JP2008274306A - Composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition excellent in weather resistance and storage stability, excellent in adherence, alkali resistance, organic chemical resistance, moisture resistance, (warm) water resistance, contamination resistance or the like as well, capable of forming a coating film having high hardness and having excellent photocatalytic functions such as functions of decomposing organic substances, making substances hydrophilic or the like. <P>SOLUTION: The composition comprises (A) organosilanes of the general formula (R<SP>1</SP>)<SB>n</SB>Si(OR<SP>2</SP>)<SB>4-n</SB>(1);(B) a photocatalyst; and (C-1) a fluoroacrylic polymer having a particular silyl group at the end and/or at the side chain of the polymeric molecular chain. The amount of component (B) used is 1-500 pts.wt. with respect to 100 pts.wt. of the organosilanes of component (A) in terms of solid content, and the amount of component (C-1) used is 30-500 pts.wt. with respect to 100 pts.wt. of the organosilanes of component (A). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition having a photocatalytic function, and more particularly to an organosilane-based composition containing a photocatalyst.

  Organosilane-based coating materials are being developed as maintenance-free coating materials with excellent weather resistance (light) resistance, contamination resistance, and the like. The performance requirements for such organosilane coating materials are becoming stricter. In recent years, coating film appearance, adhesion, weather resistance, heat resistance, alkali resistance, organic chemical resistance, moisture resistance, (warm) water resistance There is a need for a coating material that is excellent in insulation resistance, abrasion resistance, stain resistance, and the like and can form a coating film with high hardness.

  In particular, in order to improve the stain resistance, it has been recognized that the surface of the coating film should be made hydrophilic. For example, a method of adding a hydrophilic substance or a water-soluble substance has been proposed. However, in such a method, it is difficult to maintain the hydrophilicity of the coating film surface at a sufficient level for a long time because the hydrophilic substance and the water-soluble substance are gradually deteriorated by light or washed away with water. there were.

  In recent years, many coating compositions containing a photocatalytic component have been proposed. Examples thereof include titanium oxides, hydrolysates of hydrolyzable silicon compounds (alkyl silicates or silicon halides), and solvents (water or water). Alcohol) titanium oxide coating film-forming composition for photocatalyst (JP-A-8-164334), silicon compound having at least two alkoxy groups, titanium compound or zirconium compound having at least two alkoxy groups, and In addition to a surface treatment composition for imparting antibacterial and antifungal properties, comprising a hydrophilic inorganic powder such as titanium oxide treated with alkoxysilane and / or polysiloxane having a guanidyl group (Japanese Patent Laid-Open No. 8-176527) , 20 to 200 parts by weight of tetraalkoxysilane, trialkoxy A coating film obtained from a mixture of an inorganic paint having a polystyrene-equivalent weight average molecular weight of 900 or more and a powder having a photocatalytic function, prepared from 100 parts by weight of run and 0 to 60 parts by weight of dialkoxysilane. A method for forming an inorganic coating film treated with an acid or an alkali (JP-A-8-259891) is known.

  However, these coating-forming compositions and liquid mixtures are intended to be antibacterial / antifungal, deodorizing and decomposing harmful substances based essentially on photocatalyst components or alkoxysilane and / or polysiloxane components having a guanidyl group. In addition to these functions, the coating performance including the hardness, adhesion, alkali resistance, organic chemical resistance, weather resistance, and contamination resistance required for organosilane coating materials is comprehensively studied. It has not been.

  On the other hand, as a coating composition that satisfies the required performance for organosilane coating materials to some extent, a composition comprising a partial condensation product of organosilane, a dispersion of colloidal silica, and a silicone-modified acrylic resin (JP-A-60-135465) ), Organosilane condensate, zirconium alkoxide chelate compound and hydrolyzable silyl group-containing vinyl resin (JP-A 64-1769), organosilane condensate, colloidal alumina and water A composition containing a decomposable silyl group-containing vinyl resin (US Pat. No. 4,904,721) and the like have been proposed.

  However, the coating film obtained from the composition described in JP-A-60-135465 and U.S. Pat. No. 4,904,721 has a disadvantage that the gloss is lowered by long-time ultraviolet irradiation. is there. Further, the composition described in JP-A No. 64-1769 has a problem that the storage stability is not sufficient and the gelation tends to occur in a short period of time when the solid content concentration is increased.

Furthermore, the present applicant has already hydrolyzed an organosilane and / or a partial condensate thereof, a hydrolyzable and / or vinyl resin having a silyl group having a silicon atom bonded to a hydroxyl group, a metal chelate compound, and β -A coating composition (JP-A-5-345877) containing a diketone and / or a β-keto-sell is proposed, and the coating film is required for an organosilane coating material. Although the balance of performance is excellent, further improvement is also demanded for these performances.
JP-A-8-164334 JP-A-8-176527 Japanese Patent Laid-Open No. 8-259891 JP-A-60-135465 JP-A 64-1769 U.S. Pat. No. 4,904,721 JP-A-5-345877

  The present invention has been made against the background of the above-mentioned problems in the prior art, and its problem is that it contains a specific organosilane component and a photocatalyst, and is particularly excellent in weather resistance, storage stability, adhesion, and resistance. Excellent alkali resistance, organic chemical resistance, moisture resistance, (warm) water resistance, stain resistance, etc., and can form a coating film with high hardness. Another object of the present invention is to provide a composition having a photocatalytic function.

The composition of the present invention comprises:
(A) The following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2) An integer of 2. When n is 2, R ^{1 s} may be the same or different from each other, and R ² may be the same or different from each other. , At least one selected from the group consisting of a hydrolyzate of the organosilane and a partial condensate of the organosilane (hereinafter referred to as “component (A)”), (B) a photocatalyst (hereinafter referred to as “component (B)”) ), And (C-1) a fluoroacrylic polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal and / or side chain of the polymer molecular chain (hereinafter referred to as “(C -1) component ")).

  In addition, the composition of the present invention comprises (C-2) a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group, instead of the component (C-1), at the end of the polymer molecular chain and And / or containing a fluorine vinyl ether polymer (hereinafter referred to as “component (C-2)”) in the side chain.

  Hereafter, each component which comprises the composition of this invention is demonstrated sequentially.

