JP2000273396A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition which gives a coating film excellent in adhesiveness, resistances to alkali, organic chemicals, water and staining, etc., by incorporating an organosilane component, a silylated fluoropolymer and a photocatalyst into the same. SOLUTION: This composition comprises an organosilane represented by the formula: (R1)nS(OR2)4-n, preferably at least one organosilane selected from among trialkoxysilanes, dialkoxysilanes and their hydrolyzates and condensates; a copolymer having structural units represented by formula I and structural units represented by formula II and having silyl groups having Si atoms bonded to hydrolyzable groups and/or hydroxy groups; and a photocatalyst (e.g. TiO2). In the formulas, R1 is a 1-8C monovalent organic group; R2 is a 1-5C alkyl or 1-6C acyl; n is 0-2; R3 to R5 are each CmY2m+1 (wherein m is 0-5; and Y is H, F or Cl); and Rf is a fluorine-containing alkyl or alkoxy group. The composition is excellent in storage stability and gives a coating film having a high hardness and an excellent weatherability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition having a photocatalytic function, and more particularly, to an organosilane-based coating composition having a photocatalyst and a fluoropolymer having a silyl group. .

[0002]

2. Description of the Related Art The technical development of organosilane-based coating materials has been promoted as maintenance-free coating materials having excellent weather (light) resistance and stain resistance. The performance requirements for such organosilane-based coating materials are becoming more and more severe. In recent years, coating film appearance, adhesion, weather resistance, heat resistance, alkali resistance, organic chemical resistance, moisture resistance, (temperature) resistance There is a need for a coating material that is excellent in water-based properties, insulation resistance, abrasion resistance, stain resistance, and the like, and that can form a coating film having high hardness.

[0003] In recent years, many coating compositions containing a photocatalytic component have been proposed.
A titanium oxide coating film forming composition for photocatalyst comprising a titanium oxide, a hydrolyzate of a hydrolyzable silicon compound (alkyl silicate or silicon halide), and a solvent (water or alcohol) (JP-A-8-164334);
A silicon compound having at least two alkoxy groups,
For imparting antibacterial and antifungal properties, comprising a titanium compound or zirconium compound having at least two alkoxy groups and a hydrophilic inorganic powder such as titanium oxide treated with an alkoxysilane and / or polysiloxane having a guanidyl group. Surface treatment composition (Japanese Unexamined Patent Publication No.
176527), 20 to 200 parts by weight of a tetraalkoxysilane, 100 parts by weight of a trialkoxysilane and 0 to 60 parts by weight of a dialkoxysilane, and the weight average molecular weight in terms of polystyrene prepared from the raw material is 900 or more. There is known a method of forming an inorganic coating film in which a coating film obtained from a mixed solution of an inorganic coating material and a powder having a photocatalytic function is treated with an acid or an alkali (Japanese Patent Application Laid-Open No. H8-259891).

However, these compositions and liquid mixtures for forming a coating film are essentially composed of a photocatalyst component or an antibacterial and antifungal agent based on an alkoxysilane and / or polysiloxane component having a guanidyl group, deodorization and decomposition of harmful substances. In addition to these effects, the hardness, adhesion,
The film performance including alkali resistance, organic chemical resistance, weather resistance and stain resistance has not been comprehensively studied.

On the other hand, as a cog composition which satisfies the required performance of an organosilane-based coating material to some extent,
Composition containing a partial condensate of an organosilane, a dispersion of colloidal silica and a silicone-modified acrylic resin (Japanese Patent Application Laid-Open No. 60-135465), a condensate of an organosilane, a chelate compound of a zirconium alkoxide and a hydrolyzable silyl group (JP-A-64-1769), a composition comprising a condensate of organosilane, colloidal alumina and a hydrolyzable silyl group-containing vinyl resin (US Pat. , 904, 721) have been proposed.

However, the above-mentioned Japanese Patent Application Laid-Open No. 60-1354 discloses
Coatings obtained from the compositions described in JP-A-65 and US Pat. No. 4,904,721 have the disadvantage that gloss is reduced by prolonged irradiation with ultraviolet light.
Further, the composition described in JP-A-64-1769 has a problem that storage stability is not sufficient, and when the solid content concentration is increased, gelation easily occurs in a short period of time.

Further, the applicant of the present application has already disclosed a hydrolyzate of an organosilane and / or a partial condensate thereof, a vinyl resin having a hydrolyzable and / or silyl group having a silicon atom bonded to a hydroxyl group, a metal chelate. A coating composition containing a compound and β-diketones and / or β-ketoesters has been proposed (JP-A-5-345877), and the composition is used for an organosilane-based coating material. Although the required balance of the above-mentioned properties of the coating film is excellent, these properties are also required to be further improved.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has as its object to contain a specific organosilane component and a semiconductor component having photocatalytic activity, Excellent weather resistance and storage stability,
Provided is a coating composition having a photocatalytic function capable of forming a coating film having excellent adhesiveness, alkali resistance, organic chemical resistance, (hot) water resistance, stain resistance, and the like, and having high hardness. It is in.

[0009]

The present invention provides (A) the following:
General formula (1) (R¹)_nSi (OR^Two)_4-n ... (1) (where R¹Are the same or different when there are two
Represents a monovalent organic group having 1 to 8 carbon atoms;^TwoAre the same
Or different, an alkyl group having 1 to 5 carbon atoms or carbon number
Represents an acyl group of 1 to 6, and n is an integer of 0 to 2. )
An organosilane represented by the formula:
Selected from the group consisting of decomposed products and condensates of the organosilane
At least one kind (hereinafter also referred to as “component (A)”),
(B) (b-1) a structural unit represented by the following general formula (2)
(Hereinafter also referred to as “(b-1) structural unit”), and (Where R^Three~ R^FiveIs C_mY_{2m + 1}, M = an integer from 0 to 5,
Y is independently selected from F, H and Cl
You. (B-2) a structural unit represented by the following general formula (3)
(Hereinafter also referred to as “(b-2) constituent unit”)Wherein Rf is an alkyl group containing a fluorine atom or
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R of the general formula (2) ^Three~ R
^FiveAnd may be different. And a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group.
Silyl group having a child (hereinafter also referred to as "specific silyl group")
(Hereinafter also referred to as "component (B) component"),
(C) photocatalyst (hereinafter also referred to as “(C) component”).
To provide a coating composition characterized by having
Things.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The components constituting the composition of the present invention will be described below in order. (A) Component The component (A) blended in the coating composition of the present invention includes an organosilane (hereinafter referred to as “organosilane (1)”) represented by the general formula (1), and an organosilane (1). And a condensate of the organosilane (1). That is,
The component (A) may be only one of these three types, a mixture of any two types, or a mixture containing all three types. Here, the hydrolyzate of the organosilane (1) is the organosilane (1)
It is not necessary that all ² to 4 OR ² groups are hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. There may be. The condensate of the organosilane (1) is formed by condensing a silanol group of a hydrolyzate of the organosilane (1) to form a Si—O—Si bond. It is not necessary that they are all condensed, and the concept encompasses those in which a small portion of silanol groups are condensed, and mixtures of those having different degrees of condensation.

