said (A) method, For example, Halogenated silanes, such as methyldichlorosilane, a trichlorosilane, a phenyldichlorosilane; Alkoxysilanes such as methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; Acyloxysilanes, such as methyldiacetoxysilane, phenyl diacetoxysilane, and triacetoxysilane; Amine oxysilanes, such as methyldiamine oxysilane, a triamine oxysilane, and a dimethyl amine oxysilane, etc. are mentioned.

These hydrosilane compounds (A) can be used individually or in mixture of 2 or more types.

Moreover, if the unsaturated vinyl type polymer used for the said method (a) does not have a hydroxyl group, it will not specifically limit, For example, by the method of the following (A-1)-(A-2), or a combination thereof, etc. It can manufacture.

Namely, after (co) polymerizing a vinyl monomer having a (A-1) functional group (hereinafter referred to as "functional group (α)"), the functional group (i) and the functional group (i) in the (co) polymer By reacting a functional group capable of reacting (hereinafter referred to as "functional group (β)") with an unsaturated compound having a carbon-carbon double bond, an unsaturated vinyl polymer having a carbon-carbon double bond in the side chain of the polymer molecular chain can be prepared. Can be.

(A-2) A radical polymerization initiator (for example, 4,4-azobis-4-cyanovaleric acid or the like) having a functional group (α) is used, or a functional group (α) is used for both the radical polymerization initiator and the chain transfer agent. (Co) polymerizes the vinyl monomer using a compound having a compound (for example, 4,4-azobis-4-cyanovaleric acid, dithioglycolic acid, etc.), and at one or both ends of the polymer molecular chain. After synthesize | combining the (co) polymer which has a functional group ((alpha)) derived from a radical polymerization initiator and a chain transfer agent, the unsaturated compound which has a functional group ((beta)) and a carbon-carbon double bond in the functional group ((alpha)) in this (co) polymer By reacting this, an unsaturated vinyl polymer having a carbon-carbon double bond at one end or sock end of the polymer molecular chain can be prepared.

Examples of the reaction of the functional group (α) and the functional group (β) in the methods of (A-1) and (A-2) include esterification reactions of carboxyl groups and hydroxyl groups, and ring-opening esterification reactions of carboxylic anhydride groups and hydroxyl groups. , Esterification reaction of carboxyl group and epoxy group, amidation reaction of carboxyl group and amino group, ring opening amidation reaction of carboxylic anhydride group and amino group, ring opening addition reaction of epoxy group and amino group, urethanation reaction of hydroxyl group and isocyanate group, and And combinations of these reactions.

As a vinyl monomer which has a functional group ((alpha)), For example, unsaturated carboxylic acids, such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; Unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether Hydroxyl group-containing vinyl monomers such as these; 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) Acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 2-aminoethylvinylether, N, N-dimethylamino (meth) acrylamide, N, N-diethyl Amino group-containing vinyl monomers such as amino (meth) acrylamide; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylic Imide, 1,1-dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2 ' And epoxy group-containing vinyl monomers such as amineimide group-containing vinyl monomers such as -phenoxypropyl) amine (meth) acrylimide, glycidyl (meth) acrylate and allyl glycidyl ether.

The vinyl monomer which has these functional groups ((alpha)) can be used individually or in mixture of 2 or more types.

As another vinyl monomer copolymerized with the vinyl monomer which has a functional group ((alpha)), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, ( N-butyl methacrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylamide, crotonamide, maleic acid diamide, fumaric acid diamide, itacone Acid diamide, α-ethylacrylamide, N-butoxymethyl (meth) acrylamide, (meth) acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like.

These other vinyl monomers can be used individually or in mixture of 2 or more types.

As an unsaturated compound having a functional group (β) and a carbon-carbon double bond, for example, the same vinyl monomer as the vinyl monomer having a functional group (α), and the hydroxyl group-containing vinyl monomer and the diisocyanate compound are reacted at the same molar ratio. Isocyanate group containing unsaturated compound obtained, etc. are mentioned.

Moreover, as a specific example of the unsaturated silane compound (b) used for the said (b) method,

CH ₂ = CHSi (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ = CHSi (OCH ₃ ) ₃ ,

CH ₂ = CHSi (CH ₃ ) Cl ₂ , CH ₂ = CHSiCl ₃ ,

CH ₂ = CHCOO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = CHCOO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ ,

CH ₂ = CHCOO (CH ₂ ) ₂ SiCl ₃ ,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ ,

CH ₂ = CHCOO (CH ₂ ) ₃ SiCl ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ SiCl ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ SiCl ₃

Etc. can be mentioned.

These unsaturated silane compounds (B) can be used individually or in mixture of 2 or more types.

Moreover, as another vinylic monomer copolymerized with an unsaturated silane compound (b), 1 or more types, such as a vinylic monomer which has a functional group ((alpha)) illustrated by the method of said (A-1), another vinylic monomer, etc. are mentioned, for example. Can be mentioned.

If the preferable example of the (C2) component obtained as mentioned above is shown more concretely, the trialkoxy silyl group containing (meth) acrylate type copolymer represented by following formula (6) is mentioned.

In formula, R <^5> represents a hydrogen atom or a methyl group, R <^6> represents a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group having 1 to 6 carbon atoms, R ⁷ is the same as R ⁵ , R ⁸ represents an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, and R ⁹ is R ⁶ And k / (j + k) = 0.01 to 0.4, preferably 0.02 to 0.2.

Moreover, as a specific example of (C2) component, specific silyl group containing epoxy resin, specific silyl group containing polyester resin, specific silyl group containing fluororesin, etc. are mentioned.

The specific silyl group-containing epoxy resin is, for example, in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polyglycidyl ether and aliphatic polyglycidyl ester. The epoxy group can be prepared by reacting aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes and the like.

Moreover, the said specific silyl group containing polyester resin can be manufactured by making aminosilane, carboxysilane, glycidylsilane, etc. which have a specific silyl group react, for example in the carboxyl group and hydroxyl group contained in polyester resin. .