Component (A) In the present invention, the component (A) is an organosilane represented by the general formula (1) (hereinafter referred to as “organosilane (1)”), a hydrolyzate of organosilane (1) and an organosilane. It consists of at least one selected from the group of partial condensates of silane (1) and acts as the main binder in the composition of the present invention.

In the general formula (1), examples of the monovalent organic group having 1 to 8 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl. Group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups, vinyl group, allyl group, cyclohexyl group, phenyl group, acyl group In addition to groups, glycidyl groups, (meth) acryloxy groups, ureido groups, amide groups, fluoroacetamide groups, isocyanate groups, etc., substituted derivatives of these groups, and the like can 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 isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxy group. Ureido groups, ammonium bases and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent.

A plurality of R ¹ present in the general formula (1) may be the same as or different from each other.

The alkyl group having 1 to 5 carbon atoms for ^{R 2,} for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, sec- butyl group, t- butyl radical, n -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.

A plurality of R ² present in the general formula (1) may be the same as or different from each other.

  Specific examples of such organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyl Trimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltrie Xysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyl Trimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropylto Methoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acrylicoxypropyl Trialkoxysilanes such as triethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyl Didiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n- Butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n -Heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. Dialkoxysilanes; trimethylmeth Shishiran addition to mono-alkoxysilanes such as trimethyl silane, methyl triacetyl silane, dimethyl acetyl silane, trimethyl acetyloxy silane.

  Of these, trialkoxysilanes and dialkoxysilanes are preferable. As the trialkoxysilanes, methyltrimethoxysilane and methyltriethoxysilane are preferable. As dialkoxysilanes, dimethyldimethoxysilane and dimethyldimethoxysilane are preferable. Ethoxysilane is preferred.

  In the present invention, the organosilane (1) is particularly preferably a trialkoxysilane alone or a combination of trialkoxysilane 40 to 95 mol% and dialkoxysilane 5 to 60 mol%. By using dialkoxysilane in combination with trialkoxysilane, the resulting coating film can be softened and alkali resistance can be improved.

  Organosilane (1) is used as it is or as a hydrolyzate and / or partial condensate. When the organosilane (1) is used as a hydrolyzate and / or a partial condensate, it can be preliminarily hydrolyzed and partially condensed and used as the component (A). However, as described later, the organosilane (1 ) Is mixed with the remaining components to prepare the composition, it is preferable to hydrolyze and partially condense organosilane (1) by adding an appropriate amount of water to obtain component (A). When the component (A) is used as a partial condensate, the polystyrene-concentrated weight average molecular weight (hereinafter referred to as “Mw”) of the partial condensate is preferably 800 to 100,000, more preferably 1,000 to 1,000. 50,000.

  In addition, commercially available products of component (A) include MKC silicate manufactured by Mitsubishi Chemical Co., Ltd., silicate manufactured by Tama Chemical Co., Ltd., silicone resin manufactured by Toray Dow Corning Co., and silicone resin manufactured by Toshiba Silicone Co., Ltd. There are silicone oligomers manufactured by Nippon Unica Co., Ltd., and these may be used as they are or after being condensed.

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

(B) component (B) component in this invention consists of a photocatalyst, and the semiconductor which has photocatalytic capability is mentioned as a preferable photocatalyst.

Examples of the semiconductor having photocatalytic activity include TiO ₂ , TiO ₃ , SrTiO ₃ , FeTiO ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , ZnO, Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, GaP, GaAs, CdFeO ₃ , MoS ₂ , LaRhO ₃ , GaN, CdP, ZnS, ZnSe, ZnTe, Nb ₂ O ₅ , ZrO ₂ , InP, GaAsP, InGaAlP, AlGaAs, PbS, InAs, PbSe, InSb Of these, TiO ₂ and ZnO are particularly preferable.

  When the composition of the present invention is applied as a coating agent, the coating surface becomes hydrophilic in a short time even by weak light due to the photocatalytic ability of the component (B), and as a result, other coating performance is substantially improved. It was revealed that the stain resistance of the coating film can be remarkably improved without any loss. And in the coating film obtained from the composition of this invention, (B) component has a coupling | bonding with the said (A) component etc., and the hydrophilic property of a coating film and stain resistance are maintained over a long period of time.

  Further, the semiconductor is desirably used in the form of powder and / or sol. Specifically, the semiconductor is a powder, an aqueous sol dispersed in water, a polar solvent such as isopropyl alcohol, or a nonpolar solvent such as toluene. It is desirable to take any one of the three types of dispersed solvent-based sols. In the case of a solvent-based sol, depending on the dispersibility of the semiconductor, it may be further diluted with water or a solvent. The average particle diameter of the semiconductor in these existing forms is preferably as small as possible from the viewpoint of photocatalytic activity. In this case, when the average particle diameter of the semiconductor is 0.1 to 0.5 μm, the coating film becomes opaque due to the light concealing action of the semiconductor, and when it is 0.05 to 0.1 μm, the coating film becomes translucent. Furthermore, when it is 0.05 μm or less, the coating film becomes transparent, and the average particle size of the semiconductor can be appropriately selected according to the use of the composition.

  When the component (B) is an aqueous sol or a solvent sol, the solid content concentration is preferably 50% by weight or less, more preferably 40% by weight or less.

  When the semiconductor compound is used as the component (B), the method of blending the component (B) in the composition includes the component (A) and the components (C) to (G) described later. It may be added after the preparation of the composition, or may be added during the preparation of the composition to hydrolyze and partially condense the component (A) in the presence of the component (B). When component (B) is added during preparation of the composition, the semiconductor compound in component (B) can be co-condensed with component (A) and the like, and the long-term durability of the resulting coating film is improved. Further, when the component (B) is an aqueous sol, it is preferably added at the time of preparing the composition, and also when the viscosity in the system increases due to the blending of the component (F) described later, the component (B) Is preferably added during preparation of the composition. Furthermore, when the composition of the present invention is used as an enamel containing a coloring component, the component (B) may be added to the composition and then toned, and the component (B) and the coloring component may be used simultaneously. It may be added to the composition.

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

  (B) The usage-amount of a component is 1-500 weight part normally with respect to 100 weight part of organosilane (1) in (A) component, Preferably it is 5-400 weight part.

Component (C-1) Component (C-1) The component (C-1) in the present invention includes a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter referred to as “specific silyl group”). It is a fluoroacrylic polymer having at the terminal and / or side chain of the combined molecular chain.