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
Examples of the monovalent organic group of 8 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Alkyl groups such as hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group, vinyl group, allyl group, cyclohexyl group, phenyl group, acyl group, glycidyl group, (meth) acryloxy group, ureido group Amide group, fluoroacetamide group, isocyanate group and the like, and substituted derivatives of these groups.

Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) An acryloxy group, a ureido group, an ammonium base and the like can be mentioned. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. And an acyl group having 1 to 6 carbon atoms, for example, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group, and the like. A plurality of R ² in the general formula (1) may be the same or different from each other.

Specific examples of the organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane and the like. Class: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyl Trimethoxysilane, n-
Hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 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-hydroxypropyltriethoxysilane Methoxysilane, 2-hydroxypropyltriethoxysilane, 3-
Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 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) atacryloxypropyltri Trialkoxysilanes such as ethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,
n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, −
n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane,
In addition to dialkoxysilanes such as di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane , Methyltriacetyloxysilane, dimethyldiacetyloxysilane, and the like.

Of these, trialkoxysilanes,
Dialkoxysilanes are preferable, and trialkoxysilanes are preferably methyltrimethoxysilane and methyltriethoxysilane. Further, dialkoxysilanes are preferably dimethyldimethoxysilane and dimethyldiethoxysilane.

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

The organosilane (1) is used as it is or as a hydrolyzate and / or condensate. When the organosilane (1) is used as a hydrolyzate and / or condensate, it can be hydrolyzed and condensed in advance and used as the component (A). However, as described later, the organosilane (1) can be used as the component (A). When preparing a composition by mixing with the remaining components, by adding an appropriate amount of water, the organosilane (1) is hydrolyzed and condensed,
It is preferable to use the component (A). When the component (A) is used as a condensate, the condensate preferably has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”),
800 to 100,000, more preferably 1,000.
0 to 50,000.

Commercially available components (A) include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicon resin manufactured by Dow Corning Toray, and silicon resin manufactured by Toshiba Silicone Co., Ltd. Resins and silicon oligomers manufactured by Nippon Unicar Co., Ltd., etc., and these may be used as they are or after condensation.

In the present invention, the component (A) can be used alone or in combination of two or more.

Component (B) The component (B) in the present invention has the above structural units (b-1) and (b-2), and has a specific silyl group,
That is, a fluorine-based compound having a silyl group (specific silyl group) having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and preferably having a specific silyl group at a terminal and / or a side chain of a polymer molecular chain. It is a polymer. When such a component (B) hardens a coating film obtained from the composition of the present invention, a hydrolyzable group and / or a hydroxyl group in the silyl group is co-condensed with the component (A). Thereby, excellent coating film performance can be obtained.
The content of the specific silyl group in the component (B) is usually from 0.1 to 60 mol%, preferably in terms of the amount of silicon atoms, based on all the monomer components constituting the component (B). 0.
5 to 50 mol%.

The specific silyl group preferably has the following general formula (4) (Wherein X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
It represents a hydrolyzable group or a hydroxyl group such as an amino group, R ⁶
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).

The component (B) is a monomer constituting the structural unit (b-1) represented by the general formula (2) (hereinafter referred to as “(b-
1) a monomer)), a monomer constituting the (b-2) structural unit represented by the general formula (3) (hereinafter referred to as “(b-
2) monomer)) and (b-3) a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group which constitutes the specific silyl group represented by the general formula (4) (b -3) Monomer (hereinafter referred to as "(b-3) monomer")
And (b-4) another monomer copolymerizable with these monomers (hereinafter referred to as "(b-
4) Monomer ”). The (b-4) monomer may have a fluorine atom that is not included in the (b-1) monomer and the (b-2) monomer.

The component (B) is a polymer obtained by polymerizing the above-mentioned monomers (b-1) and (b-2), or a component necessary for these monomers. Accordingly, (b-
4) A (b-5) silane compound having a functional group capable of reacting with a hydrolyzable group or a hydroxyl group at a carbon-carbon double bond of a polymer obtained by polymerization further including a monomer (hereinafter, referred to as “ (Also referred to as a "silane compound").

(B-1) monomer; (b-1) monomer is
It is represented by the following general formula (2) ′. (Wherein, R ^{3 to} R ⁵ are C _m Y _{2m + 1} , m is an integer of 0 to 5,
Y is independently selected from F, H and Cl. )

The above (b-1) monomer includes, for example,
Examples include compounds having one polymerizable unsaturated double bond group and at least one fluorine atom. (B-1) Specific examples of the monomer include: (a) CF ₂ = CF ₂ , CHF = CF ₂ , CH ₂ = CF
₂ , CH ₂ = CHF, CCIF = CF ₂ , CHCl = C
F ₂ , CCl ₂ = CF ₂ , CCIF = CCLF, CHF
Fluoroethylenes such as ＝ CCl ₂ , CH ₂ ＣCCIF, CCl ₂ ＣCCIF; CF ₃ CF 3CF ₂ , CF ₃
CF = CHF, CF ₃ CH = CF ₂ , CF ₃ CF = CH
₂ , CF ₃ CF = CHF, CHF ₂ CF = CHF, CF
₃ CH = CH ₂ , CH ₃ CF = CF ₂ , CH ₃ CH = C
F ₂ , CH ₃ CF = CH ₂ , CF ₃ ClCF = CF ₂ ,
CF ₃ CCl = CF ₂ , CF ₃ CF = CFCl, CF ₂
ClCCl = CF ₂ , CF ₂ ClCF = CFCl, CF
₃ CCl = CCIF, CF ₃ CCl = CCl ₂ , CCl
₃ CF = CF ₂ , CF ₂ ClCCl = CCl ₂ , CFC
l ₂ CCl = CCl ₂ , CF ₃ CF = CHCl, CCl
F ₂ CF = CHCl, CF ₃ CCl = CHCl, CHF
₂ CCl = CCl ₂ , CF ₂ ClCH = CCl ₂ , CF
Fluoropropenes such as ₂ ClCCl = CHCl, CCl ₃ CF = CHCl;

