JP2001049181A - Coating composition for sanitary ware and sanitary ware - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To contain a specific organosilane component and a fluoropolymer having a silyl group, have excellent storage stability, and have excellent adhesion, alkali resistance, organic chemical resistance, weather resistance, and moisture resistance. ,
An object of the present invention is to provide a coating composition for sanitary ware having excellent water repellency and oil repellency and an antifouling function without reducing (warm) water resistance or the like. SOLUTION: (a) at least one selected from the group consisting of an organosilane represented by (R ¹ ) _n Si (OR ² ) _4-n , a hydrolyzate of the organosilane and a condensate of the organosilane; And (b) a hydrolyzable group and / or
Alternatively, a coating composition for sanitary ware, comprising a fluoropolymer having a silyl group having a silicon atom bonded to a hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to water repellency and oil repellency.
Coatings for sanitary ware with excellent antifouling function
For products, specifically, fluorine-based polymerization having a silyl group
Body-containing organosilane-based sanitary ware coating
Composition. [0002] 2. Description of the Related Art Organosilane coating materials are resistant to
Maintenance-free with excellent weather (light) and stain resistance
Technical development is progressing as a coating material. This
For organosilane coating materials such as
Performance has become increasingly severe, and in recent years,
Appearance, adhesion, weather resistance, heat resistance, alkali resistance, organic chemicals
Product properties, moisture resistance, (hot) water resistance, insulation resistance, abrasion resistance, resistance
Because it forms a coating film with excellent hardness and excellent hardness,
There is a need for a coating material that can cut. [0003] In particular, in order to improve the stain resistance, a coating film is required.
Although it has been recognized that it is better to make the surface hydrophilic,
This is done for the purpose of improving contamination recovery (cleanability).
Process, and the ability to recover the contamination with respect to the amount of contaminants
Only when it exceeds, the effect of stain resistance can be obtained. to this
On the other hand, according to the method of imparting water and oil repellency to the coating film,
Regardless of whether the dye is hydrophilic or lipophilic,
Adhesion to the film can be reduced. Conventionally, to coating
Of water and oil repellency of
However, such a method is not
Therefore, it is difficult to maintain stain resistance. Also light
Catalyst TiO_TwoIn a place without water or light
In this case, the antifouling effect cannot be obtained. On the other hand, organosilane-based coating materials
Coating composition that meets the required performance to some extent
As a partial condensate of organosilane, colloidal silica
Formulated with mosquito dispersion and silicone-modified acrylic resin
Composition (JP-A-60-135465), Olga
Clean of zirconium alkoxide, condensate of silane
Compounds and hydrolyzable silyl group-containing vinyl resins
The compounded composition (JP-A-64-1769),
Condensates of ganosilane, colloidal alumina and water content
Composition containing degradable silyl group-containing vinyl resin (US
Patent No. 4,904,721) has been proposed.
I have. However, Japanese Patent Application Laid-Open No. Sho 60-1354 discloses
No. 65 and US Pat. No. 4,904,721
Coatings obtained from the compositions described in
There is a disadvantage that the gloss is reduced by the ultraviolet irradiation.
Further, it is described in the above-mentioned JP-A-64-1769.
Compositions have poor storage stability and have low solids concentrations.
There is a problem that it is easy to gel in a short time if it is set high.
You. Further, the applicant of the present application has already
Orchid hydrolyzate and / or partial condensate thereof,
Has a silicon atom bonded to a decomposable and / or hydroxyl group
Vinyl resin having a silyl group, metal chelate compound
And β-diketones and / or β-ketoe
Coating composition containing swells
345877). This composition is:
The above requirements for organosilane coating materials
Excellent balance of coating performance, but new performance
In addition, new materials with water repellency, oil repellency, slipperiness, etc.
Is strongly required. On the other hand, Japanese Patent Application Laid-Open No. 8-267646 discloses
Has an inorganic hydrophilic substance and a photocatalytic function on the surface of the substrate.
Antifouling member formed with a layer of a hydrophilic substance
Japanese Patent Application Laid-Open No. 9-207263 discloses a sanitary
A thin film of photocatalytic particles or light on the surface of a methacrylic resin plate
Sanitary meta on which a thin film containing catalyst particles is formed
Krill resin plates have been proposed. However, this
All of these technologies utilize the superhydrophilicity of photocatalysts.
The amount of contaminants deposited in the presence of light and water
Only when the pollution recovery performance exceeds the
Fruit is obtained. In addition, a hydrophilic coating using a photocatalyst
And in places without light, the antifouling effect does not appear. Also,
JP-A-9-228073 discloses a water-repellent coating on the surface.
In the water-repellent member having the water-repellent coating formed thereon,
As a layer containing photocatalyst particles and electron trapping metal
Water repellent members have been proposed. However, this
In this technology, the water-repellent coating is deteriorated by the photocatalyst of the underlayer.
Polytet used for water-repellent coatings
Lafluoroethylene is difficult or expensive
It has some disadvantages. [0008] SUMMARY OF THE INVENTION The present invention relates to a specific
It contains a fluorinated polymer having a silyl group and a ganosilane component.