  When such a component (C-1) cures the coating film obtained from the composition of the present invention, the hydrolyzable group and / or hydroxyl group in the silyl group co-condenses with the component (A). Thus, excellent coating film performance can be brought about.

  The content of the specific silyl group in the component (C-1) is usually 0.001 to 20% by weight in terms of the amount of silicon atoms with respect to the polymer before the introduction of the specific silyl group.

The specific silyl group is preferably the following general formula (2)

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

  The component (C-1) includes (Ca) a fluorine atom-containing monomer (hereinafter referred to as “(Ca) monomer”), (Cb) alkyl (meth) acrylate (hereinafter referred to as “Ca”). "(Cb) monomer"), (Cc) obtained by polymerizing a monomer having a silyl group (hereinafter referred to as "(Cc) monomer"), and necessary. Depending on the case, (Cd) may be obtained by polymerizing by further including other monomers copolymerizable with these monomers (hereinafter referred to as “(Cd) monomers”). .

  Moreover, (C-1) component is a polymer obtained by superposing | polymerizing said (Ca) monomer and (Cb) monomer, or these monomers, as needed. In addition, the (Cg) monomer may be added to the carbon-carbon double bond of the polymer obtained by further polymerizing the (Cd) monomer.

Examples of the (Ca) monomer include compounds having at least one polymerizable unsaturated double bond group and at least one fluorine atom. Specifically, tetrafluoro Fluoroolefins such as ethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, tetrafluoroethylene;
CH ₂ = CH-O-Rf
(Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom) (fluoroalkyl) vinyl ether or (fluoroalkoxyalkyl) vinyl ethers represented by: perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as fluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ethers) such as perfluoro (propoxypropyl vinyl ether); 2,2 , 2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) ) Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 1H, 1H, 5H-octafluoro Fluorine-containing (meth) acrylic acid esters such as pentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate;

  These monomers containing fluorine atoms may be used alone or in combination of two or more. In particular, it is preferable to use hexafluoropropylene in combination with perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether as the fluorine-containing monomer.

  As said (Cb) monomer, a C4-C12 thing is preferable, and, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) ) Acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, Examples include cyclohexyl methacrylate.

  These can be used alone or in combination of two or more.

Examples of the (Cc) monomer include the following general formula (3):

(X in the ^{formula, R} 3, i is the general formula (2 respectively ^X, in) has the same meaning as ^R 3, i, ^{R 4} is an organic group shows a having a polymerizable double bond) represented by Examples thereof include silane compounds (hereinafter referred to as “unsaturated silane compounds”).

を挙げることができる。 Specific examples of the unsaturated silane _{compound, 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 S i (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 ,

Can be mentioned.

  These can be used alone or in combination of two or more.

Examples of the (Cd) monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 4-ethylstyrene. 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4- Aromatic vinyl monomers such as dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene; hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate , Hydroxyamyl (meth) acrylate, hydroxy Hydroxyalkyl (meth) acrylates such as hexyl (meth) acrylate; Epoxy compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, and methyl glycidyl (meth) acrylate; divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene Glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylo Polyfunctional monomers such as lepropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate;
(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc. Acid amide compounds; vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl esters; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl -1,3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, isoprene, alkyl group, halogen atom, substituted linear conjugated pentadiene substituted with a substituent such as cyano group , Aliphatic such as linear and side chain conjugated hexadiene Conjugated dienes; ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, itaconic acid, monoalkylitaconic acid, maleic acid, crotonic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid; acrylonitrile, meta Vinyl cyanides such as acrylonitrile; fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate; 4- (meth) acryloyloxy-2,2,6,6-tetramethyl Piperidine monomers such as piperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine;
Examples include dicaprolactone.

  These can be used alone or in combination of two or more.

(Cg) Monomers include halogenated silanes such as methyldichlorosilane, trichlorosilane, phenyldichlorosilane; methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane Alkoxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, and the like; aminoxysilanes such as methyldiaminoxysilane, triaminoxysilane, dimethylaminoxysilane, and the like be able to.
These can be used alone or in combination of two or more.

  Examples of the polymerization method for producing the component (C-1) include, for example, a method in which a monomer is added all at once and a polymerization is performed. Or the method of adding intermittently or the method of adding a monomer continuously from the beginning of superposition | polymerization etc. are mentioned. Moreover, the polymerization method which combined these polymerization methods is also employable. A preferred polymerization method includes solution polymerization. As the solvent used for the solution polymerization, usual solvents can be used, and among them, ketones and alcohols are preferable. In this polymerization, known polymerization initiators, molecular weight regulators, chelating agents, and inorganic electrolytes can be used.

  The number average molecular weight (hereinafter referred to as “Mn”) of the component (C-1) in terms of polystyrene is preferably 1,000 to 50,000, more preferably 5,000 to 30,000.

  In this invention, (C-1) component can be used individually or in mixture of 2 or more types obtained by making it above.

  The amount of component (C-1) used in the present invention is usually 30 to 500 parts by weight, preferably 40 to 400 parts by weight, more preferably 100 parts by weight of organosilane (1) in component (A). 50 to 300 parts by weight. In this case, if the usage-amount of (C-1) component is less than 30 weight part, there exists a tendency for the alkali resistance and crack resistance of the coating film obtained to fall. On the other hand, when it exceeds 500 weight part, there exists a tendency for the weather resistance of a coating film to fall.

(C-2) Component The (C-2) component in the present invention is a fluorovinyl ether polymer having the specific silyl group at the terminal and / or side chain of the polymer molecular chain.

  When such a component (C-2) cures the coating film obtained from the composition of the present invention, the hydrolyzable group and / or hydroxyl group in the silyl group co-condenses with the component (A). Thus, excellent coating film performance can be brought about.

  The content of the specific silyl group in the component (C-2) is usually 0.001 to 20% by weight in terms of the amount of silicon atoms with respect to the polymer before the introduction of the specific silyl group.

  The component (C-2) includes the above (Ca) monomer, the above (Cc) monomer, and the (Ce) vinyl ether monomer (hereinafter referred to as “(Ce) monomer”. And (Cf) another monomer copolymerizable with these monomers (hereinafter referred to as “(Cf) monomer”). And may be obtained by polymerization.