(B) CF_ThreeCF_TwoCF = CF_Two, CF_Three
CF = CFCF_Three, CF_ThreeCH = CFCF_Three, CF_Two=
CFCF_TwoCHF_Two, CF_ThreeCF_TwoCF = CH_Two, CF
_TwoCH = CHCF_Three, CF_Two= CFCF_TwoCH_Three, CF
_Two= CFCH_TwoCH_Three, CF _ThreeCH_TwoCH = CH_Two, C
F_ThreeCH = CHCH_Three, CF_Two= CHCH_TwoCH_Three, C
H_ThreeCF_TwoCH = CH_Two, CFH_TwoCH = CHCF
H_Two, CH_ThreeCF_TwoCH = CH_Two, CH_Two= CFCH_Two
CH_Three, CF_Three(CF_Two)_TwoCF = CF_Two, CF_Three(C
F_Two)_TwoCF = CF_TwoFluoro having 4 or more carbon atoms such as
Refins; and the like. These fluorine atoms
The contained (b-1) monomer may be used alone or in combination of two or more.
A combination of the above may be used.

(B-2) a monomer; (b-2) a monomer
It is represented by the following general formula (3) ′. [In the formula, Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom, and R ^{3 to} R ⁵ represent the general formula (2) ′
And within the same meaning, R ³ of the general formula (2) ′
~R ⁵ and may be different. ]

As the monomer (b-2), for example,
Compounds having one polymerizable unsaturated double bond group, an ether bond and at least one fluorine atom can be mentioned. (B-2) Specific examples of the monomer include (a) CH ₂ ＣＨCH—O—Rf (Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom) (fluoroalkyl) Vinyl ether or (fluoroalkoxyalkyl) vinyl ethers; (ii) perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether)
(C) Perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether); and the like. These (b-2) monomers containing a fluorine atom may be used alone or in combination of two or more.

As the combination of the monomer (b-1) and the monomer (b-2), hexafluoropropylene is used in combination with perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether. Is preferred.

(B-3) monomer; (b-3) monomer is
Monomer containing a polymerizable unsaturated double bond and a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group in one molecule. As the monomer (b-3), for example, the following general formula (4) ′ [Wherein X, R ^6, i has the same meaning as X, R ^6, i respectively in the general formula (4), R ⁷ represents an organic group having a polymerizable double bond] is represented by (Hereinafter referred to as "unsaturated silane compound").

Specific examples of the unsaturated silane compound include CH ₂ CHSi (CH ₃ ) (OCH ₃ ) ₂ and CH ₂ ＝
CHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OC ₂ H ₅ )
₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHS
iCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ )
(OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (O
_{CH 3) 3, CH 2 =} CHCOO (CH 2) 3 Si (CH 3)
(OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (O
CH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ )
Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ SiCl ₃ , C
H ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH
₂ ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH ₂ ＣC (C
H ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CH
₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C
H ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OC
H ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (O
CH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si
(CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂
SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si
(CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃
SiCl ₃ ,

[0032]

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And the like. These are 1
Species can be used alone or in combination of two or more.

(B-4) monomers; (b-1) to (b)
-3) Another monomer copolymerizable with the monomer (b-
4) As the monomer, for example, (a) 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
Alkyl (meth) acrylates having 4 to 12 carbon atoms, such as -ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl methacrylate; (ii) styrene, α-methylstyrene, 4-methylstyrene, -Methylstyrene, 3-methylstyrene, 4-
Methoxystyrene, 2-hydroxymethylstyrene, 4
-Ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, Aromatic vinyl monomers such as 1,4-dichlorostyrene, 2,6-dichlorostyrene and 1-vinylnaphthalene;

(C) hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyamyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylate; epoxy compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, and methyl glycidyl (meth) acrylate;

(D) 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, trimethylolpropane tri (meth) Polyfunctional monomers such as acrylates and pentaerythritol tetra (meth) acrylate;

(E) (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic amide,
Acid amide compounds such as maleimide; (f) vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl ester; (g) 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, substituted straight-chain conjugated pentadienes substituted with a substituent such as an alkyl group, a halogen atom, a cyano group, straight-chain and side-chain conjugated hexadienes, etc. (H) (meth) acrylic acid, fumaric acid, itaconic acid, monoalkylitaconic acid, maleic acid, crotonic acid, 2-
Ethylenically unsaturated carboxylic acids such as (meth) acryloyloxyethyl hexahydrophthalic acid;

(Ii) vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; (nu) 4- (meth) acryloyloxy-2,2,6
6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine,
4- (meth) acryloyloxy-1,2,2,6,6
-Piperidine monomers such as pentamethylpiperidine;

(V) Vinyl glycidyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl Vinyl ethers such as vinyl ether;

(II) Allyl ethers such as allyl glycidyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; (V) 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-
Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether;

(F) 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, pentadecafluorooctyl (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-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl And fluorine-containing (meth) acrylates such as (meth) acrylate; and dicaprolactone. These can be used alone or in combination of two or more.

(B-5) Silane compounds; (b-5) silane compounds used in the addition reaction include halogenated silanes such as methyldichlorosilane, trichlorosilane, phenyldichlorosilane; methyldiethoxysilane, methyl Alkoxysilanes such as dimethoxysilane, phenyldimethoxysilane, trimethoxysilane, and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, and triacetoxysilane; methyldiaminoxysilane, triaminoxysilane; Examples thereof include aminoxysilanes such as dimethylaminoxysilane. These can be used alone or in combination of two or more.