Has excellent storage stability, adhesion, alkali resistance,
Low resistance to organic chemicals, weather, moisture, (temperature) and water
Anti-fouling machine with excellent water and oil repellency without lowering
To provide a coating composition for sanitary ware having a function.
And there. [0009] The present invention provides (I) (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, and (B) (b-1) a structural unit represented by the following general formula (2)
(Hereinafter also referred to as “(b-1) constituent unit”), (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. ) And / or (B-2) a structural unit represented by the following general formula (3)
(Also referred to as “(b-2) constituent unit”) [In the formula, Rf represents an alkyl group containing a fluorine atom or an alkyl group.
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R in general formula (2) ^Three~ R
^FiveAnd may be different. ] And hydrolyzable
Having a silicon atom bonded to a group and / or a hydroxyl group
Polymers containing a silyl group (hereinafter referred to as “silyl group-containing fluorine-based polymer”
At least one member selected from the group of
Coating composition for sanitary ware characterized by having
(Hereinafter also referred to as “composition (I)”).
You. In addition, the present invention provides a sanitary ware
Of sanitary ware with a coating composed of a coating composition
Is what you do. Further, the present invention provides the following (i) or
(Ii) having a coating film comprising the composition, and further comprising:
A coating film comprising the coating composition for sanitary ware according to 1 above
Providing sanitary ware characterized by having
You. (I) Coating composition containing component (a) above
(Hereinafter also referred to as “composition (i)”). (Ii) component (a), and (b ′) a hydrolyzable group
And / or silicon compounds having a silicon atom bonded to a hydroxyl group.
Polymers containing a silyl group (hereinafter "silyl group-containing polymers")
(Hereinafter referred to as “composition”).
Object (ii) ”). [0010] BEST MODE FOR CARRYING OUT THE INVENTIONCoating composition for sanitary ware (A) component; Formulated in the coating composition of the present invention
The component (a) is an organosilic represented by the above general formula (1).
Orchid (hereinafter also referred to as "organosilane (1)")
Hydrolyzate of ganosilane (1) and organosilane
It is at least one selected from the condensates of (1).
That is, component (a) is only one of these three types.
Or a mixture of any two types, and 3
It may be a mixture containing all types. Where
The hydrolyzate of the organosilane (1) is
OR containing 2 to 4 pieces in (1)^TwoAll groups are hydrolyzed
Need not be, for example, only one
One, two or more of which are hydrolyzed,
Or a mixture thereof. In addition,
The condensate of the organosilane (1) is
The silanol groups of the hydrolyzate condense to form Si-O-Si bonds.
In the present invention, a silanol group is formed.
Need not all be condensed, and only a small
Condensed or different degrees of condensation
And the like. In the general formula (1), R¹Has 1 to 1 carbon atoms
Examples of the monovalent organic group of 8 include a methyl group and an ethyl group
Group, n-propyl group, i-propyl group, n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Hexyl group, n-heptyl group, n-octyl group, 2-E
Alkyl group such as tylhexyl group, acetyl group,
Onyl, butyryl, valeryl, benzoyl,
Acyl groups such as lioil group, vinyl group, allyl group,
Rohexyl, phenyl, glycidyl, (meth) a
Kuryloxy group, ureide group, amide group, fluoroal
Kill group, fluoroacetamide group, isocyanate group
Other than these, there may be mentioned substituted derivatives of these groups.
it can. R¹As a substituent in substituted derivatives of
Is, for example, a halogen atom, a substituted or unsubstituted
Group, hydroxyl group, mercapto group, isocyanato group, glycine
Doxyl group, 3,4-epoxycyclohexyl group,
TA) acryloxyl group, ureide group, ammonium base
And the like. However, these substitution induction
R consisting of body¹The carbon number of includes the carbon atom in the substituent
Is 8 or less. In the general formula (1), R¹There are two
May be the same or different from each other. Further, R^TwoAnd an alkyl group having 1 to 5 carbon atoms
For example, for example, methyl group, ethyl group, n-propyl
Group, i-propyl group, n-butyl group, sec-butyl
Group, t-butyl group, n-pentyl group and the like.