  In addition, the component (C-2) is a polymer obtained by polymerizing the above (Ca) monomer and (Ce) monomer, or, if necessary, (Cf) It may be obtained by addition-reacting a monomer (Cg) to a carbon-carbon double bond of a polymer obtained by further polymerizing the monomer.

  Examples of the (Ce) monomer include vinyl glycidyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5- Vinyl ethers such as hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; allyl ethers such as allyl glycidyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; methyl vinyl ether, ethyl vinyl ether, n- Propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl Vinyl ether, n- pentyl vinyl ether, n- hexyl vinyl ether, n- octyl vinyl ether, n- dodecyl vinyl ether, 2-ethylhexyl vinyl ether, alkyl vinyl ethers or cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; and the like. These can be used alone or in combination of two or more.

  The (Ca) monomer and the (Cc) monomer are the same as those in the (C-1) fluoroacrylic polymer. Further, as the (Cf) monomer, the component (Cb) can be applied in addition to the component (Cd) shown in the component (C-1).

  (C-2) The polymerization method at the time of manufacturing a component can apply the polymerization method illustrated in (C-1) component, and solvent polymerization is mentioned as a preferable polymerization method. As the solvent used in the solution polymerization, usual solvents can be used, and preferably, ketones and alcohols can be mentioned. In this polymerization, well-known polymerization initiators, molecular weight regulators, chelating agents and inorganic electrolytes can be used.

  Mn of (C-2) component becomes like this. Preferably it is 5,000-70,000, More preferably, it is 10,000-30,000.

  In this invention, (C-2) component can be used individually or in mixture of 2 or more types obtained as mentioned above.

  The amount of component (C-2) used in the present invention is usually 50 to 800 parts by weight, preferably 60 to 700 parts by weight, more preferably 100 parts by weight of organosilane (1) in component (A). 80 to 500 parts by weight. In this case, if the usage-amount of (C) component is less than 50 weight part, there exists a tendency for the alkali resistance and crack resistance of the coating film obtained to fall. On the other hand, when it exceeds 800 weight part, there exists a tendency for the weather resistance of a coating film to fall.

  In addition, you may obtain the composition of this invention by mixing the said (C-1) component and the said (C-2) component.

  Furthermore, the following (D)-(G) component can be mix | blended with the composition of this invention.

(D) Component (D) A component consists of water and / or an organic solvent.

  The composition of the present invention essentially comprises the components (A), (B) and (C), and optionally contains the components (E) to (G) described below. In preparing the composition, water is added to cause the organosilane (1) or (C) component to undergo hydrolysis / partial condensation reaction or to disperse the particulate component.

  The usage-amount of the water in this invention is 0.5-3 mol normally with respect to 1 mol of organosilane (1) in (A) component, Preferably it is about 0.7-2 mol.

  In addition, the organic solvent mainly mixes (A) component, (B) component, (C) component, (E) to (G) component, etc., and adjusts the total solid content concentration of the composition, It is used to make it applicable to various coating methods and to further improve the dispersion stability and storage stability of the composition.

  Such an organic solvent is not particularly limited as long as the above components can be mixed uniformly. For example, one or more kinds of alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be used. 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, ethylene glycol monoethyl ether acetate, etc. can be mentioned.

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

  These organic solvents can be used alone or in admixture of two or more.

  The total solid concentration of the composition of the present invention is preferably 50% by weight or less, and is appropriately adjusted according to the purpose of use. For example, when it is intended to impregnate a thin film forming substrate, it is usually 5 to 30% by weight. When it is used for the purpose of forming a thick film, it is usually 20 to 50% by weight, preferably 30 to 45% by weight. %. When the total solid concentration of the composition exceeds 50% by weight, the storage stability tends to decrease.

(E) component (E) A component is a catalyst which accelerates | stimulates hydrolysis and condensation reaction, such as (A) component and (C) component.

  In the present invention, by using the component (E), the curing rate of the resulting coating film is increased, and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the organosilane component used is increased. In addition, a coating film excellent in long-term durability and the like can be obtained, and the coating film can be thickened and painted easily.

  As such component (E), acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter referred to as organometallic compounds and / or partial hydrolysates thereof) "Organic metal compound etc.") is preferred.

  Among the components (E), examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, phthalic acid, and the like, and preferably acetic acid.

  Moreover, as an alkaline compound, sodium hydroxide, potassium hydroxide etc. can be mentioned, for example, Preferably it is sodium hydroxide.

  Examples of the salt compound include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.

  Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, 3-aminopropyl, Trimethoxysilane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3- (2- Aminoethyl) -aminopropyl-methyl-dimethoxysilane, 3-anilinopropyl-trimethoxysilane, alkylamine salts, quaternary ammonium salts, and various modifications used as curing agents for epoxy resins It can be exemplified Min like, preferably 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl) - aminopropyl triethoxysilane.

  Moreover, as an organometallic compound etc., for example, a compound represented by the following general formula (4) (hereinafter referred to as “organometallic compound (4)”), having 1 to 10 carbon atoms bonded to the same tin atom. An organometallic compound of tetravalent tin having 1 to 2 alkyl groups (hereinafter referred to as “organotin compound”), a partial hydrolyzate of these compounds, or the like can be given.

M (OR ¹⁰ ) _p (R ¹¹ COCHCOR ¹² ) _q (4)
(In the formula, M represents zirconium, titanium or aluminum, and R ¹⁰ and R ¹¹ each independently represents an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group. A monovalent hydrocarbon group having 1 to 6 carbon atoms such as a group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group, and R ¹² is the same as C 1 to R ^{11 in the} same manner as R ¹⁰ and R ¹¹ . 6 monovalent hydrocarbon group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, stearyloxy group, etc. And an alkoxyl group having 1 to 16 carbon atoms, p and q are integers of 0 to 4, and (p + q) = (valence of M).)
Specific examples of the organometallic compound (4) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris ( Organic zirconium compounds such as ethyl acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; tetra-i-propoxytitanium, di-i-propoxy- Organo titanium compounds such as bis (ethyl acetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium; -I-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetonato aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonate) Examples thereof include organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate-bis (ethylacetoacetate) aluminum.

  Among these organometallic compounds (4) and partial hydrolysates thereof, tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxy ethylacetate Acetate aluminum, tris (ethyl acetoacetate) aluminum, or a partial hydrolyzate of these compounds is preferred.