As the polymerization method for producing the component (B), for example, a method in which a monomer is added in a lump and polymerization is performed, a part of the monomer is polymerized, and then the remaining part is continuously polymerized. Or a method of adding the monomer intermittently, or a method of continuously adding the monomer from the beginning of the polymerization.
Further, a polymerization method in which these polymerization methods are combined may be employed. Preferred polymerization methods include solution polymerization. As the solvent used for the solution polymerization, a usual solvent 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 content of the structural unit (b-1) constituting the component (B) is usually 0.5 to 60 mol%, preferably 1 to 50 mol%, in the component (B). If the amount is less than 0.5 mol%, it may be difficult to obtain a coating film having excellent stain resistance, while if it exceeds 60 mol%, the obtained coating film may have poor long-term weather resistance. The content of the structural unit (b-2) in the component (B) is generally 0.1 to 60 mol%, preferably 0.5 to 50 mol%. If it is less than 0.1 mol%, it may be difficult to obtain a coating film having excellent stain resistance, while if it is more than 60 mol%, the solubility of the coating composition in a solvent is reduced, and the transparency is reduced. In some cases, it is difficult to obtain an excellent coating film. In the component (B), the total content of the structural units (b-1) and (b-2) is preferably 80 mol% or less. 8
If it exceeds 0 mol%, the adhesion of the obtained coating film to the substrate may be poor. Further, the content of (b-3) the specific silyl group is, as described above, usually 0.1 to 60 mol% in the component (B) in terms of the amount of silicon atoms.
Preferably, the amount is 0.5 to 50 mol%. 0.
If it is less than 1 mol%, the effect of co-condensation with the component (A) cannot be obtained, while if it exceeds 60 mol%, the storage stability of the obtained coating composition tends to be poor. The structural unit composed of the monomer (b-4), which is another copolymerizable monomer [(b-4) structural unit], is usually 90 mol% or less in the component (B). Preferably, 80 mol%
Below.

The component (B) preferably has a number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) of preferably 1,000.
~ 50,000, more preferably 5,000 ~ 3
It is 0000.

In the present invention, the component (B) can be used alone or as a mixture of two or more kinds obtained as described above.

The amount of the component (B) used in the present invention is as follows:
Usually, 20 to 500 parts by weight, preferably 2 parts by weight, per 100 parts by weight of the organosilane (1) in the component (A) is used.
It is 5 to 400 parts by weight, more preferably 50 to 300 parts by weight. In this case, if the amount of the component (B) is less than 20 parts by weight, the resulting coating film tends to have reduced alkali resistance and crack resistance. On the other hand, if it exceeds 500 parts by weight, the weather resistance of the coating film tends to decrease.

Component (C) The component (C) in the present invention comprises a photocatalyst, and a preferable photocatalyst is a semiconductor having photocatalytic ability.

As a semiconductor having photocatalytic ability, for example,
For example, TiO_Two, TiO_Three, SrTiO _Three, FeTi
O_Three, WO_Three, SnO_Two, Bi_TwoO_Three, In_TwoO_Three, Z
nO, Fe _TwoO_Three, RuO_Two, CdO, CdS, CdS
e, GaP, GaAs, CdFeO _Three, MoS_Two, La
RhO_Three, GaN, CdP, ZnS, ZnSe, ZnT
e, Nb_TwoO_Five, ZrO_Two, InP, GaAsP, In
GaAlP, AlGaAs, PbS, InAs, PbS
e, InSb, and the like.
Preferred is TiO_Two, ZnO.

In the present invention, the balance between the function of imparting hydrophilicity by the photocatalytic activity of the component (C) and the water / oil repellency of the component (B) allows hydrophobic contamination of hydrophilic contaminants. Excellent contaminant resistance can be exhibited even with respect to contaminants having a property. Moreover, in the coating film obtained from the coating composition of the present invention, the component (C) has a bond with the components (A) and (B), and the stain resistance of the coating film is maintained for a long time. Is done.

The semiconductor is desirably used in the form of powder and / or sol. Specifically, it is desirable to adopt any one of the three modes of powder, an aqueous sol dispersed in water, a polar solvent such as isopropyl alcohol, and a solvent sol dispersed in a non-polar solvent such as toluene. In the case of a solvent-based sol, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor. The average particle size of the semiconductor in these existing forms is preferably as small as possible from the viewpoint of photocatalytic ability. In this case, when the average particle diameter of the semiconductor is 0.3 μm or more, the coating film becomes opaque due to the light hiding effect of the semiconductor. When the thickness is less than 0.3 μm, the coating film becomes transparent. Therefore, the average particle diameter of the semiconductor can be appropriately selected according to the use of the composition.

When the component (C) 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.

As a method of blending the component (C) into the composition, the composition may be added after the composition comprising the components (A) to (B) and the components (D) to (G) described later. Alternatively, it can be added during the preparation of this composition to hydrolyze and condense the components (A) and (B) in the presence of the component (C). When the component (C) is added during the preparation of the composition, the semiconductor compound in the component (C) can be co-condensed with the components (A) and (B), and the long-term durability of the obtained coating film is improved. You. When the component (C) is an aqueous sol, it is preferably added at the time of preparation of the composition. Further, when the viscosity in the system increases due to the incorporation of the component (G) described later, the component (C) is added. It is preferred to add the component) during the preparation of the composition. Further, when the composition of the present invention is used as an enamel containing a coloring component, toning may be performed after adding the component (C) to the composition. May be simultaneously added to the composition.

In the present invention, the component (C) is used alone or as a mixture of two or more. The amount of the component (C) used is the same as that of the organosilane (1) 10 in the component (A).
0 parts by weight and solid content are usually 0.1 to 500 parts by weight, preferably 1 to 400 parts by weight. If the amount is less than 0.1 part by weight, the photocatalytic function may not be sufficiently exhibited, while if it exceeds 500 parts by weight, the film-forming property of the coating composition may decrease.

Further, the following components (D) to (G) can be added to the composition of the present invention. Hereinafter, these components will be described.

(D) Component The component (D) comprises water and / or an organic solvent. The composition of the present invention comprises the above components (A) to (C) as essential components,
In some cases, the composition contains components (E) to (G) described below and the like. Usually, when a composition is prepared, water is used to cause hydrolysis and condensation of the organosilane (1) and the component (B). Alternatively, it is added to disperse the particulate component. The amount of water used in the present invention is generally 0.5 to 0.5 mol per 1 mol of the organosilane (1) in the component (A).
It is about 3 mol, preferably about 0.7 to 2 mol.

The organic solvent is mainly composed of (A)
To (C) components, (E) to (G) components, etc., to uniformly adjust the total solids concentration of the composition, to be applicable to various coating methods, and to disperse the composition in a stable manner. And used to further improve the storage stability.

The organic solvent is not particularly limited as long as it can uniformly mix the above components.
For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be mentioned.
Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol,
sec-butyl alcohol, t-butyl alcohol, n
-Hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether,
Examples include ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, and propylene glycol monomethyl ether.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and the like. Specific examples of esters such as methyl isobutyl ketone and diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more.

The total solid content 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, and when it is used for forming a thick film, it is usually 20 to 50% by weight.
Preferably it is 30 to 45% by weight. If the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease.