As an acyl group having 1 to 6 carbon atoms, for example,
Tyl, propionyl, butyryl, valeryl,
Proyl groups and the like can be mentioned. In general formula (1)
Multiple R^TwoMay be the same or different from each other
No. Specific examples of such an organosilane (1)
As tetramethoxysilane, tetraethoxysila
, Tetra-n-propoxysilane, tetra-i-pro
Tet such as oxysilane and tetra-n-butoxysilane
Laalkoxysilanes; methyltrimethoxysilane,
Tiltriethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, n-propyltrimethoxy
Silane, n-propyltriethoxysilane, i-propyl
Rutrimethoxysilane, i-propyltriethoxysila
N-butyltrimethoxysilane, n-butyltrie
Toxisilane, n-pentyltrimethoxysilane, n-
Hexyltrimethoxysilane, n-heptyltrimethoxy
Sisilane, n-octyltrimethoxysilane, vinyl
Limethoxysilane, vinyltriethoxysilane, cyclo
Hexyltrimethoxysilane, cyclohexyltriet
Xysilane, phenyltrimethoxysilane, phenylt
Liethoxysilane, 3-chloropropyltrimethoxysi
Orchid, 3-chloropropyltriethoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane,
3,3,3-trifluoropropyltriethoxysila
, Nonafluorohexyltrimethoxysilane, hepta
Decafluorodecyltrimethoxysilane, tridecaful
Orooctyltrimethoxysilane, 3-aminopropyl
Trimethoxysilane, 3-aminopropyltriethoxy
Silane, 2-hydroxyethyltrimethoxysilane, 2
-Hydroxyethyltriethoxysilane, 2-hydroxy
Cypropyltrimethoxysilane, 2-hydroxypropyl
Lutriethoxysilane, 3-hydroxypropyl trime
Toxisilane, 3-hydroxypropyltriethoxy
Orchid, 3-mercaptopropyltrimethoxysilane, 3
-Mercaptopropyltriethoxysilane, 3-isocyanate
Anatopropyltrimethoxysilane, 3-isocyana
Propyltriethoxysilane, 3-glycidoxyp
Ropirtrimethoxysilane, 3-glycidoxypropyl
Triethoxysilane, 2- (3,4-epoxycyclo
Xyl) ethyltrimethoxysilane, 2- (3,4-E)
Poxycyclohexyl) ethyltriethoxysilane, 3
-(Meth) acryloxypropyltrimethoxysila
, 3- (meth) attacryloxypropyltriethoxy
Silane, 3-ureidopropyltrimethoxysilane,
Tria such as 3-ureidopropyltriethoxysilane
Lucoxysilanes; dimethyldimethoxysilane, dimethyl
Ludiethoxysilane, diethyldimethoxysilane, die
Tildiethoxysilane, di-n-propyldimethoxy
Orchid, di-n-propyldiethoxysilane, di-i-propyl
Ropirdimethoxysilane, di-i-propyldiethoxy
Silane, di-n-butyldimethoxysilane, di-n-butyl
Tildiethoxysilane, di-n-pentyldimethoxysi
Orchid, di-n-pentyldiethoxysilane, di-n-f
Xyldimethoxysilane, di-n-hexyldiethoxy
Silane, di-n-heptyldimethoxysilane, di-n-
Heptyldiethoxysilane, di-n-octyldimethoxy
Sisilane, di-n-octyldiethoxysilane, di-n
-Cyclohexyldimethoxysilane, di-n-cyclohexane
Xyldiethoxysilane, diphenyldimethoxysila
, Diphenyldiethoxysilane, heptadecafluoro
Dialkoxysila such as decylmethyldimethoxysilane
Methyl acetyloxysilane, dimethyl
And rudiacetyloxysilane. Of these, trialkoxysilanes,
Dialkoxysilanes are preferred, and trialkoxy
Examples of silanes include methyltrimethoxysilane, methyl
Lutriethoxysilane is preferred, and dialkoxy
Examples of silanes include dimethyldimethoxysilane,
Tildiethoxysilane is preferred. In the present invention, the organosilane (1) and
In particular, only trialkoxysilane only, or
Trialkoxysilane 40-95 mol% and dialkoxy
The combination with 60 to 5 mol% of silane is preferred. Zia
Using alkoxysilane with trialkoxysilane
Softens the resulting coating and improves alkali resistance
Can be done. The organosilane (1) is intact
Or used as a hydrolyzate and / or condensate
You. Hydrolyzate and / or organosilane (1)
When used as a condensate, hydrolyze and condense in advance.
Can be used as component (a), but will be described later.
And mix the organosilane (1) with the rest of the components
When preparing the composition, add an appropriate amount of water.
The organosilane (1) is hydrolyzed and condensed,
It is preferable to use the component (a). (A) Component is a condensate
When used as polystyrene equivalent weight of the condensate
The weight average molecular weight (hereinafter also referred to as “Mw”) is preferably
Is from 800 to 100,000, more preferably 1,
000 to 50,000. In addition, commercially available products of the component (a) include Mitsubishi Chemical Corporation.
MKC silicate manufactured by Co., Ltd.
Like, a silicon cash register manufactured by Dow Corning Toray
Silicon resin manufactured by Toshiba Silicone Co., Ltd., Shin-Etsu
Silicon resin manufactured by Gaku Kogyo Co., Ltd.
Silicon oligomers, etc.
Alternatively, they may be used after condensation. In the present invention, the component (a) is used alone.
Alternatively, two or more kinds can be used as a mixture. [0020](B) a silyl group-containing fluoropolymer;Departure
The component (b) in the above description is composed of the above (b-1) structural unit and
And / or having the structural unit (b-2), and
A silicon atom bonded to a decomposable group and / or a hydroxyl group
Having a silyl group (hereinafter, also referred to as “specific silyl group”)
And preferably has a specific silyl group at the terminal of the polymer molecular chain.
And / or a fluoropolymer having a side chain. This
The component (b) is a coating composition of the present invention.
When the resulting coating film is cured,
The water-decomposable group and / or the hydroxyl group are combined with the component (a).