（Ｃ_４Ｈ_９）Ｓｎ（ＯＣＯＣ_１１Ｈ_２３）_３、（Ｃ_４Ｈ_９）Ｓｎ（ＯＣＯＮａ）_３等のカルボン酸型有機錫化合物；（Ｃ_４Ｈ_９）_２Ｓｎ（ＳＣＨ_２ＣＯＯＣ_８Ｈ_１７）_２、（Ｃ_４Ｈ_９）_２Ｓｎ（ＳＣＨ_２ＣＨ_２ＣＯＯＣ_８Ｈ_１７）_２、（Ｃ_８Ｈ_１７）_２Ｓｎ（ＳＣＨ_２ＣＯＯＣ_８Ｈ_１７）_２、（Ｃ_８Ｈ_１７）_２Ｓｎ（ＳＣＨ_２ＣＨ_２ＣＯＯＣ_８Ｈ_１７）_２、（Ｃ_８Ｈ_１７）_２Ｓｎ（ＳＣＨ_２ＣＯＯＣ_１２Ｈ_２５）_２、（Ｃ_８Ｈ_１７）_２Ｓｎ（ＳＣＨ_２ＣＨ_２ＣＯＯＣ_１２Ｈ_２５）_２、（Ｃ_４Ｈ_９）Ｓｎ（ＳＣＯＣＨ＝ＣＨＣＯＯＣ_８Ｈ_１７）_３、（Ｃ_８Ｈ_１７）Ｓｎ（ＳＣＯＣＨ＝ＣＨＣＯＯＣ_８Ｈ_１７）_３、

等のメルカプチド型有機錫化合物；（Ｃ_４Ｈ_９）_２Ｓｎ＝Ｓ、（Ｃ_８Ｈ_１７）_２Ｓｎ＝Ｓ、

等のスルフィド型有機錫化合物；（Ｃ_４Ｈ_９）ＳｎＣｌ_３、（Ｃ_４Ｈ_９）_２ＳｎＣｌ_２、（Ｃ_８Ｈ_１７）_２ＳｎＣｌ_２、

等のクロライド型有機錫化合物；（Ｃ_４Ｈ_９）_２ＳｎＯ、（Ｃ_８Ｈ_１７）_２ＳｎＯ等の有機錫オキサイドや、これらの有機錫オキサイドとエチルシリケート、マレイン酸ジメチル、マレイン酸ジエチル、フタル酸ジオクチル等のエステル化合物との反応生成物等を挙げることができる。 Specific examples of the 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 _{7) 2 Sn (OCOCH = CHCOOC} 18 H 37) 2, (C 8 H 17) 2 Sn (OCOCH = CHCOOC 20 H 41) 2,

Carboxylic acid type organic tin compounds such as (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ and (C ₄ H ₉ ) Sn (OCONa) ₃ ; (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) Sn (SCOCH} = CHCOOC 8 H 17) 3, (C 8 H 17) Sn (SCOCH = CHCOOC 8 H 17) 3,

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

Sulfide type organotin compounds such as (C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ SnCl ₂ , (C ₈ H ₁₇ ) ₂ SnCl ₂ ,

Chloride-type organotin compounds such as: (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO and other tin oxides, these organotin oxides and ethyl silicate, dimethyl maleate, diethyl maleate, phthalate A reaction product with an ester compound such as dioctyl acid can be used.

  (E) A component can be used individually or in mixture of 2 or more types, and can also be used in mixture with a zinc compound and another reaction retarder.

  The component (E) may be blended when the composition is prepared, and may be blended with the composition at the stage of forming the coating film. Furthermore, both the preparation of the composition and the formation of the coating film are performed. You may mix | blend in the step.

  The amount of component (E) used is usually 0 to 100 parts by weight, preferably 0.01 to 80 parts per 100 parts by weight of organosilane (1) in component (A), except for organometallic compounds. Parts by weight, more preferably 0.1 to 50 parts by weight. In the case of an organometallic compound, etc., usually 0 to 100 parts by weight, preferably 100 parts by weight of the organosilane (1) in the component (A). Is 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight. In this case, when the amount of the component (E) used exceeds 100 parts by weight, the storage stability of the composition tends to decrease, or cracks tend to occur in the coating film.

(F) component (F) component is following General formula (5).
R ¹¹ COCH ₂ COR ¹² (5)
^{(Wherein, R 11} and ^{R 12,} the organometallic compound (the in 4) is synonymous with, respectively ^{R 11} and ^{R 12} in each general formula.) Beta-diketones represented by and / or beta-ketoester And at least one selected from the group consisting of carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds. Such a component (F) is preferably used in combination when an organometallic compound or the like is used as the component (E).

  Component (F) acts as a stability improver for the composition. That is, by coordinating the component (F) to a metal atom such as the organometallic compound, the co-condensation reaction of the components (A), (B) and (C) with the organometallic compound is promoted. It is considered that the effect of further improving the storage stability of the resulting composition is achieved by appropriately controlling the action.

  Specific examples of the component (F) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate -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, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, salicylua And the like can be given dehydrogenase. Of these, acetylacetone and ethyl acetoacetate are preferred.

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

  (F) The usage-amount of a component is 2 mol or more normally with respect to 1 mol of organometallic compounds in the said organometallic compound etc., Preferably it is 3-20 mol. In this case, if the amount of component (F) used is less than 2 mol, the effect of improving the storage stability of the resulting composition tends to be insufficient.

Component (G) The component (G) is composed of a powder 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 _{(G), SiO 2, Al 2 O 3} , Al (OH) 3, Sb 2 O 5, Si 3 N 4, Sn-In 2 O 3, Sb-In 2 O 3 MgF, CeF ₃ , CeO ₂ , SiO ₂ , Al ₂ O ₃ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Al ₂ O ₃ , Fe, Fe ₂ O ₃ , Co, Co—FeO _X , CrO _{2, Fe} 4 N, Ba _{ferrite, SmCO 5, YCO 5, CeCO} 5, PrCO 5, Sm 2 CO 17, Nd 2 Fe 14 B, ZrO 2, Al 4 O 3, AlN, SiC, α-Si, SiN _{4, CoO, Sb-SnO 2} , Sb 2 O 5, MnO 2, MnB, Co 3 O 4, Co 3 B, LiTaO 3, MgO, MgAl 2 O 4, BeAl 2 O 4, ZrS iO ₄ , ZnSb, PbTe, GeSi, FeSi ₂ , CrSi ₂ , CoSi ₂ , MnSi _1.73 , Mg ₂ Si, β-B, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , BaTiO _{3 3, PbTiO 3, BaO-Al} 2 O 3 -SiO 2, Al 2 TiO 5, Zn 2 SiO 4, Zr 2 SiO 4, 2MgO 2 -Al 2 O 3 -5SiO 2, Li 2 O-Al 2 O 3 - 4SiO _2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, can be cited Sr ferrite.