Component (E) The component (E) is a catalyst for promoting the hydrolysis / condensation reaction of the components (A) and (B). By using the component (E), the curing rate of the obtained coating film is increased, and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the organosilane component used is increased,
A coating film with excellent strength and long-term durability can be obtained,
In addition, the thickness of the coating film and the painting work are also facilitated.

The component (E) includes 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 a component (E)).
Organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organometallic compounds or the like”). Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, and phthalic acid, and acetic acid is preferred. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide. Further, as the salt compound, for example, naphthenic acid, octylic acid,
Examples thereof include alkali metal salts such as 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, and the like. -Aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3 -(2-aminoethyl) -aminopropylmethyldimethoxysilane, 3
-Anilinopropyl trimethoxysilane, alkylamine salts, quaternary ammonium salts, and various modified amines used as a curing agent for epoxy resins, and the like, preferably 3-aminopropyl trimethoxysilane. , 3-aminopropyl-triethoxysilane and 3- (2-aminoethyl) -aminopropyl-triethoxysilane.

Examples of the organometallic compound include a compound represented by the following general formula (5) (hereinafter referred to as “organometallic compound (5)”), a compound having 1 to 1 carbon atoms bonded to the same tin atom. Examples thereof include organometallic compounds of tetravalent tin having 1 to 2 alkyl groups of 10 (hereinafter referred to as "organotin compounds"), and partially hydrolyzed products of these compounds.

M (OR ⁸ _p (R ⁹ COCHCOR ¹⁰ ) _q (5) wherein M represents zirconium, titanium or aluminum, and R ⁸ and R ⁹ are the same or different and represent an ethyl group, Monovalent having 1 to 6 carbon atoms such as n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group and phenyl group. Wherein R ¹⁰ is
In addition to the same monovalent hydrocarbon groups having 1 to 6 carbon atoms as R ⁸ and R ⁹ , methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t -Represents an alkoxyl group having 1 to 16 carbon atoms such as a butoxy group, a lauryloxy group and a stearyloxy group, p and q are integers of 0 to 4, and (p + q) = (valence of M). ]

Specific examples of the organometallic compound (5) include (a) tetra-n-butoxyzirconium and tri-n-
Butoxy ethyl acetoacetate zirconium, di-
n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. Organic zirconium compounds;

(B) Tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetone) Organic titanium compounds such as titanium; (c) tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-
aluminum i-propoxy acetylacetonate,
i-propoxybis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate)
Organic aluminum compounds such as aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum; and the like.

Among these organometallic compounds (5) and partial hydrolysates thereof, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-i-propoxy・ Ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or
Partial hydrolysates of these compounds are preferred.

Further, specific examples of the organotin compound include:
(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 = CHC
OOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = C
HCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (O
COCH = CHCOOC ₁₆ H ₃₃ ) ₂ , (C ₈ H ₁₇ ) ₂ S
n (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 = CHC
OOC ₂₀ H ₄₁ ) ₂ ,

[0070] (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ , (C ₄ H ₉ )
Carboxylic acid type organotin compounds such as 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 COO
C 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 CO
OC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO)
C ₁₂ H ₂₅ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ C)
OOC ₁₂ H ₂₅ ) ₂ , (C ₄ H ₉ ) Sn (SCOCH = C
HCOOC ₈ H ₁₇ ) ₃ , (C ₈ H ₁₇ ) Sn (SCOCH)
ＣＨCHCOOC ₈ H ₁₇ ) ₃ ,

[0072] 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 , (C ₄ H ₉ ) ₂ Sn
Organic tin oxides such as O, (C ₈ H ₁₇ ) ₂ SnO, and these organic tin oxides and ethyl silicate;
Reaction products with ester compounds such as dimethyl maleate, diethyl maleate, and dioctyl phthalate;

The component (E) can be used alone or as a mixture of two or more kinds, and can also be used as a mixture with a zinc compound or another reaction retarder.

The component (E) may be blended when preparing the composition, or may be blended with the composition at the stage of forming the coating film. May be blended at both stages. The amount of the component (E) used is
In the case other than the organometallic compound or the like, the amount is usually 0 to 100 parts by weight of the organosilane (1) in the component (A).
To 100 parts by weight, preferably 0.01 to 80 parts by weight,
More preferably 0.1 to 50 parts by weight, and in the case of an organometallic compound or the like, usually 0 to 100 parts by weight, preferably 100 parts by weight based on 100 parts by weight of the organosilane (1) in the component (A). 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight. In this case, when the use amount of the component (E) exceeds 100 parts by weight, the storage stability of the composition tends to decrease, and the coating film tends to crack.

Component (F) The component (F) is represented by the following general formula (6): R ⁹ COCH ₂ COR ¹⁰ (6) wherein R ⁹ and R ¹⁰ are the same as defined above in the organometallic compound (5). Which are the same as R ⁹ and R ^{10 in} each of the general formulas], are selected from the group consisting of β-diketones and β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds At least one type. Such a component (F) is particularly preferably used together when an organometallic compound or the like is used as the component (E).

The component (F) functions as a stability improver for the composition. That is, the component (F) coordinates to a metal atom of the above-mentioned organometallic compound or the like, and the action of promoting the co-condensation reaction of the above-mentioned component (A) and component (B) by the organometallic compound or the like is appropriately controlled. Thus, it is presumed that the composition acts to further improve the storage stability of the obtained composition.

Specific examples of the component (F) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, and sec-butyl acetoacetate. Tert-butyl acetoacetate, 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, salicylaldehyde and the like. Of these, acetylacetone and ethyl acetoacetate are preferred. The component (F) can be used alone or in combination of two or more.

The amount of the component (F) is usually 2 to 1 mole of the organometallic compound in the organometallic compound or the like.
Mol or more, preferably 3 to 20 mol. in this case,
When the amount of the component (F) is less than 2 mol, the effect of improving the storage stability of the obtained composition tends to be insufficient.

(G) Component The (G) component is composed of a powder and / or a sol or a colloid of an inorganic compound, and is blended according to the desired properties of the coating film.