Providing excellent coating performance by co-condensation
Can be. Content of specific silyl group in component (b)
Is usually 0.1 to 60 mol% in component (b),
Preferably, it is 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, acetoxy
Group, phenoxy group, thioalkoxy group, amino group, etc.
A hydrolyzable group or a hydroxyl group;⁶Is hydrogen atom, charcoal
An alkyl group having 1 to 10 carbon atoms or an ara group having 1 to 10 carbon atoms
Represents an alkyl group, and i is an integer of 1 to 3)
You. The component (b) is represented by the above general formula (2).
(B-1) a monomer that constitutes a structural unit (hereinafter referred to as a monomer)
Below, also referred to as “(b-1) monomer”) and / or
Constituting (b-2) a structural unit represented by the general formula (3)
Monomer (hereinafter also referred to as “(b-2) monomer”)
) And the (b-3) specific system represented by the general formula (4).
A hydrolyzable group and / or a hydroxyl group that constitutes a ril group
(B-3) monomer containing a silicon atom bonded to
And, if necessary, (b-4)
Other monomers copolymerizable with the monomer (hereinafter referred to as “(b-4)
Monomer)).
No. The (b-4) monomer is composed of the (b-1) monomer and the (b)
-2) those having a fluorine atom which is not included in the monomer
There may be. The component (b) is composed of the component (b-1)
Obtained by polymerizing the monomer and / or the monomer (b-2).
Polymer, or these monomers, if necessary,
(B-4) Polymerization obtained by further polymerizing a monomer
The above-mentioned hydrolyzable group or water
A silane compound having a functional group capable of reacting with an acid group (hereinafter referred to as a silane compound)
"(B-5) silane compound").
May be obtained. (B-1) monomer; (b-1) monomer is
It is represented by the following general formula (2) '. (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. ) The above (b-1) monomer includes, for example,
One polymerizable unsaturated double bond and at least one
Compounds having a fluorine atom can be given. (B-1) Specific examples of the monomer include: (A) CF_Two= CF_Two, CHF = CF_Two, CH_Two= CF
_Two, CH_Two= CHF, CCIF = CF_Two, CHCl = C
F_Two, CCl_Two= CF_Two, CCIF = CCLF, CHF
= CCl_Two, CH_Two= CCIF, CCl_Two= CCLF
Any fluoroethylenes; CF_ThreeCF = CF_Two, CF_Three
CF = CHF, CF_ThreeCH = CF_Two, CF_ThreeCF = CH
_Two, CF_ThreeCF = CHF, CHF_TwoCF = CHF, CF
_ThreeCH = CH_Two, CH_ThreeCF = CF_Two, CH_ThreeCH = C
F_Two, CH_ThreeCF = CH_Two, CF_TwoClCF = CF_Two,
CF_ThreeCCl = CF_Two, CF_ThreeCF = CFCl, CF_Two
ClCCl = CF_Two, CF_TwoClCF = CFCl, CF
_TwoCCl = CCIF, CF_TwoCCl = CCl_Two, CCl
_ThreeCF = CF_Two, CF_TwoClCCl = CCl_Two, CFC
l_TwoCCl = CCl_Two, CF_ThreeCF = CHCl, CCl
F_TwoCF = CHCl, CF_ThreeCCl = CHCl, CHF
_TwoCCl = CCl_Two, CF_TwoClCH = CCl_Two, CF
_TwoClCCl = CHCl, CCl_ThreeCF = CHCl etc.
Fluoropropenes; (B) CF_ThreeCF_TwoCF = CF_Two, CF_ThreeCF = CFC
F_Three, CF_ThreeCH = CFCF_Three, CF_Two= CFCF_TwoC
HF_Two, CF_ThreeCF_TwoCF = CH_Two, CF_TwoCH = CH
CF_Three, CF_Two= CFCF_TwoCH_Three, CF_Two= CFCH
_TwoCH_Three, CF _ThreeCH_TwoCH = CH_Two, CF_ThreeCH = C
HCH_Three, CF_Two= CHCH_TwoCH_Three, CH_ThreeCF_TwoC
H = CH_Two, CFH_TwoCH = CHCFH_Two, CH_ThreeCF
_TwoCH = CH_Two, CH_Two= CFCH_TwoCH_Three, CF
_Three(CF_Two)_TwoCF = CF_Two, CF_Three(CF_Two)_TwoCF
= CF_TwoSuch as fluoroolefins having 4 or more carbon atoms
And so on. (B-1) containing these fluorine atoms
Monomers may be used alone or in combination of two or more.
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 containing a fluorine atom or an alkyl group.