  Component (G) is present in the form of powder, an aqueous sol or colloid dispersed in water, a solvent sol or colloid 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, it may be further diluted with water or a solvent, or may be used after a surface treatment to improve the dispersibility.

  When the component (G) is an aqueous sol or colloid and a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less.

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

  As a method of blending the component (G) in the composition, it may be added after the preparation of the composition, or it may be added during the preparation of the composition, and the component (G) ) Component, (C) component and the like may be cohydrolyzed and partially condensed.

  The amount of component (G) used is usually 0 to 500 parts by weight, preferably 0.1 to 400 parts by weight, based on 100 parts by weight of organosilane (1) in component (A). .

(Other additives)
In addition, a filler can be added to and dispersed in the composition of the present invention for coloring, thickening, and the like of the resulting coating film.

  Examples of such fillers include water-insoluble organic pigments and inorganic pigments, particulate, fibrous or scale-like ceramics, metals or alloys, and oxides or hydroxides of these metals, other than pigments. , Carbides, nitrides, sulfides and the like.

  Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigment, aluminum oxide, chromium oxide, manganese oxide, iron oxide, and oxidation. Zirconium, 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, magnesium carbonate, barium sulfate, bentonite, Mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chromium green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bitumen, Pigment green, Rock ultramarine, Cobalt blue, Cerulean blue, Boric acid Copper, molybdenum blue, copper sulfide, cobalt purple Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium Red Chrome vermilion, bengara, 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, Examples thereof include graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

  These fillers can be used alone or in admixture of two or more. The amount of the filler used is usually 300 parts by weight or less with respect to 100 parts by weight of the total solid content of the composition.

  Furthermore, the composition of the present invention may contain, as desired, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, Dispersants such as polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt, polyethylene glycol; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc. Thickeners such as cellulose, castor oil derivatives, ferrosilicates; inorganics such as ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrite, sodium borohydride, calcium azide In addition to foaming agents, azo compounds such as azobisisobutyronitrile, hydrazine compounds such as diphenylsulfone-3,3′-disulfohydrazine, semicarbazide compounds, triazole compounds, N-nitroso compounds, and other organic foaming agents Other additives such as an activator, a silane coupling agent, a titanium coupling agent, and a dye can also be blended.

  Moreover, a leveling agent can be mix | blended in order to improve the coating property of a composition more. Among such leveling agents, examples of the fluorine-based leveling agent (trade name; hereinafter the same) include BM1000 and BM1100 of BM-CHEMIE; Fuka 772 and Fuka 777 of Fuka Chemicals; Kyoeisha Chemical Co., Ltd. Fluoren series manufactured by Sumitomo 3M Co., Ltd .; Fluoronal TF series manufactured by Toho Chemical Co., Ltd. and the like. Examples of silicone leveling agents include BYK series manufactured by BYK Chemie; (Sshmegmann) Sshmego series; EFKA 30, EFKA 31, EFKA 34, EFKA 35, EFKA 36, EFKA 39, EFKA 83, EFKA 86, EFKA 88, etc. of EFKA Chemicals, Inc. System level The grayed agents, for example, Kafinoru of Nissin Chemical Industry Co., Kao Corp. Emulgen include a Homogenol like.

  By blending such a leveling agent, the finished appearance of the coating film is improved, and it can be uniformly applied as a thin film.

  The amount of the leveling agent used is preferably 0.01 to 5% by weight, more preferably 0.02 to 3% by weight, based on the total composition.

  As a method of blending the leveling agent, it may be blended when preparing the composition, or may be blended into the composition at the stage of forming the coating film, and further, preparation of the composition and formation of the coating film. And may be blended in both stages.

  In preparing the composition of the present invention, when the (E) component and the (F) component are not used, the mixing method of each component is not particularly limited, but the (E) component and the (F) component are used. When doing, Preferably, after obtaining the mixture except (F) component among (A)-(F) components, the method of adding (F) component to this is employ | adopted.

  Specific examples of the method for preparing the composition include the following methods (i) to (iv).

  (I) Hydrolysis by adding a predetermined amount of water to a mixture composed of organosilane (1), (B) component, (C) component, (E) component and a necessary amount of organic solvent constituting component (A). A method of adding the component (F) after performing a partial condensation reaction.

  (Ii) A predetermined amount of water is added to a mixture comprising the organosilane (1) and the component (B) constituting the component (A) and the required amount of an organic solvent to perform hydrolysis and partial condensation reaction, and then (C ) Component and (E) component are added and mixed, and after further performing a partial condensation reaction, a method of adding component (F).

  (Iii) A predetermined amount of water is added to a mixture comprising the organosilane (1), the component (B), the component (E) and the necessary amount of an organic solvent constituting the component (A) to effect hydrolysis and partial condensation reaction. Followed by adding and mixing the component (C), further performing a partial condensation reaction, and then adding the component (F).

  (Iv) A predetermined amount of water is added to a mixture comprising a part of the organosilane (1) constituting the component (A), the component (B), the component (C), the component (E) and the required amount of organic solvent. Then, the hydrolysis / partial condensation reaction is performed, then the remainder of the organosilane (1) is added, the hydrolysis / partial condensation reaction is further performed, and then the component (F) is added. Also, the composition of the present invention may optionally

(V) After the method (i), (ii), (iii) or (iv) is carried out using each component except the component (B), it is also prepared by adding the component (B). be able to.

  In the present invention, components other than the components (A) to (F) can be added at an appropriate stage for adjusting the composition.

  The composition of the present invention has excellent photocatalytic functions such as an organic substance decomposing function and a hydrophilizing function, and can be suitably used as a coating composition for the purpose of utilizing the functions.