Specific examples of the compound constituting the component (G)
Is SiO_Two, Al_TwoO_Three, AlGaAs, Al (O
H)_Three, Sb_TwoO_Five, Si_ThreeN_Four, Sn-In_TwoO_Three,
Sb-In_TwoO_Three, InGaAlP, MgF, Ce
F_Three, CeO_Two, 3Al_TwoO_Three・ 2SiO_Two, BeO,
SiC, AlN, Fe, Co, Co-FeO_x, CrO
_Two, Fe_FourN, BaTiO_Three, BaO-Al_TwoO_Three-S
iO_Two, Ba ferrite, SmCO_Five, YCO_Five, Ce
CO_Five, PrCO_Five, Sm_TwoCO₁₇, Nd_TwoFe₁₄B,
Al_FourO_Three, SiC, α-Si, SiN_Four, CoO, S
b-SnO_Two, Sb_TwoO _Five, MnO_Two, MnB, Co_Three
O_Four, Co_ThreeB, LiTaO_Three, MgO, MgAl_TwoO
_Four, BeAl_TwoO_Four, ZrSiO_Four, ZnSb, PbT
e, PbS, PbSe, GeSi, FeSi_Two, CrS
i_Two, CoSi_Two, MnSi_1.73, Mg_TwoSi, β-
B, BaC, BP, TiB_Two, ZrB_Two, HfB_Two, R
u_TwoSi_Three, PbTiO_Three, Al_TwoTiO_Five, Zn_TwoS
iO_Four, Zr_TwoSiO_Four, 2MgO_Two-Al_TwoO_Three-5
SiO_Two, Nb_TwoO_Five, Li_TwoO-Al_TwoO_Three-4Si
O_Two, Mg ferrite, Ni ferrite, Ni-Zn ferrite
Ferrite, Li ferrite, Sr ferrite, etc.
Can be These (G) components may be used alone or
A mixture of more than one species can be used.

The component (G) may be in the form of a powder, an aqueous sol or colloid dispersed in water, a polar solvent such as isopropyl alcohol, or a solvent sol or colloid dispersed in a nonpolar solvent such as toluene. There is. 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 being surface-treated to improve the dispersibility.

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

As a method for blending the component (G) into the composition, the component (G) may be added after the preparation of the composition, or may be added during the preparation of the composition, and the component (G) is added to the composition (A). The components may be co-hydrolyzed / condensed with the component (B).

Component (G) is used in an amount of usually 0 to 500 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of organosilane (1) in component (A).
４００400 parts by weight.

Other Additives In the composition of the present invention, a filler may be separately added and dispersed for the purpose of coloring the obtained coating film and increasing the thickness of the coating film. Such fillers include, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, such as particulate, fibrous or scaly ceramics, metals or alloys, and oxides and hydroxides of these metals. , 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, and manganese oxide. Iron, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide,
Silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica,
Zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth, manganese green, pigment green, ultramarine blue, navy blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, copper borate, Molybdenum blue, copper sulfide, cobalt purple, mars purple, manganese purple, pigment violet, lead oxide, calcium lead oxide, zinc yellow, lead sulfide, chrome yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge,
Pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate,
Zircon oxide, tungsten white, lead, zinc white, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. Can be mentioned. These fillers can be used alone or in combination of two or more. The amount of the filler used is based on 100 parts by weight of the total solid content of the composition.
Usually, it is 300 parts by weight or less.

Further, a known dehydrating agent such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt,
Dispersants such as polyethylene glycol; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropylcellulose, celluloses such as hydroxypropylmethylcellulose, castor oil derivatives, thickeners such as ferrosilicate; ammonium carbonate,
Inorganic foaming agents such as ammonium bicarbonate, ammonium nitrite, sodium borohydride and calcium azide; azo compounds such as azobisisobutyronitrile; hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine; semicarbazide compounds , A triazole compound, an N-nitroso compound, and the like, and other additives such as a surfactant, a silane coupling agent, a titanium coupling agent, and a dye.

Further, a leveling agent can be blended in order to further improve the coating property of the composition. Among such leveling agents, examples of a fluorine-based leveling agent (trade name; the same applies hereinafter) include BM1000 and BM11 manufactured by BM-CHEMIE.
00; Efka 772, Efka 77 of Efka Chemicals
7; Floren series manufactured by Kyoeisha Chemical Co., Ltd .; FC series manufactured by Sumitomo 3M Co., Ltd .; Fluonal TF series manufactured by Toho Chemical Co., Ltd., and the like. BYK series; Shmegma
nn) Sshmego series; Efka Chemicals Efka30, Efka31, Efka34, Efka3
5, Efka 36, Efka 39, Efka 83, Efka 8
6, Efka 88 and the like. Examples of the ether-based or ester-based leveling agent include Carfinol of Nissin Chemical Industry Co., Ltd .; Emulgen and Homogenol of Kao Corporation.

By incorporating such a leveling agent, the finished appearance of the coating film is improved, and the coating film can be uniformly applied. The amount of leveling agent used is
Preferably 0.01 to 5% by weight, based on the total composition,
More preferably, the content is 0.02 to 3% by weight.

As a method of blending the leveling agent, it may be blended at the time of preparing the composition, or may be blended with the composition at the stage of forming the coating film. It may be blended at both stages of film formation.

In preparing the composition of the present invention,
When the component (E) and the component (F) are not used, the method of mixing the components is not particularly limited, but the components (E) and (F)
When a component is used, preferably, (A) to (F)
After obtaining a mixture from which the component (F) is removed, a method of adding the component (F) to the mixture is adopted.

Specific examples of the method for preparing the composition include the following methods (i) to (iv). (I) organosilane (1) constituting component (A),
A method in which an organic solvent and / or water is added to a mixture comprising the component (B), the component (C) and the component (E) as needed to carry out a hydrolysis / condensation reaction, and then the component (F) is added. . (Ii) organosilane (1) constituting component (A),
(C) A predetermined amount of water is added to a mixture composed of the component and, if necessary, an organic solvent to carry out a hydrolysis / condensation reaction,
Next, a method of adding and mixing the components (B) and (E), further performing a condensation reaction, and then adding the component (F).

(Iii) Hydrolysis / condensation by adding a predetermined amount of water to a mixture of the organosilane (1), the component (C), the component (E) and the required amount of the organic solvent constituting the component (A). A method in which the reaction is carried out, then the component (B) is added and mixed, a condensation reaction is further carried out, and then the component (F) is added. (Iv) A predetermined amount of water is added to a mixture of a part of the organosilane (1) constituting the component (A), the component (B), the component (C), the component (E) and a necessary amount of an organic solvent. To carry out hydrolysis and condensation reactions, and then organosilane (1)
Is added, and after the hydrolysis / condensation reaction is further performed, the component (F) is added.