Moreover, the said specific silyl group containing fluororesin makes the carboxyl group and hydroxyl group contained in (co) polymers, such as ethylene fluoride, react with aminosilane, carboxysilane, glycidylsilane, etc. which have a specific silyl group, for example. It can manufacture.

The polystyrene reduced number average molecular weight (hereinafter, referred to as "Mn") of the component (C2) is preferably 2,000 to 100,000, more preferably 4,000 to 50,000.

In the second composition, the component (C2) may be used alone or in combination of two or more thereof.

The amount of the component (C2) used in the second composition is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 200 parts by weight based on 100 parts by weight of the organosilane constituting the component (A). It is wealth. In this case, when the usage-amount of (C2) component is less than 2 weight part, there exists a tendency for the alkali resistance of the coating film obtained to fall, and when it exceeds 900 weight part, there exists a tendency for the weather resistance of a coating film to fall.

In addition, the following (D)-(F) component can be mix | blended with the composition (1st and 2nd composition) of this invention.

(D) component

(D) component is a catalyst which accelerates hydrolysis and condensation reactions, such as (A) component. In this invention, by using (D) component, the hardening rate of the coating film obtained becomes high and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the hydrolyzable organosilane component used becomes large, and it is excellent in strength, long-term durability, etc. A coating film can be obtained, and the thickening and painting of the coating film also become easy.

As the component (D), an acidic compound, an alkaline compound, a salt compound, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter, referred to as an organic metal compound and / or a partial hydrolyzate thereof) may be referred to as an "organic metal compound. Etc. "is preferred.

Among the components (D), for example, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, phthalic acid, and the like, preferably acetic acid.

As an alkaline compound, sodium hydroxide, potassium hydroxide, etc. are mentioned, for example, Preferably it is sodium hydroxide.

As a salt compound, alkali metal salts, such as naphthenic acid, octylic acid, nitrous acid, a sulfurous acid, aluminic acid, a carbonic acid, etc. are mentioned, for example.

As the amine compound, for example, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanol Amine, triethylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl Epoxy in addition to) -aminopropyl triethoxysilane, 3- (2-aminoethyl) -aminopropyl methylene dimethoxysilane, 3-anilinopropyl trimethoxysilane, alkylamine salts, and quaternary ammonium salts Various modified amine etc. which are used as hardening | curing agent of resin are mentioned. Preferably, they are 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and 3- (2-aminoethyl) -aminopropyl triethoxysilane.

Examples of the organometallic compound include compounds represented by the following general formula (2) (hereinafter referred to as "organic metal compound (2)") having 1 to 2 alkyl groups having 1 to 10 carbon atoms bonded to the same tin atom. The organometallic compound of tetravalent tin (henceforth "organic tin compound"), the partial hydrolyzate of these compounds, etc. are mentioned.

<Formula 2>

M (OR ¹⁰ ) _p (R ¹¹ COCHCOR ¹² ) _q

In the formula, M represents zirconium, titanium or aluminum, and R ¹⁰ and R ¹¹ each independently represent an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n -A monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a pentyl group, n-hexyl group, a cyclohexyl group, or a phenyl group, R ¹² represents a methoxy group, in addition to a monovalent hydrocarbon group having 1 to 6 carbon atoms identical to R ¹⁰ and R ¹¹ ; Alkoxy groups having 1 to 16 carbon atoms, such as an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group and stearyloxy group, p and q are integers of 0 to 4, where (p + q) = (valence of M).

Specific examples of the organometallic compound (2) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium and n-butoxy Tris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tri-n-butoxyacetylacetonate zirconium, di-n-butoxybis (acetylacetonate) zirconium, n-part Organic zirconium compounds such as oxytris (acetylacetonate) zirconium and tetrakis (ethylacetoacetate) zirconium; Tetra-i-propoxytitanium, tetra-n-propoxytitanium, tri-i-propoxy (ethylacetoacetate) titanium, tri-i-propoxy (acetylacetonate) titanium, tri-n-propoxy (ethyl Acetoacetate) titanium, tri-n-propoxy (acetylacetate) titanium, i-propoxy tris (ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-prop Organic titanium compounds such as foxy bis (acetylacetate) titanium and di-i-propoxy bis (acetylacetone) titanium; Tri-i-propoxy aluminum, di-i-propoxy ethylacetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy Organoaluminum compounds such as bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum, and partial hydrolysates of these compounds Can be mentioned.

Among these, tri-n-butoxy ethyl acetoacetate zirconium, di-i-propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethylacetoacetate) aluminum, Or partial hydrolyzate of these compounds is preferable.

Moreover, as a specific example of an organic tin compound,

(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 = CHCOOC ₄ H ₉ ) ₂ ,

(C ₈ H ₁₇ ) ₂ Sn (OCOC ₈ H ₁₇ ) 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 = CHCOOC ₄ H ₉ ) ₂ ,

(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₈ H ₁₇ ) ₂ ,

(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₁₆ H ₃₃ ) ₂ ,

(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₁₇ H ₃₅ ) ₂ ,

(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₁₈ H ₃₇ ) ₂ ,

(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₂₀ H ₄₁ ) ₂ ,

,

,

(C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ ,

(C ₄ H ₉ ) Sn (OCONa) ₃

Carboxylic acid type tin compounds, such as these;

(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 ,

(C ₄ H ₉ ) ₂ Sn (SCOCH = CHCOOC ₈ H ₁₇ ) ₃ ,

(C ₈ H ₁₇ ) ₂ Sn (SCOCH = CHCOOC ₈ H ₁₇ ) ₃ ,

Mercaptied organic tin compounds such as these;

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

Sulfide type organic tin compounds such as these;

(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ SnCl ₂ ,

(C ₈ H ₁₇ ) ₂ SnCl ₂ ,

Chloride type organic tin compounds such as these;

Organic tin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) SnO, and reaction products of these organic tin oxides with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate, and dioctyl phthalate; Can be mentioned.