A oxyalkyl group;^Three~ R^FiveIs the general formula
(2) ′, and within the same meaning, within the general formula (2)
R^Three~ R^FiveAnd may be different. ] As the monomer (b-2), for example,
One polymerizable unsaturated double bond, one ether bond and
List compounds having at least one fluorine atom
Can be. (B-2) Specific examples of the monomer include: (A) CH_TwoＣＨCH—O—Rf (Rf represents a fluorine atom
Including alkyl or alkoxyalkyl groups)
(Fluoroalkyl) vinyl ether represented by
Is (fluoroalkoxyalkyl) vinyl ether
Kind; (B) Perfluoro (methyl vinyl ether), perf
Luoro (ethyl vinyl ether), perfluoro (pro
Pill vinyl ether), perfluoro (butyl vinyl ether)
-Tel), perfluoro (isobutyl vinyl ether)
Perfluoro (alkyl vinyl ether) s such as; (C) Perfluoro (propoxypropyl vinyl ether)
Perfluoro (alkoxyalkyl vinyl ether)
-Tel); and the like. These foots
The (b-2) monomer containing an elemental atom is one kind alone
Alternatively, two or more kinds may be used in combination. The (b-1) monomer and the (b-2) monomer
When using a combination of
-Fluoroalkyl perfluorovinyl ether or
Perfluoroalkoxyalkyl perfluorovinyl ester
It is preferable to use them in combination with a telomer. (B-3) monomer; (b-3) monomer is
Polymerizable unsaturated double bond in one molecule and hydrolysis
Contains a silicon atom bonded to a functional group and / or a hydroxyl group
Monomer. Examples of the monomer (b-3) include:
For example, the following general formula (4) ' [X, R in the formula⁶, I are the values in the general formula (4).
X, R respectively⁶, I, R⁷Is a polymerizable double
Represents an organic group having a bond]
(Hereinafter also referred to as “unsaturated silane compound”) and the like.
be able to. Specific examples of the above unsaturated silane compounds
Is CH_Two= CHSi (CH_Three) (OCH_Three)_Two, CH
_Two= CHSi (OCH_Three)_Three, CH_Two= CHSi (OC
_TwoH_Five)_Three, CH_Two= CHSi (CH_Three) Cl_Two, CH
_Two= CHSiCl_Three, CH_Two= CHCOO (CH_Two)_Two
Si (CH_Three) (OCH_Three)_Two, CH_Two= CHCOO
(CH_Two)_TwoSi (OCH_Three)_Three, CH_Two= CHCOO
(CH_Two)_ThreeSi (CH_Three) (OCH_Three)_Two, CH_Two=
CHCOO (CH_Two)_ThreeSi (OCH_Three)_Three, CH_Two=
CHCOO (CH_Two)_TwoSi (CH_Three) Cl_Two, CH_Two
= CHCOO (CH_Two)_TwoSiCl_Three, CH_Two= CHC
OO (CH_Two)_ThreeSi (CH_Three) Cl_Two, CH_Two= CH
COO (CH_Two)_ThreeSiCl_Three, CH_Two= C (CH_Three)
COO (CH_Two)_TwoSi (CH_Three) (OCH_Three)_Two, C
H_Two= C (CH_Three) COO (CH_Two)_TwoSi (OC
H_Three)_Three, CH_Two= C (CH_Three) COO (CH_Two)_ThreeS
i (CH_Three) (OCH_Three)_Two, CH_Two= C (CH_Three) C
OO (CH_Two)_ThreeSi (OCH_Three)_Three, CH_Two= C (C
H_Three) COO (CH_Two)_TwoSi (CH_Three) Cl_Two, CH
_Two= C (CH_Three) COO (CH_Two)_TwoSiCl_Three, CH
_Two= C (CH_Three) COO (CH_Two)_ThreeSi (CH_Three) C
l_Two, CH_Two= C (CH_Three) COO (CH_Two)_ThreeSiC
l_Three, [0032] Embedded image Embedded image Embedded image Embedded image And the like. These are 1
Can be used alone or in combination of two or more
You. (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
Chill (meth) acrylate, i-butyl (meth) acryl
Rate, amyl (meth) acrylate, i-amyl (meth)
(T) acrylate, hexyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, n-octyl
(Meth) acrylate, cyclohexyl methacrylate
Alkyl (meth) acrylate having 4 to 12 carbon atoms such as
Kind; (B) Styrene, α-methylstyrene, 4-methylstyrene
Len, 2-methylstyrene, 3-methylstyrene, 4-
Methoxystyrene, 2-hydroxymethylstyrene, 4
-Ethylstyrene, 4-ethoxystyrene, 3,4-di
Methylstyrene, 3,4-diethylstyrene, 2-chloro
Rostyrene, 3-chlorostyrene, 4-chloro-3-meth
Butyl styrene, 4-t-butyl styrene, 2,4-dic
Lorostyrene, 2,6-dichlorostyrene, 1-vinyl
Aromatic vinyl monomers such as naphthalene; (C) Hydroxymethyl (meth) acryle
Acid, hydroxyethyl (meth) acrylate, hydro
Xypropyl (meth) acrylate, hydroxybutyl
(Meth) acrylate, hydroxyamyl (meth) ac
Related to hydroxyhexyl (meth) acrylate
Any hydroxyalkyl (meth) acrylate; allyl
Glycidyl ether, glycidyl (meta) acrylate
Epo such as methyl glycidyl (meth) acrylate
Xy compound; (D) Divinylbenzene, ethylene glyco
Rudi (meth) acrylate, diethylene glycol di
(Meth) acrylate, triethylene glycol di
Acrylate, tetraethylene glycol di (meth)
TA) acrylate, propylene glycol di (meth) a
Acrylate, dipropylene glycol di (meth) acryl
Rate, tripropylene glycol di (meth) acryle
, Tetrapropylene glycol di (meth) acrylic
Rate, butanediol di (meth) acrylate, hex
Sundiol di (meth) acrylate, trimethylol
Propane tri (meth) acrylate, pentaerythritol
Multifunctional monomer such as oletetra (meth) acrylate
body; (E) (meth) acrylamide, N-methyl
Roll (meth) acrylamide, N-methoxymethyl
(Meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N, N'-methylenebisacrylamido
, Diacetone acrylamide, maleic amide,
Acid amide compounds such as maleimide; (F) Vinyl chloride, vinylidene chloride, fatty acid vinyl S
Vinyl compounds such as ter; (G) 1,3-butadiene, 2-methyl-1,3-buta
Diene, 2,3-dimethyl-1,3-butadiene, 2-
Neopentyl-1,3-butadiene, 2-chloro-1,
3-butadiene, 2-cyano-1,3-butadiene, i
Soprene, alkyl group, halogen atom, cyano group, etc.