The composition of the present invention may optionally be prepared by using (v) each component except for the component (C),
After performing any one of the methods (iv) to (iv), it can also be prepared by adding the component (C). In the present invention, components other than the components (A) to (F) can be added at an appropriate stage of preparing the composition.

When the composition of the present invention is applied to a substrate,
Use brush, roll coater, flow coater, centrifugal coater, ultrasonic coater, etc., dip coat,
By a coating method such as flow coating, spraying, a screen process, electrodeposition, and vapor deposition, the thickness is 0.1 to 20 μm in a single coating.
When applied about 2 to 3 times, a coating film having a thickness of about 0.2 to 50 μm can be formed. Then, it is dried at room temperature, or at a temperature of about 30 to 200 ° C for 10 to 60.
By heating and drying for about a minute, a coating film can be formed on various substrates.

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 ceramics such as cement, concrete, ALC, flexible board, mortar, slate, gypsum, ceramics and brick. System materials: phenolic resin, epoxy resin, polyester, polycarbonate, polyethylene,
Plastic molded products such as polypropylene and ABS resin (acrylonitrile-butadiene-styrene resin); polyethylene, polypropylene, polyvinyl alcohol,
Plastic films such as polycarbonate, polyethylene terephthalate, polyurethane, and polyimide,
Examples include wood, paper, and glass. The composition of the present invention is also useful for repainting a deteriorated coating film.

These substrates may be subjected to a surface treatment in advance for the purpose of adjusting the base, improving the adhesion, filling the porous substrate, smoothing, patterning and the like.

Examples of the surface treatment for the metal-based substrate include polishing, degreasing, plating, chromate treatment, flame treatment, and coupling treatment. Examples of the surface treatment for the plastic-based substrate include: Blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and the like can be mentioned. As the surface treatment for the inorganic ceramics-based substrate, for example, Polishing, filling,
Patterning and the like can be mentioned. Examples of the surface treatment for the wood substrate include polishing, filling, and insect repellent treatment. Examples of the surface treatment for the paper substrate include the filling and insect repellent treatment. The surface treatment for the deteriorated coating film includes, for example, kerosene.

The application operation using the composition of the present invention varies depending on the type and condition of the substrate and the application method. For example, in the case of a metal-based substrate, a primer is used if rust prevention is necessary, and in the case of an inorganic ceramic-based substrate, the characteristics of the substrate (surface roughness, impregnation,
Opacity, etc.)
Usually, a primer is used, and also in the case of an organic resin-based substrate, a primer is usually used. In the case of repainting of a deteriorated coating film, a primer is used when the old coating film is significantly deteriorated.

In the case of other substrates, for example, metals, woods, papers, tiles, glass, etc., which do not require rust prevention, a primer may or may not be used depending on the application.

The type of the primer is not particularly limited as long as it has an effect of improving the adhesion between the substrate and the composition, and is selected according to the type of the substrate and the purpose of use. The primers can be used alone or as a mixture of two or more kinds, and may be an enamel containing a coloring component such as a pigment or a clear containing the coloring component.

Examples of the type of primer include 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 silicone emulsion. , Polysiloxane, a composition comprising the component (A) and the component (B) in the present invention, and a composition comprising the component (A), the component (B) and the component (G) in the present invention. it can. In addition, these primers can be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, a glycidyl group, an alkoxysilyl group, an alkylsilyl group, an ether bond, and an ester bond.

On the surface of a coating film formed from the composition of the present invention, for the purpose of further increasing the abrasion resistance and gloss of the coating film, for example, US Pat. No. 3,986,997, A clear layer composed of a siloxane resin-based coating such as a stable dispersion of colloidal silica and a siloxane resin described in U.S. 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 of the present invention (clear, enamel) (b) Substrate / coating material of composition obtained by removing photocatalyst from the composition of the present invention (clear, enamel) / composition of the present invention (clear) Here, the clear is a composition containing no coloring component,
Enamel is a composition that includes a coloring component. In the above cases (a) and (b), the base material may be provided with a primer layer in advance as required, as described above.

[0107]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified.

Various Measurements in Examples and Comparative Examples
The evaluation was performed by the following method. (1) Mw and Mn Measured by gel permeation chromatography (GPC) under the following conditions. Sample: Prepared by dissolving 1 g of organosilane condensate or 0.1 g of silyl group-containing vinyl resin in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA was used. Apparatus: High-temperature, high-speed gel permeation chromatogram (model 150-C ALC / GPC) manufactured by Waters, Inc. Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1cc / min

(2) Storage stability The composition without the addition of a curing accelerator 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 cause gelation, the viscosity was measured using a BM viscometer manufactured by Tokyo Keiki Co., Ltd., and those with a change rate of 20% or less were regarded as "no change". (3) Adhesion Cross-cut test according to JIS K5400
), The tape peel test was performed three times, and the average was used. (4) Hardness Based on pencil hardness according to JIS K5400.

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

(6) Resistance to Organic Chemicals 2 cc of isopropyl alcohol was dropped on the coating film, and after 5 minutes, wiped off with a cloth, and the state of the coating film was visually observed. (7) Moisture Resistance After the test piece was kept under an environment of a temperature of 50 ° C. and a humidity of 95% for 1,000 hours, the test piece was taken out and the state of the coating film was visually observed. (8) Weather Resistance According to JIS K5400, an irradiation test was performed for 3,000 hours with a sunshine weather meter, and the appearance (crack, peeling, etc.) of the coating film was visually observed.

(9) Water resistance After the test piece was immersed in tap water at normal temperature for 60 days, the state of the coating film was visually observed. (10) Warm Water Resistance A test piece using an inorganic base material was immersed in warm water at 60 ° C. for 14 days, and the state of the coating film was visually observed.

(11) Stain resistance Carbon black / kerosene = 1/2 (weight ratio) on the coating film
Was left at room temperature for 24 hours, washed with water using a sponge, the state of contamination of the coating film was observed, and evaluated according to the following criteria. ；: No contamination △: slightly contaminated X: Contamination is remarkable.

(12) Stain resistance Coal tar was applied on the coating film, allowed to stand at room temperature for 24 hours, wiped off with a cloth, and observed for the contamination state of the coating film.
Evaluation was made according to the following criteria. ○: Removal of contamination by wiping. Δ: Pollution removed by washing with water. X: Contamination remains even after washing with water.