The above-mentioned (D) component may be used individually by 1 type, or may be used in mixture of 2 or more types, and may be used in mixture with a zinc compound or another reaction retardant.

(D) component may be mix | blended when preparing the composition of this invention, may be mix | blended with the composition of this invention in the step of forming a coating film, and may be mix | blended in the composition preparation of this invention and both coating film formation steps.

In the composition of the present invention, the amount of the component (D) is usually 0 to 100 parts by weight, preferably 0.01 to 80 parts by weight based on 100 parts by weight of the total organosilane of the component (A), except for an organometallic compound or the like. More preferably, it is 0.1-50 weight part. Moreover, in the case of an organometallic compound etc., it is 0-100 weight part normally with respect to 100 weight part of organosilanes of the said (A) component, Preferably it is 0.1-80 weight part, More preferably, it is 0.5-50 weight part. . In this case, when the usage-amount of (D) component exceeds 100 weight part, there exists a tendency for the storage stability of a composition to fall or a crack arises easily in a coating film.

(E) component

The component (E) is at least one member selected from the group consisting of β-diketones and / or β-ketoesters represented by the following general formula (3), a carboxylic acid compound, a dihydroxy compound, an amine compound and an oxyaldehyde compound. Is done. It is preferable to use together these (E) components, especially when using an organometallic compound etc. in (D) component.

<Formula 3>

R ¹³ COCH ₂ COR ¹⁴

In the formula, R ¹³ to R ¹⁴ are the same as R ¹¹ to R ¹² in the formula (2).

(E) component acts as a stability improver of a composition. That is, by coordinating (E) component to metal atoms, such as an organometallic compound, the effect of promoting the cocondensation reaction of the said (A) component and (B) component by this organometallic compound etc. is adjusted suitably, It is thought to act to further improve storage stability.

Specific examples of the component (E) include acetylacetone, methyl acetoacetate, acetoacetic acid, acetoacetic acid-n-propyl, acetoacetic acid-i-propyl, acetoacetic acid-n-butyl, acetoacetic acid-sec-butyl, 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, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-piperidine, 1,10-phenanthrone, diethylene Triamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, salicylaldehyde and the like. Among these, acetylacetone, ethyl acetoacetate and 2-ethanolamine are preferable.

The above (E) component can be used individually or in mixture of 2 or more types.

The usage-amount of (E) component in the composition of this invention is 2 mol or more normally, Preferably it is 3-20 mol with respect to 1 mol of organometallic compounds corresponded to the said organometallic compound. In this case, when the usage-amount of (E) component is less than 2 mol, there exists a tendency for the effect of improving the storage stability of the composition obtained to become inadequate.

(F) component

(F) component consists of microparticles | fine-particles of inorganic compounds other than the said (B) component, and / or a sol or colloid, and mix | blends according to the desired characteristic of a coating film.

Specific examples of the inorganic compound forming the component (F) include SiO ₂ , Al ₂ O ₃ , Al (OH) ₃ , and Sb ₂ O ₅ .

The presence of component (F) includes powder composed of fine particles, an aqueous sol or colloid in which fine particles are dispersed in water, and a solvent-based sol or colloid in which fine particles are dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. In the case of a solvent-based sol or colloid, depending on the dispersibility of the semiconductor fine particles, it may be diluted with water and a solvent again. These microparticles | fine-particles and sol may add or surface-treat surfactant, a dispersing agent, a coupling agent, a thickener, etc. in order to improve dispersibility.

The solid content concentration when the component (F) is an aqueous sol or a colloid and a solvent-based sol or a colloid is preferably 60% by weight or less.

(F) A component can be used individually or in mixture of 2 or more types.

As a method of mix | blending (F) component in a composition, you may add after preparation of a composition, or it adds at the time of preparation of a composition, and adds (F) component with the said (A) component, (B) component, etc. in a 1st composition. Hydrolysis and partial condensation may be sufficient, and in a 2nd composition, you may carry out cohydrolysis and partial condensation of the said (A) component, (B) component, (C2) component, etc.

The usage-amount of (F) component in the composition of this invention is 0-500 weight part normally, Preferably it is 0.1-400 weight part as solid content with respect to 100 weight part of organosilanes of the said (A) component.

In the coating composition of the present invention, an additional filler may be added and dispersed for coloring, thickening and the like of the coating film obtained.

Such fillers include, for example, water-insoluble organic pigments and inorganic pigments, particulate, fibrous or fish scale ceramics, metals or alloys other than pigments, 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, hydrated lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, zinc rust, chromium rust, cobalt Rust, viridian, guinenock, cobalt chromium rust, sherrenox, nocturnal earth, manganese rust, pigment green, dark blue, dark blue, pigment green, dark blue, cobalt blue, cellulian blue, copper borate, molybdenum blue, copper sulfide , Cobalt purple, mars purple, manganese purple, pigment violet, lead oxide, calcium calcium, zinc yellow, lead sulfide, chromium sulfur, ocher, cadmium sulfur, strontium sulfur, titanium sulfur, research, pigment yellow, nitrous oxide Cadmium Red, Selenium Red, Chromium Vermilion, Bengara, Zinc Bag, Antimony Bag, Basic Lead Sulfate, Titanium Bag, Litphone, Lead Silicate, Zirconium Oxide, Tungsten Bag, Lead Zinc, Van Tison Bag, Lead Phthalate, Manganese Bag, Lead sulfate, graphite, bone black, diamond black, thermochromic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like.

The usage-amount of these fillers is 300 weight part or less normally with respect to 100 weight part of total solids of this composition.

Moreover, according to the objective, the composition of this invention contains well-known dehydrating agents, such as methyl ortho formate, methyl ortho acetate, and tetraethoxysilane, a silane coupling agent, a titanium coupling agent, a dye, a dispersing agent, a thickener, a homogenizer, an ultraviolet stabilizer, etc. You may mix | blend other additives of.