Substituted linear conjugated pentadienes substituted with a substituent, linear
Conjugated hexadiene such as linear and side chain conjugated hexadiene
En; (H) (meth) acrylic acid, fumaric acid, itaconic acid,
Noalkyl itaconic acid, maleic acid, crotonic acid, 2-
(Meth) acryloyloxyethylhexahydrophthale
Ethylenically unsaturated carboxylic acids such as acids; (I) acrylonitrile, methacrylonitrile
Vinyl cyanide compounds such as tolyl; (Nu) 4- (meth) acryloyloxy-2,2,6
6-tetramethylpiperidine, 4- (meth) acryloyl
Ruamino-2,2,6,6-tetramethylpiperidine,
4- (meth) acryloyloxy-1,2,2,6,6
-Piperidine monomers such as pentamethylpiperidine
ー ； (R) vinyl glycidyl ether, 2-h
Droxyethyl vinyl ether, 3-hydroxypropyl
Vinyl ether, 2-hydroxypropyl vinyl A
Ter, 4-hydroxybutyl vinyl ether, 3-hydr
Roxybutyl vinyl ether, 5-hydroxypentyl
Vinyl ether, 6-hydroxyhexyl vinyl ether
Vinyl ethers such as (ヲ) Allyl glycidyl ether, 2-h
Droxyethyl allyl ether, 4-hydroxybutyl
Allyl ether, glycerol monoallyl ether, etc.
Allyl ethers of (W) methyl vinyl ether, ethyl vinyl ether,
n-propyl vinyl ether, isopropyl vinyl A
Ter, n-butyl vinyl ether, isobutyl vinyl ether
-Tel, tert-butyl vinyl ether, n-pliers
Vinyl ether, n-hexyl vinyl ether, n-
Octyl vinyl ether, n-dodecyl vinyl ether
, 2-ethylhexyl vinyl ether, cyclohexyl
Alkyl vinyl ether such as vinyl ether
Is cycloalkyl vinyl ethers; (F) 2,2,2-trifluoroethyl
(Meth) acrylate, 2,2,3,3,3-pentaf
Fluoropropyl (meth) acrylate, 2- (perful
Orobutyl) ethyl (meth) acrylate, 2- (per
Fluorohexyl) ethyl (meth) acrylate, 2-
(Perfluorooctyl) ethyl (meth) aclay
G, 2- (perfluorodecyl) ethyl (meth) acryl
Rate, 1H, 1H, 5H-octafluoropentyl
(Meth) acrylate, 1H, 1H, 2H, 2H-hep
Fluoride such as tadecafluorodecyl (meth) acrylate
(Meth) acrylic acid esters;
And caprolactone. These are one kind alone
Alternatively, two or more kinds can be used in combination. (B-5) silane compound; used for addition reaction
(B-5) The silane compound includes methyl dichlor
Orchid, trichlorosilane, phenyldichlorosilane, etc.
Halogenated silanes: methyldiethoxysilane, methyl
Ludimethoxysilane, phenyldimethoxysilane, tri
Alkoxy such as methoxysilane and triethoxysilane
Silanes: methyl diacetoxy silane, phenyl diacet
Acyloxy such as toxic silane and triacetoxy silane
Silanes: methyldiaminoxysilane, triaminoxy
Aminoxy such as silane and dimethylaminoxysilane
Examples include silanes. These are single types
They can be used alone or in combination of two or more. The polymerization method for producing the component (b) and
For example, the method of adding monomers at once and polymerizing
After polymerizing a part of the monomer, the rest is continuously
Alternatively, a method of intermittent addition, or
And a method of continuously adding them from the beginning of the mixture.
In addition, a polymerization method combining these polymerization methods is adopted.
You can also. Preferred polymerization methods include solution weight
Case. Solvents used for solution polymerization are usually
Can be used, including ketones and alcohol
Are preferred. In this polymerization, polymerization initiator, molecular weight
Use known regulators, chelating agents and inorganic electrolytes.