(13) Stain resistance After the coating film was left outdoors at a 45 ° angle toward the southwest for 6 months, the color difference from the initial state was measured and evaluated according to the following criteria. ；: Color difference less than 1 △: Color difference 1 or more and less than 3 ×: Color difference 3 or more

(14) Transparency Each composition was applied on quartz glass so as to have a dry film thickness of 10 μm, and the transmittance of visible light was measured, and evaluated according to the following criteria. A: The transmittance exceeds 80%. ；: Transmittance is 60 to 80% △: transmittance is less than 60%

REFERENCE EXAMPLE 1 [Polymerization of Component (B)] After a stainless steel autoclave equipped with an electromagnetic stirrer was sufficiently replaced with nitrogen gas, 150 parts of methyl isobutyl ketone, 86 parts of ethyl vinyl ether and peroxide in the autoclave were added. Lauroyl (radical polymerization initiator)
After charging 1.5 parts and cooling the solution in the autoclave to -50 ° C with dry ice-methanol,
Oxygen in the system was removed again with nitrogen gas. Then
Hexafluoropropylene 2 parts, perfluoro (propyl vinyl ether) 2 parts, vinyltrimethoxysilane 1
0 parts were added and the temperature was raised. When the temperature in the autoclave reached 60 ° C., the pressure in the autoclave was 5 kgf / cm ² . The temperature of the reaction system is 60 ° C
, The polymerization reaction was continued for 20 hours, and the pressure in the autoclave was 1.5 kgf /
At the time of drop to cm ² , the reaction was stopped by water cooling to obtain a silyl group-containing fluoropolymer (B-1) having a solid content of 40%.

Reference Examples 2 to 3 [Polymerization of Component (B)] Except that the monomer components shown in Table 1 were used, the procedures of (B-2) to (B-3) were repeated in the same manner as in Reference Example 1. (B) component was obtained.

Reference Example 4 (Synthesis of acrylic polymer) In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of γ-methacryloxypropyltrimethoxysilane, and acrylic acid 5 parts, 2-hydroxyethyl methacrylate 13
Part, 1,1,1-trimethylamine methacrylimide 2
And 150 parts of i-propyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed, and the mixture was heated to 80 ° C. with stirring, and 4 parts of azobisisovaleronitrile was dissolved in 10 parts of xylene in this mixture. After the solution was added dropwise over 30 minutes, the mixture was reacted at 80 ° C. for 5 hours to obtain an acrylic polymer solution having a solid content of 40% (hereinafter referred to as “(b-1)”).

Reference Example 5 (Preparation of primer) The component (b-1) obtained in Reference Example 4 was added to zinc oxide ZS-
303 (manufactured by Sumitomo Osaka Cement Co.) was added at 10% to the solid content of the component (b-1) to obtain a primer solution having a solid content of 38% (hereinafter referred to as "(b-1 ')"). .

Reference Example 6 (Preparation of primer) In a reactor equipped with a stirrer and a reflux condenser, 100 parts of methyltrimethoxysilane and 50 parts of dimethyldimethoxysilane were added.
And a solution prepared by dissolving 50 parts of the component (b-1) obtained in Reference Example 4 and 25 parts of di-i-propoxyethyl acetoacetate aluminum in 50 parts of i-propyl alcohol, and then adding ion-exchanged water. Add 40 parts, 60 ° C
For 4 hours. Then, after the reaction solution was cooled to room temperature, 30 parts of acetylacetone was added thereto, and a primer was added.
A solution (hereinafter, referred to as “(b-2)”) was obtained.

Reference Example 7 (Preparation of Primer) The component (b-2) obtained in Reference Example 6 was added to zinc oxide ZS-
303 (manufactured by Sumitomo Osaka Cement Co.) was added at 10% to the solid content of component (b-2) to obtain a primer solution having a solid content concentration of 20% (hereinafter referred to as "(b-2 ')"). .

Examples 1 to 9 Tables 2 and 3 were placed in a reactor equipped with a reflux condenser and a stirrer.
(A), (B), (C), (D) and (E) were mixed and reacted at 60 ° C. for 4 hours. Next, the component (F) was added to obtain a composition of the present invention having a solid content of 30%. To 100 parts of the obtained composition, 10 parts of a 10% solution of i-propyl alcohol as a curing agent composed of dibutyltin diacetate / alkoxysilane condensate was added, and an alkali-degreased aluminum plate (JIS H
4000, A1050P) by a spray method so as to have a dry film thickness of 1 μm, and dried by heating at 150 ° C. for 10 minutes to produce test pieces, and various evaluations were made. The evaluation results of the storage stability of the composition and various evaluation results of the test pieces,
The results are shown in Tables 4 and 5, respectively.

Example 10 Various primers shown in Table 6 were applied to various substrates shown in Table 6 and dried, and the composition used in Example 1 was applied and dried on the obtained coating film. Thus, a coating film was formed. The obtained test pieces were evaluated for adhesion and weather resistance. The results are shown in Table 6.

[0125]

[Table 1]

[0126]

[Table 2]

[0127]

[Table 3]

[0128]

[Table 4]

[0129]

[Table 5]

[0130]

[Table 6]

[0131]

Since the composition of the present invention contains a specific organosilane component and a fluoropolymer having a silyl group and a photocatalyst, it has excellent weather resistance, storage stability, adhesion, and alkali resistance. In addition, it is possible to form a coating film having excellent hardness, organic chemical resistance, moisture resistance, (warm) water resistance, stain resistance and the like, and high hardness.

Continuation of the front page F term (reference) 4J038 CD092 CD102 CD112 CD122 CD132 CE052 CL002 DL021 DL031 DL051 GA03 GA15 JC32 KA04

Claims (1)

[Claims] (A) The following general formula (1):¹)_nSi (OR^Two)_4-n ... (1) (where R¹Are the same or different when there are two
Represents a monovalent organic group having 1 to 8 carbon atoms;^TwoAre the same
Or different, an alkyl group having 1 to 5 carbon atoms or carbon number
Represents an acyl group of 1 to 6, and n is an integer of 0 to 2. )
An organosilane represented by the formula:
Selected from the group consisting of decomposed products and condensates of the organosilane
(B) (b-1) a structural unit represented by the following general formula (2)
and (Where R^Three~ R^FiveIs C_mY_{2m + 1}, M = an integer from 0 to 5,
Y is independently selected from F, H and Cl
You. (B-2) Structural unit represented by the following general formula (3)Wherein Rf is an alkyl group containing a fluorine atom or
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R of the general formula (2) ^Three~ R
^FiveAnd may be different. And a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group.
Copolymer containing a silyl group having a dimer, and (C) light
Composition for coating characterized by containing a catalyst
object.