Moreover, when using (B2) organic type ultraviolet absorber as a component (B), an efficient ultraviolet absorber can be obtained by using together an ultraviolet stabilizer (radical remover). Examples of the ultraviolet stabilizer include steric hindrance amines (HALS), and for example, Asahi Denka Co., Ltd., Adecaster LA-77, Sangyo Co., Ltd., Sonol LS 770 (all of which have a molecular weight of 480.7 and a melting point of 81 to 81). 85 ° C), Ciba Specialty Chemicals Co., Ltd., Sinuvin 292, Sangyo Co., Ltd., Sonol LS 770 (above, all molecular weight 508.8, liquid), Ciba Specialty Chemicals Co., Ltd., Shinubin 123 (molecular weight) 737.2, liquid), Shiva Specialty Chemicals Co., Ltd., Sinuvin 144 (molecular weight 685.0, melting point 146 to 150 ℃), manufactured by BF Goodrich, Goodfrite UV 3034 (molecular weight 338.5) , Melting point 136 ° C), Ciba Specialty Chemicals Co., Ltd., Sinuvin 440, Sangyo Co., Ltd., Sunol LS 440 (all molecular weight 435.6, melting point 72 to 78 ° C), Asahi Denka Co., Ltd., Adecasterb LA-87 (molecular weight 225.3, melting point 50 to 60 ° C), manufactured by Asahi Denka Co., Ltd., Adecaster LA-82 (molecular weight 239.4, liquid phase), manufactured by Asahi Denka Co., Ltd., Adecaster LA-52 (molecular weight 847.2, melting point more than 50 degrees Celsius), product made in Asahi Denka Co., Ltd., Adeka tub LA-57 (molecular weight 791.1, melting point 132 degrees Celsius), product made in Asahi Denka Co., Ltd., Ade caster LA-62 ( Molecular weight 900, liquid phase), Asahi Denka Co., Ltd., Adecaster LA-63 (molecular weight 900, melting point about 80-90 degreeC), Asahi Denka Co., Ltd., Adecaster LA-68 (molecular weight 900, melting point about 70-80 degreeC), the Cytec company make, Cysorb UV 3346 (molecular weight 2,000 or more, melting | fusing point 100-130 degreeC), the Ciba specialty chemicals company make, Kimasov 944 (molecular weight 2,000 or more) And melting point 100 to 135 ° C), Ciba Specialty Chemicals Co., Ltd., and Sinuvin 622 (molecular weight 3,000 or more, melting point 130 to 146 ° C).

These ultraviolet stabilizers may be post-added to the composition of the present invention, and in the case of the polymerizable ultraviolet stabilizer, may be co-condensed with the component (C2).

Moreover, as a polymeric ultraviolet stabilizer, what introduce | transduced a polymeric unsaturated group into ultraviolet stable compounds, such as a sterically hindered amine compound and a salicylic acid compound, Among these, the sterically hindered amine compound containing a polymerizable unsaturated group is preferable, and a polymerizable unsaturated Particular preference is given to piperidine compounds containing groups.

The addition amount of this ultraviolet stabilizer is 15 weight part or less normally with respect to 100 weight part of total solids of this composition, Preferably it is 10 weight part or less.

When preparing a 1st composition, when the organometallic compound etc. are not used in (D) component, the mixing method of each component is not specifically limited, When organometallic compound etc. (E) component are used Preferably, after obtaining a mixture except the component (E) from the components (A) to (E), a method of adding the component (E) to it, specifically, the following methods (1) to (2) are employed.

(1) After a predetermined amount of water is added to the mixture consisting of the organosilane constituting the component (A), the component (B), the required amount of the organic solvent, and the component (D), hydrolysis and partial condensation reaction are carried out, and then (E) How to add ingredients.

(2) A predetermined amount of water is added to the mixture consisting of the organosilane constituting the component (A), the component (B) and the required amount of the organic solvent to perform hydrolysis and partial condensation reaction, and then the component (D) is added and mixed. And after performing partial condensation reaction again, the method of adding (E) component.

In addition, in some cases, the first composition

(3) It can also be prepared by the method of adding (B) component after implementing the method of said ① or ② using each component except (B) component.

In addition, in the 1st composition, components other than (A)-(E) component can be added at the appropriate step of preparing a composition.

Moreover, when preparing a 2nd composition, when the organometallic compound etc. and (E) component are not used in (D) component, the mixing method of each component is not specifically limited, However, using an organometallic compound etc. (E) component In this case, Preferably, after obtaining the mixture except component (E) in (A)-(E) component, the method of adding (E) component here, specifically, the method of following (4)-(6) is employ | adopted.

(4) A predetermined amount of water was added to the mixture consisting of the organosilane constituting the component (A), the component (B), the component (C2), the component (D) and the required amount of the organic solvent to perform a hydrolysis and partial condensation reaction. Then, the method of adding (E) component.

(5) A predetermined amount of water is added to the mixture consisting of the organosilane constituting the component (A), the component (B) and the required amount of the organic solvent to perform a hydrolysis and partial condensation reaction, followed by the components (C2) and (D) The method of adding (E) component after adding and mixing a component and performing partial condensation reaction again.

(6) A predetermined amount of water is added to the mixture consisting of the organosilane constituting the component (A), the component (B), the component (D) and the required amount of the organic solvent to perform a hydrolysis and partial condensation reaction, followed by (C2) The method of adding (E) component after adding and mixing a component and performing partial condensation reaction again.

In addition, in some cases, the coating composition of the second invention,

(7) After performing the method (4), (5) or (6) above using each component except the component (B), it can also be prepared by the method of adding the component (B).

Components other than the components (A) to (E) in the second composition may be added at appropriate steps in preparing the composition.

When the composition of the present invention is applied to a substrate, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, or the like is used, or once by a coating method such as dipping, flushing, spraying, screening, electrodeposition, or deposition. It is possible to form a coating film having a thickness of about 1 to 40 μm by coating and 2 to 3 times of coating by about 2 to 80 μm thick. Thereafter, the coating film can be formed on various substrates by drying at room temperature or by heating for 10 to 60 minutes at a temperature of about 30 to 200 ° C.