Can be used. (B) Structural unit constituting component (b-1)
And (b-2) the total content of the structural units is the component (b)
Usually, 0.5 to 80 mol%, preferably 1 to 70 mol%
Mol%. If it is less than 0.5 mol%, water repellency and oil repellency may be reduced.
Good balance of transparency, adhesion, etc.
It may be difficult to obtain a good coating. On the other hand, 80 mol%
If it exceeds, the resulting coating film has poor adhesion to the substrate
It may be. Of these, (b-1)
The amount is preferably 0.5 to 70 moles in the component (b).
%. Further, the content of the (b-2) structural unit is as follows:
In component (b), the content is preferably 0.5 to 70 mol%.
You. Furthermore, the content of the structural unit (b-3) is determined by
The content of the hydroxyl group in the component (b) is usually 0.1 to 60.
Mol%, preferably 0.5 to 50 mol%.
You. If it is less than 0.1 mol%, the effect of co-condensation with the component (a) will
No result. On the other hand, when it exceeds 60 mol%,
Storage stability of coating compositions
You. The other copolymerizable monomer (b-4) was used.
The structural unit [(b-4) structural unit] composed of a monomer is
In the component (b), usually 90 mol% or less, preferably
It is about 80 mol% or less. The Mw of the component (b) is preferably 1,0
00 to 50,000, more preferably 5,000 to
30,000. In the present invention, the component (b) is used alone.
Or a mixture of two or more obtained as described above
can do. The amount of the component (b) used in the present invention is as follows:
(R) in component (a)¹)_nSiO_{(4-n ) / 2}[R¹and
n is the same as in the above formula (1). Hereinafter, the same applies)
20 to 800 weight per 100 weight parts
Parts, preferably 25 to 750 parts by weight, more preferably
Is 50 to 700 parts by weight. In this case, the component (b)
If the amount of used is less than 20 parts by weight, the resulting coating film has a high Al resistance.
There is a tendency that potability and crack resistance are reduced. On the other hand, 8
If it exceeds 00 parts by weight, the weather resistance of the coating film tends to decrease.
is there. In the present invention, together with the component (b),
Containing a specific silyl group without a fluorine atom
Vinyl copolymer (hereinafter also referred to as “(b ′) component”)
May be used in a range that does not impair the effects of the present invention. This
The component (b ') is composed of the monomer (b-3) and the component (b-4)
Copolymerized with a monomer, or (b-4) a monomer
(B-5) silanization to a polymer obtained by polymerizing
It can be obtained by subjecting the compound to an addition reaction. (B ') component
Is usually added to 100 parts by weight of the component (a).
500 parts by weight or less. The composition of the present invention and a primer set described below
The composition is usually prepared by adding water to the
Hydrolysis / condensation reaction of silane (1) or
It is added to disperse the particulate components described below. Departure
The amount of water used in Ming was determined by (R)¹)_nS
iO_{(4-n) / 2}Per mole of the structural unit represented by
Usually 0.5 to 3 mol, preferably about 0.7 to 2 mol
It is. Further, the composition of the present invention and an undercoat
The composition for use mainly includes the component (a) and the components (c) to
(E) The components are uniformly mixed, and the total solid content of the composition is concentrated.
The degree of dispersion and the dispersion and storage stability of the composition
In order to further improve the organic solvent, an organic solvent is used. As such an organic solvent, the above components
Are not particularly limited as long as they can be uniformly mixed,
For example, alcohols, aromatic hydrocarbons, ethers
, Ketones, esters and the like.
Among these organic solvents, specific examples of alcohols
Is methanol, ethanol, n-propyl alcohol
, I-propyl alcohol, n-butyl alcohol,
sec-butyl alcohol, t-butyl alcohol, n
-Hexyl alcohol, n-octyl alcohol, ethyl
Len glycol, diethylene glycol, triethylene
Glycol, ethylene glycol monobutyl ether,
Ethylene glycol monoethyl ether acetate, di
Ethylene glycol monoethyl ether, propylene glycol
Recol monomethyl ether, propylene monomethyl ether
-Tel acetate, diacetone alcohol, etc.
be able to. As specific examples of aromatic hydrocarbons,
Represents benzene, toluene, xylene, etc.
Specific examples of tetrahydrofuran, dioxane
Examples of ketones include acetone and methyl ether.
Tyl ketone, methyl isobutyl ketone, diisobutyl ketone
Examples of esters include ethyl acetate.
Propyl acetate, butyl acetate, propylene carbonate, etc.
Can be mentioned. These organic solvents can be used alone or
Can be used as a mixture of two or more. As described above, the coating composition of the present invention
Excellent antifouling properties due to its water and oil repellency properties
It is possible to provide sanitary ware that is
Provides long-term adhesion and functions such as blocking ultraviolet rays
It is preferable to apply a primer to the surface of the base material for the purpose.
As the undercoating composition for forming the undercoating layer,
Preferred is composition (i) or composition (ii).
And composition (ii) is particularly preferred.