  When applying the composition of the present invention to a substrate, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, etc. are used, dip coating, flow coating, spraying, screen process, electrodeposition, vapor deposition, etc. With this coating method, it is possible to form a coating film having a thickness of about 1 to 40 μm by a single coating and a coating thickness of about 2 to 80 μm by a second to third coating. Then, it can dry at normal temperature, or can form a coating film on various base materials by heating and drying for about 10 to 60 minutes at the temperature of about 30-200 degreeC.

  Examples of the substrate to which the composition of the present invention can be applied include metals such as iron, aluminum, and stainless steel; inorganic ceramic materials such as cement, concrete, ALC, flexible board, mortar, slate, gypsum, ceramics, and bricks; Plastic molded products such as phenol resin, epoxy resin, polyester, polycarbonate, polyethylene, polypropylene, ABS resin (acrylonitrile-butadiene-styrene resin); plastic films such as polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, polyimide, , Wood, paper, glass and the like. The composition of the present invention is also useful for recoating a deteriorated coating film.

  These base materials can be subjected to surface treatment in advance for the purpose of adjusting the foundation, improving adhesion, sealing the porous base material, smoothing, patterning, and the like.

  For example, examples of the surface treatment for the metal base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment, coupling treatment, and the like. Examples of the surface treatment for the plastic base material include blasting. 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 the surface treatment for inorganic ceramic base materials include polishing. In addition, examples of the surface treatment for the wood base material include polishing, sealing, insect repellent treatment, etc., and examples of the surface treatment for the paper base material include, for example, eyes. Examples of the surface treatment for the deteriorated coating film include kelen and the like.

  Application | coating operation by the composition of this invention changes with kinds and states of a base material, and the application | coating method. For example, in the case of a metal-based base material, a primer is used if rust prevention is necessary, and in the case of an inorganic ceramic base material, the coating concealability differs depending on the characteristics of the base material (surface roughness, impregnation, alkalinity, etc.) Therefore, a primer is usually used. In the case of recoating a deteriorated coating film, a primer is used when the deterioration of the old coating film is significant.

  In the case of other substrates such as plastic, wood, paper, glass, etc., a primer may or may not be used depending on the application.

  The kind of primer is not particularly limited, and any primer may be used as long as it has an effect of improving the adhesion between the base material and the composition, and is selected according to the kind of base material and the purpose of use. The primer can be used alone or in admixture of two or more, and may be an enamel containing a coloring component such as a pigment or a clear containing no coloring component.

  As a kind of primer, for example, alkyd resin, amino alkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluororesin, acrylic silicone resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, and ( The composition which consists of A) component and (C) component, the composition which consists of (A) component in this invention, (C) component, and (G) component, etc. can be mentioned. These primers can also 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, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond.

  In addition, the surface of the coating film formed from the composition of the present invention has, for example, US Pat. No. 3,986,997, US Pat. A clear layer made of a siloxane resin-based paint such as a stable dispersion of colloidal silica and a siloxane resin described in US Pat. No. 4,027,073 can also be formed.

  Examples of the form in which the composition of the present invention is applied to a substrate include the following.

(A) Substrate / Composition (Clear, Enamel)
(B) Substrate / Composition (Enamel) / Composition (Clear)
(C) Substrate / Composition (Clear, Enamel) / Other organic paint / 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), the primer layer can be provided on the substrate in advance as necessary as described above.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified.

Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods.
(Mw and Mn)
It measured by the gel permeation chromatography (GPC) method by the following conditions.

  Sample: Tetrahydrofuran was used as a solvent, and 1 g of organosilane partial condensate or 0.1 g of silyl group-containing vinyl resin was dissolved in 100 cc of tetrahydrofuran, respectively.

  Standard polystyrene: Standard polystyrene manufactured by US Pressure Chemical Company was used.

Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA
Column: SHODEX A-80M (length: 50 cm) manufactured by Showa Denko K.K.
Measurement temperature: 40 ° C
Flow rate: 1cc / min (storage stability)
The composition to which no curing accelerator was added was sealed in a polyethylene bottle at room temperature for 3 months, and the presence or absence of gelation was visually determined. For those that did not gel, the viscosity was measured with a BM viscometer manufactured by Tokyo Keiki Co., Ltd., and those with a change rate of 20% or less were regarded as “no change”.

(Adhesion)
A tape peeling test was performed three times by a cross-cut test (100 squares) according to JIS K5400, and the average was obtained.

(hardness)
It was based on pencil hardness according to JIS K5400.

(Alkali resistance (1))
1 cc of a 1-40% sodium hydroxide aqueous solution was dropped on the coating film, allowed to stand for 6 hours in a petri dish with a lid, washed with water, and then visually observed for the state of the coating film. The maximum concentration of an aqueous sodium hydroxide solution without water was determined.

(Alkali resistance (2))
After immersing the test piece in a saturated calcium hydroxide aqueous solution for 60 days, the state of the coating film was visually observed.

(Organic chemical resistance)
After 2 cc of isopropyl alcohol was dropped onto the coating film and wiped off with a cloth after 5 minutes, the state of the coating film was visually observed.

(Moisture resistance)
The test piece was continuously kept for 1,000 hours in an environment of a temperature of 50 ° C. and a humidity of 95%, then taken out and the state of the coating film was visually observed.

(Weatherability)
According to JIS K5400, an irradiation test was conducted with a sunshine weather meter for 3,000 hours, and the appearance (cracking, peeling, etc.) of the coating film was visually observed.

(water resistant)
After immersing the test piece in tap water at room temperature for 60 days, the state of the coating film was visually observed.

(Hot water resistance)
After the test piece using the inorganic base material was immersed in warm water at 60 ° C. for 14 days, the state of the coating film was visually observed.

(Contamination resistance)
Apply a paste consisting of a mixture of carbon black / kerosene = 1/2 (weight ratio) on the coating, leave it at room temperature for 24 hours, and then wash with water using a sponge and observe the contamination of the coating. The evaluation was based on the following criteria.

No contamination: ○
Slightly contaminated: △
Contamination is remarkable: ×
(transparency)
Each composition was coated on quartz glass so as to have a dry film thickness of 10 μm, and then the visible light transmittance was measured and evaluated according to the following criteria.

Transmittance exceeds 80%: ◎
Transmittance is 60 to 80%: ○
Transmittance is less than 60%: △
(Hydrophilic)
The coating film was irradiated with a 1 mW / cm ² black light fluorescent lamp for 5 hours, and then the contact angle of water was measured.