Here, as the base material to which the composition of the present invention can be applied, for example, metal such as iron, aluminum, stainless steel; Inorganic ceramic materials such as cement, concrete, ALC, flexible boards, mortars, slate, gypsum, ceramics and bricks; Plastic molded articles such as phenol resin, epoxy resin, polyester, polycarbonate, polyethylene, polypropylene, and ABS resin (acrylonitrile-butadiene-styrene resin); And plastic films such as polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, and polyimide, and wood, paper, and glass. The composition of the present invention is also useful for repainting a deteriorated coating film.

These substrates can also be subjected to surface treatment in advance for the purpose of adjusting the base material, improving the adhesion, filling the porous substrate, smoothing the shape, and the like.

Examples of the surface treatment for the metal substrate include polishing, degreasing, plating treatment, chromate treatment, flame treatment, coupling treatment, and the like. For the surface treatment for the plastic substrate, for example, blast treatment, chemicals, etc. Treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and the like. Surface treatments for inorganic ceramic substrates include, for example, polishing, filling, Shape | gum provision etc. are mentioned, As surface treatment with respect to a wooden base material, grinding | polishing, filling, insect repellent treatment etc. are mentioned, for example, As surface treatment with respect to a paper base material, a filling, insect repellent treatment, etc. are mentioned Moreover, as a surface treatment to a deterioration coating film, keren etc. are mentioned, for example.

Application | coating operation by the composition of this invention changes with the kind and state of a base material, and an application | coating method. For example, in the case of metal-based substrates, primers are used if the rust prevention is necessary, and in the case of inorganic urethane industry substrates, since the concealability of the coating film varies depending on the characteristics of the substrate (surface roughness, impregnation, alkali, etc.), Uses a primer. In the case of repainting of deteriorated coating film, a primer is used when the deterioration of the old coating film is remarkable.

In the case of other base materials, for example, plastic, wood, paper, glass, etc., you may or may not use a primer depending on a use. When the primer is not used, in the second composition, the component (C2) preferably contains at least 0.5% by weight or more of a carboxyl group, an acid anhydride group, a hydroxyl group, a carbonyl group or a glycidyl group, more preferably a primer treatment. The surface treatment is performed before.

Although the kind of primer is not specifically limited, What is necessary is just to have an effect which improves the adhesiveness of a base material and the composition of this invention, and it selects according to the kind of base material and a use purpose. A primer can be used individually or in mixture of 2 or more types, and clear which does not contain the enamel and coloring component containing coloring components, such as a pigment, may be sufficient.

As a kind of primer, an alkyd resin, an amino alkyd resin, an epoxy resin, polyester, an acrylic resin, a urethane resin, a fluorine resin, an acrylic silicone resin, an acrylic emulsion, an epoxy emulsion, a polyurethane emulsion, a polyester emulsion, a silicone, Acrylic resin emulsion, fluororesin emulsion, etc. are mentioned. Moreover, these primers can also be provided with various functional groups, when the adhesiveness of a base material and a coating film is required even in strict conditions. As such a functional group, a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, glycidyl group, an alkoxy silyl group, an ether bond, ester bond, etc. are mentioned, for example.

In addition, the surface of the coating film formed from the composition of the present invention has a colloidal silica and siloxane resin described in, for example, US Pat. No. 3,986,997, US Pat. No. 4,027,073 for the purpose of further increasing the wear resistance and gloss of the coating. A clear layer can also be formed with siloxane resin paint etc. like a stable dispersion liquid.

The form which applied the composition of this invention to a base material has the following things.

(a) Substrate / Coating Composition (Clear)

(b) Coating layer / coating composition (clear), such as base material / other paints

Here, clear is a composition which does not contain a coloring component, and enamel is a composition which contains a coloring component. Moreover, as coating layers, such as another coating of said (b), layers, such as an organic coating and a printing ink, are mentioned.

In addition, in the case of said (a)-(b), it is as above-mentioned that a primer layer can be previously made to a base material as needed.

As described above, the coating composition of the present invention has excellent storage stability, excellent coating film appearance, adhesion, weather resistance, and the like, high hardness, ultraviolet absorbing ability, and can prevent deterioration of the substrate and substrate. As a silanosilane-based coating material, it has a very high balance of properties.

<Example>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to these Examples at all.

In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice. In addition, various measurements and evaluation of an Example and a comparative example were performed by the following method.

Mw and Mn

It measured by the gel permeation chromatography (GPC) method of the following conditions.

sample ; Tetrahydrofuran was used as a solvent, and 1 g of partial condensates of organosilanes or 0.1 g of silyl group-containing vinyl resins were dissolved in 100 cc of tetrahydrofuran to prepare.

Standard polystyrene; Standard polystyrene manufactured by U.S. Pressure Chemical was used.

Device ; High temperature high speed gel permeation chromatogram (Model 150-C ALC / GPC) made by US Waters

column ; SHODEX A-80M (50cm in length) made by Showa Denko Corporation

Measured temperature; 40 ℃

Flow rate; 1 cc / min

Retention stability

The composition to which the hardening accelerator was not added was kept sealed for 3 months at room temperature in a polyethylene bin, and the presence or absence of gelation was visually determined. About the thing which gelation did not generate | occur | produce, the viscosity measurement by the BM type viscometer by the Tokai Keiki Co., Ltd. was performed, and the thing with a change rate within 20% was unchanged (O) and the thing exceeding 20% was changed (X).

Hardness

Pencil hardness according to JIS K5400 was followed.

UV absorbance

The transmittance curve of 30 nm or less was measured with the Hitachi magnetic spectrophotometer.

◎; UV absorption rate is over 90%

○; UV absorption rate is more than 80%, less than 90%

△; UV absorption rate is more than 50%, less than 80%

X; UV absorption is less than 50%

Transparency (visible light transmittance)

After apply | coating each composition on quartz glass so that it might be set to a dry film thickness of 10 micrometers, visible light transmittance was measured and evaluated by the following reference | standard.

◎; Transmittance is more than 90%

○; Transmittance is more than 80%, less than 90%

△; Transmittance is more than 70%, less than 80%

X; Transmittance is less than 70%

Adhesion

Adhesiveness was performed 3 times of the tape peeling test by the check board test (100 checkerboard eyes) method based on JISK5400, and it processed on the average.

○; 100 unchecked checkerboard eyes

△; 80 or more, less than 100, non-peeler checkerboard eyes

X; Less than 80 checkerboard eyes not peeled off

Tensile Properties (Elongation)

Tensile tests were performed using autoclave 100 kg load cells and elongation changes were measured.

Weather resistance

The irradiation test was performed for 3000 hours with the sunshine weather meter according to JISK5400, and the adhesiveness and elongation of the coating film after weather resistance evaluation were evaluated according to the above.

<Example 1>

100 parts of methyl trimethoxysilane (MTMS), 20 parts of silicone resin (polymethylhydroxy silsesquioxane, Mw = 10,000), di-i-propoxy ethylacetoacetate aluminum in the reactor equipped with a reflux cooler and a stirrer. After adding 15 parts, 50 parts of ZnO toluene dispersion (ZnO concentration 30%, toluene 70%), 150 parts of i-propyl alcohol (IPA) and 20 parts of ion-exchanged water, mixed and stirred, and reacted at 60 ° C. for 4 hours. And 15 parts of acetylacetone were added, it cooled to room temperature, and the composition (Ia) of 20% of solid content concentration was prepared.

Subsequently, 20 parts of a 20% IPA solution of dibutyltin dimaleate was added to 100 parts of the composition (Ia), followed by stirring, followed by coating with a bar coater on a quartz glass plate and heating and drying at 100 ° C. for 10 minutes to give hardness, ultraviolet absorbency and transparency. The test piece for a test was obtained. The storage stability evaluation results of each composition and various evaluation results of the test pieces are shown in Table 1 below.

<Examples 2 to 8>

Except having made the compounding composition as shown in Table 1, it carried out similarly to Example 1, and prepared the composition (I-b)-(I-h) of 20% of solid content concentration, and produced each test piece. Table 1 shows the storage stability evaluation results of each composition and various evaluation results of each test piece.

Example 9

To a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane, 75 parts of a solvent-based sol (silica 30%) of silica (solution), and 125 parts of i-propyl alcohol were added and mixed thereto, followed by di-i-pro After adding 15 parts of epoxy / ethylacetoacetate aluminum and 20 parts of ion-exchanged water and reacting at 60 DEG C for 4 hours under stirring, 15 parts of acetylacetone were added, cooled to room temperature, and ZnO i-propyl alcohol dispersion (ZnO 30% , Alcohol 70%) 50 parts, 3-aminopropyltrimethoxysilane 20 parts and 20 parts of dibutyltin dimaleate ester was added thereto to prepare a composition (Ii) having a solid concentration of 20%. Moreover, the test piece was obtained like Example 1 except having used the composition (I-i). Table 1 shows the storage stability evaluation results of the composition (I-i) and various evaluation results of the test pieces.

<Comparative Examples 1 to 3>

Except having carried out the compounding composition as shown in Table 2 below, it carried out similarly to Example 1, and prepared the composition (i-a)-(i-c) of 20% of solid content concentration, and produced each test piece. However, the post-addition (D) component in each comparative example was added after cooling to room temperature after completion | finish of reaction. The storage stability evaluation results of each composition and various evaluation results of each test piece are shown in Table 2.

Example number One 2 3 4 5 6 7 8 9 Composition name I-a I-b I-c I-d I-e I-f I-g I-h I-i Compounding composition (part) MTMS (methyltrimethoxysilane) 100 - 80 100 100 100 100 100 100 TEOS (tetraethoxysilane) - 100 - - - - - - - DMDMS (dimethyldimethoxysilane) - - 20 - - - - - - Di-i-propoxy-ethylacetoacetate aluminum 15 15 15 15 15 15 15 15 15 Ion exchange water 20 - 20 20 20 20 20 20 20 IPA 125 125 125 - - - - 125 - Silica sol 75 - 75 75 75 75 - 75 Acetylacetone 15 15 15 15 15 15 15 15 15 ZnO / toluene 50 30 30 - - - 10 - - ZnO / IPA - - - - 15 15 - 15 150 TiO ₂ / IPA - - - 50 - - - - - CeO ₂ / IPA - - - - 15 - - - - Organic UV Absorber A - - - - - 4.5 - - - UV stabilizer A - - - - - - - 4.5 - Evaluation results Retention stability ○ ○ ○ ○ ○ ○ ○ ○ ○ Hardness 3H 2H 2H 3H 3H 3H 3H 3H 4H UV absorbance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Visible light transmittance ○ ○ ○ ○ ○ ○ ○ ○ ○

Organic ultraviolet absorbent A; 2-hydroxyphenylbenzotriazine

UV stabilizer A; Three-dimensional obstacle amine system, Kimasov 944LD (product of Ciba specialty chemicals)

Comparative example number One 2 3 Composition name i-a i-b i-c Compounding composition (part) MTMS 100 100 100 Silica sol 75 75 75 ZnO / IPA - 550 0.05 3-aminopropyltrimethoxysilane [(D) component] 20 20 20 Evaluation results Retention stability O X O Hardness 2H 4H 2H UV absorbance X ◎ △ Visible light transmittance ◎ X ◎

<Reference Example 1 [Preparation of (C2) Component]>

70 parts of methyl methacrylate, 20 parts of cyclohexyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of 3-methacryloxypropyltrimethoxysilane, 4-methacryl to a reactor equipped with a reflux cooler and a stirrer 10 parts of oxypiperidine (manufactured by Asahi Denka Co., Ltd., Adecastab LA-87), 100 parts of i-propyl alcohol and 60 parts of methyl ethyl ketone were added and mixed, followed by heating to 80 ° C. under stirring, and the mixture was To the solution obtained by adding 4 parts of azobisisovaleronitrile to 10 parts of xylene was added dropwise over 30 minutes, and further reacted at 80 ° C for 5 hours to obtain a solution of component (C2) having a solid content concentration of 50%.