Reference Example 1 (component (C-1))
In a reactor equipped with a reflux condenser and a stirrer, the monomer components shown in Table 1, 105 parts of isobutyl alcohol, 70 parts of methyl ethyl ketone, and 35 parts of methanol were added and mixed, and then heated to 80 ° C. with stirring. To this mixture, a solution of 4 parts of azobisisovaleronitrile in 10 parts of xylene was added dropwise over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to obtain a fluoroacrylic polymer (( C-1) component) is obtained.

Reference Example 2 (component (C-2))
After adding and mixing the monomer component shown in Table 1 and 320 parts of methyl isobutyl ketone to a reactor equipped with a reflux condenser and a stirrer, the mixture was heated to 100 ° C. with stirring, and this mixture was mixed with a siloxane unit. 3 parts of an azo-based initiator and 0.5 part of lauryl peroxide are added dropwise, and further reacted at 100 ° C. for 5 hours to obtain a fluorine vinyl ether polymer (component (C-2)) having a solid content of 24%.

Reference Example 3 (component (C-3))
An acrylic polymer (component (C-3)) having a solid content of 40% is obtained in the same manner as in Reference Example 1 except that the monomer component shown in the column of the component (C-3) in Table 1 is used. .

Reference Example 4 ((C-4) component)
A vinyl ether polymer (component (C-4)) having a solid content of 40% is obtained in the same manner as in Reference Example 2 except that the monomer component shown in the column of the component (C-4) in Table 1 is used. .

(Examples 1-4)
The components (A), (B), (C), (D) and (E) shown in Table 2 were added to a reactor equipped with a reflux condenser and a stirrer and mixed. The reaction was carried out at 5 ° C. for 5 hours. Subsequently, the component (F) was post-added and cooled to room temperature to obtain a composition having a solid content concentration of 20%.

  Further, the composition obtained here was applied to an alkali degreased aluminum plate (JIS H4000, A1050P) by a spray method so as to have a dry film thickness of 20 μm, dried by heating at 150 ° C. for 10 minutes, and a test piece. Was made.

  Table 4 shows the evaluation results of the storage stability of the composition and various evaluation results of the test pieces.

  As described above, the composition of the present invention is particularly excellent in weather resistance and storage stability, and has excellent adhesion, alkali resistance, organic chemical resistance, moisture resistance, (warm) water resistance, stain resistance, and the like. A coating film having high hardness can be formed, and has an extremely high balance of properties as an organosilane-based coating material.

(Comparative Examples 1-4)
(A) component, (B) component, (C) component, (D) component or (E) component shown in Table 3 was added to a reactor equipped with a reflux condenser and a stirrer and mixed. The reaction was carried out at 5 ° C. for 5 hours. Subsequently, the component (F) was post-added and cooled to room temperature to obtain a composition having a solid content concentration of 20%.

  Moreover, the test piece was produced like the Example 1 using the composition obtained here.

  Table 5 shows the evaluation results of the storage stability of the composition and various evaluation results of the test pieces.

  Since the composition of Comparative Example 1 and Comparative Example 2 does not use the component (C-1) or (C-2) which is an essential constituent of the present invention, the composition is outside the technical scope of the present invention. As is apparent from Table 5, the results are poor in alkali resistance and crack resistance.

  The compositions of Comparative Example 3 and Comparative Example 4 consisted of (C-3) component or (C-4) component obtained by polymerizing monomer components not containing (Ca) monomer. In other words, since it is an acrylic polymer or vinyl ether polymer that does not contain fluorine as a constituent component, it is a composition outside the technical scope of the present invention. The result is inferior.

Claims (8)

(A) The following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2) An integer of 2. When n is 2, R ^{1 s} may be the same or different from each other, and R ² may be the same or different from each other. , At least one selected from the group consisting of a hydrolyzate of the organosilane and a partial condensate of the organosilane,
(B) a photocatalyst, and (C-1) a fluoroacrylic polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal and / or side chain of the polymer molecular chain,
A composition comprising:
The amount of the component (B) used is 1 to 500 parts by weight in solid content with respect to 100 parts by weight of the organosilane in the component (A).
The use amount of the component (C-1) is 30 to 500 parts by weight with respect to 100 parts by weight of the organosilane in the component (A). In claim 1,
The component (C-1) includes (Ca) a monomer containing a fluorine atom, (Cb) an alkyl (meth) acrylate, a monomer having a (Cc) silyl group, and (Cd) obtained by polymerizing other monomers copolymerizable with the monomers (Ca), (Cb), and (Cc). Characteristic composition. In claim 1 or claim 2,
The content of the silyl group in the component (C-1) is 0.001 to 20% by weight with respect to the polymer before introduction of the silyl group in terms of the amount of silicon atoms. And a composition. In any one of Claims 1 to 3,
The specific silyl group in the component (C-1) is represented by the following general formula (2)

(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, or an amino group, or a hydroxyl group, and R ³ represents a hydrogen atom, having 1 to 10 carbon atoms. An alkyl group or an aralkyl group having 1 to 10 carbon atoms, wherein i is an integer of 1 to 3). (A) The following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is 0 to 2) An integer of 2. When n is 2, R ^{1 s} may be the same or different from each other, and R ² may be the same or different from each other. , At least one selected from the group consisting of a hydrolyzate of the organosilane and a partial condensate of the organosilane,
(B) a photocatalyst, and (C-2) a fluorine vinyl ether polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal and / or side chain of the polymer molecular chain,
A composition comprising:
The amount of the component (B) used is 1 to 500 parts by weight in solid content with respect to 100 parts by weight of the organosilane in the component (A).
The amount of the component (C-2) used is 50 to 800 parts by weight with respect to 100 parts by weight of the organosilane in the component (A). In claim 5,
The component (C-2) includes (Ca) a monomer containing a fluorine atom, (Ce) a vinyl ether monomer, and (Cf) the (Ca) used as necessary. And a composition obtained by polymerizing another monomer copolymerizable with the monomer (Ce). In claim 5 or claim 6,
The content of the silyl group in the component (C-2) is 0.001 to 20% by weight with respect to the polymer before introduction of the silyl group in terms of the amount of silicon atoms. And a composition. In any one of Claims 5 thru | or 7,
The silyl group in the component (C-2) is represented by the following general formula (2)

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