Mn of obtained component (C2) was 12,000, and contained 6 silyl groups on average per molecule of polymer.

<Reference Example 2 [Preparation of (C2) Component]>

40 parts of methyl methacrylate, 50 parts of 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer, 2-ethylhexyl acrylate in a reactor equipped with a reflux cooler and a stirrer 40 parts, 20 parts of 3-methacryloyloxypropyltrimethoxysilane, 10 parts of 4-methacryloyloxy-N-methylpiperidine (manufactured by Asahi Denka Co., Ltd., Adecaster LA-82), 100 parts of i-propyl alcohol and 60 parts of methyl ethyl ketone were added and mixed, followed by warming to 80 ° C. under stirring, and a solution of 4 parts of azobisisovaleronitrile dissolved in 10 parts of xylene was added dropwise to the mixture over 307 minutes. The mixture was further reacted at 80 ° C. for 5 hours to obtain a component (C2) B solution having a solid content concentration of 50%.

Mn of the obtained component (C2) B was 12,000, and contained 6 silyl groups on average per molecule.

<Example 10>

100 parts of methyltrimethoxysilane (MTMS), 50 parts of dimethyldimethoxysilane (DMDMS), 50 parts of a solvent dispersion of ZnO (30% ZnO concentration, 70% i-propyl alcohol) in a reactor equipped with a reflux condenser and a stirrer. , 100 parts of (C2) Component A (50% solid content) obtained in Reference Example 1, 20 parts of di-i-propoxyethylacetoacetate aluminum and 100 parts of i-propyl alcohol were added and mixed, and stirred at 60 ° C. The reaction was carried out for 4 hours. Subsequently, 30 parts of acetylacetone were post-added to obtain a composition (II-a) having a solid content concentration of 30%.

Subsequently, 20 parts of IPA 20% solutions of tri-n-butoxyethylacetoacetate zirconium were added to 100 parts of the composition (II-a), followed by stirring, and then applied to a quartz glass plate with a bar coater for 10 minutes, It dried by heating and obtained the test piece for hardness, ultraviolet absorbency, and transparency test.

The storage stability evaluation results of the composition (II-a) and various evaluation results of the test pieces are shown in Table 3 below.

<Examples 11 to 22>

Preparation of the composition (II-b)-(II-m) of 30% of solid content concentration, and each test piece preparation were carried out similarly to Example 10 except having mix | blended composition and reaction conditions as having shown to Tables 3-4. It was. However, the aqueous sol of titanium oxide of Example 16 is 30% titanium oxide content, 20% water and 50% i-propyl alcohol, and the aqueous sol of cerium oxide of Example 17 is 30% cerium oxide, i-propyl alcohol 70 Was%.

The storage stability evaluation result of each composition and various evaluation results of each test piece were shown to Tables 3-4.

<Example 23>

100 parts of methyltrimethoxysilane (MTMS), 50 parts of dimethyldimethoxysilane (DMDMS) in a reactor equipped with a stirrer and a reflux condenser, 100 parts of C2 component A (50% solid content) obtained in Reference Example 1, di-i -20 parts of propoxy ethyl acetate aluminum and 100 parts of i-propyl alcohol were added and mixed, 30 parts of ion-exchanged water was added thereto, and the mixture was reacted at 60 ° C for 4 hours under stirring. Subsequently, after cooling to room temperature, 50 parts of ZnO solvent-based sol (30% ZnO concentration, 70% i-propyl alcohol) and 20 parts of tri-n-butoxyethylacetoacetate zirconium were added to the composition to obtain a solid content concentration of 30%. (II-n) was obtained. Next, the test piece was produced and evaluated similarly to Example 10 except having used the composition (II-n).

The storage stability evaluation results of the composition (II-n) and various evaluation results of the test pieces are shown in Table 4 below.

<Comparative Examples 4 to 6>

Except as shown in Table 5, the formulation composition and the reaction conditions were prepared in the same manner as in Example 9 to prepare compositions (ii-a) to (ii-c) having a solid content concentration of 30% and to prepare each test piece. It was.

The storage stability evaluation result of each composition and the various evaluation results of each test piece were shown in Table 5, respectively.

Example number 10 11 12 13 14 15 Composition name II-a II-b II-c II-d II-e II-f Compounding composition (part) MTMS 100 - 100 100 100 100 TEOS - 100 - - - - DMDMS 50 50 50 50 50 50 (C2) Component A 100 100 800 - 100 - (C2) Component B - - - - - 100 Epoxysilane - - - 100 - - Di-i-propoxyethylacetoacetate aluminum 20 20 20 20 20 20 Ion exchange water 30 30 30 30 30 30 Acetylacetone 30 - - 15 - - Ethyl acetoacetate - - - 15 - - 2-ethanolamine - - 40 - - - i-propyl alcohol 100 100 560 100 - 100 ZnO / IPA 50 50 150 50 200 50 TiO ₂ / IPA - - - - - - CeO ₂ / IPA - - - - - - Evaluation results Retention stability O O O O O O Hardness 2H 2H 2H 2H 3H 2H UV absorbance ◎ ◎ ◎ ◎ ◎ ◎ Visible light transmittance ◎ ◎ ◎ ◎ O ◎

Example number 16 17 18 19 20 21 22 23 Composition name II-g II-h II-i II-j II-k II-l II-m II-n Compounding composition (part) MTMS 100 100 100 100 100 100 100 100 TEOS - - - - - - - - DMDMS 50 50 50 50 50 50 50 50 (C2) Component A 100 100 100 100 100 100 100 100 (C2) Component B - - - - - - - - Epoxysilane - - - - - - - - Di-i-propoxyethylacetoacetate aluminum 20 20 20 20 20 20 20 20 Ion exchange water 30 30 30 30 30 30 30 30 Acetylacetone - - - - - - - - Ethyl acetoacetate - - - - - - - - 2-ethanolamine - - - - - - - - i-propyl alcohol 100 50 100 100 100 100 100 100 ZnO / IPA 10 - 25 25 25 50 50 50 TiO ₂ / IPA - 50 - - - - - - CeO ₂ / IPA - - 25 - - - - - Organic UV Absorber B - 50 - 5 - - - - Organic UV Absorber C - - - - 5 - - - UV stabilizer B - - - - - 5 - - UV stabilizer B - - - - - - 5 - Tri-n-butoxyethylacetoacetate zirconium - 20 20 - - - - - [Component (D)] Dioctyl Tin Dimaleate Ester [Component (D)] - - - 50 50 50 50 - Evaluation results Retention stability O O O O O O O O Hardness 2H 2H 2H 2H 2H 2H 2H 2H UV absorbance O ◎ ◎ ◎ ◎ ◎ ◎ ◎ Visible light transmittance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Organic ultraviolet absorber B; 2- (5-octapropionato-2-hydroxy-3-butoxyphenyl) -2H-benzotriazole

Organic ultraviolet absorbent C; 2,2 ', 4,4'-tetrahydroxybenzophenone

UV stabilizer B; Bis (2,2 ', 6,6'-tetramethyl-4-piperidyl) sebacate

UV stabilizer C; Three-dimensional obstacle amine system, Kimasov 944LD [product made by Ciba specialty chemicals]

Comparative example number 4 5 6 Composition name ii-a ii-b ii-c Compounding composition (part) MTMS 100 100 100 TEOS - - - DMDMS 50 50 50 C2 100 100 100 Epoxysilane - - - Di-i-propoxyethylaceto acetatealuminum 20 20 20 Ion exchange water 30 30 30 Acetylacetone 30 30 30 Ethyl acetoacetate - - - 2-ethanolamine - - - i-propyl alcohol 100 - 100 ZnO / IPA - 350 0.1 TiO ₂ / IPA - - - CeO ₂ / IPA - - - Tri-n-butoxyethylaceto acetate zirconium 50 50 50 Dioctyl tin dimaleate ester - - - Evaluation results Retention stability O X O Hardness 2H 3H 2H UV absorbance X ◎ △ Visible light transmittance ◎ △ (dispersion) ◎

Reference Example 3 (Preparation of Primer)

In order to ensure long-term adhesiveness with respect to each base material, the primer was prepared. Although the primer may be used as it is, in the same manner as in the composition of the present invention, when the primer is directly irradiated with light, long-term weather resistance can be further obtained by using the one that gives ultraviolet absorbency. Therefore, as a primer, the thing which disperse | distributed ZnO (ZnO concentration 30%) dispersed in toluene 10% with respect to 100 parts of alkyd resin solid content was used, for example. Also in the case of other solvent-type resin, it prepared similarly. In addition, the thing which added and disperse | distributed the water dispersion ZnO (30% of ZnO concentration) 10% with respect to resin solid content was used for emulsion. In addition, in the case of acrylic resin and acrylic silicone resin, the thing which added 15% of acrylic copolymer type ultraviolet absorbers [made by BASF, UVA-635L] was used.

<Test Example>

The primer prepared in Reference Example 3 was applied to the base material of inorganic ceramics, foamed concrete, metal (SUS), plastic, glass, ETFE, and wood in the same manner as in Example 1 without performing primer treatment or primer treatment, and evaluated for weather resistance. Was performed.

That is, the composition (I-a) obtained in Example 1 or the composition (I-b) obtained in Example 2 was apply | coated to various base materials on application | coating conditions similar to Example 1, and the adhesiveness and the weather resistance regarding elongation were evaluated. The results are shown in Table 6 below.

Comparative Test Example

The composition (i-a) obtained in the comparative example 1 was apply | coated to the various base materials treated with the primer prepared in the reference example 3, or the primer process was not performed on the same application conditions as Example 1, and the adhesiveness and the weather resistance regarding elongation were evaluated. The results are shown in Table 7 below.

The coating composition of the present invention is excellent in storage stability, at the same time excellent in coating appearance, adhesion, weather resistance, etc., has a high hardness, UV absorption ability, and can prevent degradation of the base or substrate, very high as an organosilane-based coating material It has a characteristic balance of.

Claims (4)

(A) hydrolyzate and / or partial condensate of organosilane represented by the following formula (1), (B) ultraviolet light which is a combination of TiO ₂ , ZnO and CeO ₂ fine particles or sol of rutile crystals having ultraviolet absorbing ability, and TiO ₂ , ZnO and CeO ₂ fine particles or sol of rutile crystals having ultraviolet absorbing ability and an organic compound having ultraviolet absorbing ability Absorption components, and (C1) water and / or organic solvents Coating composition, characterized in that it contains. <Formula 1> (R ¹ ) _n Si (OR ² ) _4-n In the formula, R ¹ is the same or different and represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different, represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, n Is an integer of 0 to 2. (A) hydrolyzate and / or partial condensate of organosilane represented by the following formula (1), (B) ultraviolet light which is a combination of TiO ₂ , ZnO and CeO ₂ fine particles or sol of rutile crystals having ultraviolet absorbing ability, and TiO ₂ , ZnO and CeO ₂ fine particles or sol of rutile crystals having ultraviolet absorbing ability and an organic compound having ultraviolet absorbing ability Absorption components and (C2) polymers having silyl groups having silicon atoms bonded to hydrolyzable groups and / or hydroxyl groups at the terminal and / or side chains of the polymer molecular chain Coating composition, characterized in that it contains. <Formula 1> (R ¹ ) _n Si (OR ² ) _4-n In the formula, R ¹ is the same or different and represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ² is the same or different, represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, n Is an integer of 0 to 2. The hardened | cured material obtained by apply | coating the composition for coating of Claim 1 or 2 to a base material, and drying it. The cured body obtained by apply | coating a primer to a base material, and apply | coating and drying the coating composition of Claim 1 or 2 on a primer.