Commonly used. Hereinafter, the composition (i) for undercoating and the composition
(Ii) will be described.Composition (i) The composition (i) for undercoating is, as described above, the above (a)
It contains components and usually an organic solvent. The composition (i) comprises the above-mentioned organosilane
By adding an appropriate amount of water to (1),
It is preferable to hydrolyze and condense the run (1). What
As described above, as the component (a), organosila
Using the hydrolyzate and / or condensate of (1)
You can also. [0056]Composition (ii) The undercoating composition (ii) is, as described above,
And (b ') a silyl group-containing polymer. [0057](B ′) a silyl group-containing polymer;(B ')
The component contains no fluorine atom and has a specific
Ryl groups are preferably added at the end of the polymer molecular chain and / or
Is a polymer having a side chain. In composition (ii):
The component (b ') contains a silyl group when the coating film is cured.
The hydrolyzable groups and / or hydroxyl groups in the above (a)
To provide excellent coating performance
Component. Content of silicon atom in component (b ')
Is usually 0.001 to 20 times the component (b ').
%, Preferably 0.01 to 15% by weight. Preferred
The specific silyl group is a group represented by the general formula (4).
You. (B ') The silyl group-containing polymer is
(B) In the production of a silyl group-containing fluoropolymer,
Without using (b-1) monomer and (b-2) monomer,
(B-4) Fluorine among the above-mentioned monomers as a monomer
Except that at least one monomer not containing is used
It is obtained in the same manner as in the method for producing the component (b). Another example of the component (b ') is as follows.
Constant silyl group-containing epoxy resin, specific silyl group-containing polyether
Steal resin and the like can be mentioned. The above specific silyl
Group-containing epoxy resins include, for example, bisphenol A type
Epoxy resin, bisphenol F type epoxy resin, hydrogenated vinyl
Sphenol A type epoxy resin, aliphatic polyglycidyl
Epoxy such as ether and aliphatic polyglycidyl ester
Amino having a specific silyl group in the epoxy group in the resin
Silanes, vinylsilanes, carboxysilanes, grease
It can be manufactured by reacting
Can be. Further, the specific silyl group-containing polyester
The resin is, for example, the calories contained in the polyester resin.
An amino group having a specific silyl group in the boxyl group or hydroxyl group
Orchids, carboxysilanes, glycidylsilanes, etc.
Can be produced by reacting The Mw of the component (b ') is preferably 2,0
00 to 100,000, more preferably 4,000 to
50,000. The composition (b ′) in the composition (ii)
Amount of (R) in component (a)¹)_nSiO
_{(4-n) / 2}100 parts by weight of the structural unit represented by
Usually 2 to 900 parts by weight, preferably 10 to 800 parts by weight
Parts, more preferably 20 to 700 parts by weight. This
When the amount of the component (b ') is less than 2 parts by weight,
Coating film may have poor alkali resistance.
On the other hand, if it exceeds 900 parts by weight, the long-term weather resistance of the coating film
Tends to decrease. In the present invention, the component (b ') is used alone
Alternatively, a mixture of two or more obtained as described above may be used.
Can be used. In the composition (ii), the above
(B ') component in the presence of water and / or an organic solvent
It is preferable to co-condense with the component (a). The composition
In the product (ii), the type and amount of the component (a)
The description is omitted because it is the same as the coating composition. The coating composition of the present invention and, if necessary,
To compositions (i) to (ii) for undercoating
Respectively further comprises the following components (c) to (e).
Can be combined. The following describes these components.
I will tell. [0063](C) component;The component (c) is a component (a),
The hydrolysis / condensation reaction of the component (b) and the component (b ′)
A catalyst that promotes. By using the component (c)
Increase the curing speed of the resulting coating,
Generated by the polycondensation reaction of the organosilane component
The molecular weight of the polysiloxane resin increases, and the strength and long-term
A coating film with excellent durability etc. can be obtained, and
Thickening and painting work are also easy. The component (c) includes an acid compound
Substances, alkaline compounds, metal salts, amine compounds, organic gold
Genus compound and / or its partial hydrolyzate (hereinafter
Metal compound and / or its partial hydrolyzate
(Also referred to as “organic metal compound”). the above
As the acidic compound, for example, acetic acid, hydrochloric acid, sulfuric acid, phosphorus
Acid, alkyl titanic acid, p-toluenesulfonic acid, lid
And acetic acid.
You. Further, as the alkaline compound, for example, water
Examples include sodium oxide and potassium hydroxide.
And preferably sodium hydroxide. Also,
Examples of the metal salt include naphthenic acid, octylic acid,
Alkali metal salts such as nitric acid, sulfurous acid, aluminate and carbonic acid
And the like. Examples of the above amine compound include, for example,
For example, ethylenediamine, hexamethylenediamine, die
Tylenetriamine, triethylenetetramine, tetraet
Tylenepentamine, piperidine, piperazine, m-fe
Nilendiamine, p-phenylenediamine, ethanol
Amine, triethylamine, 3-aminopropyl tri
Methoxysilane, 3-aminopropyl triethoxy
Orchid, 3- (2-aminoethyl) -aminopropyl
Limethoxysilane, 3- (2-aminoethyl) -amino
Propyl triethoxysilane, 3- (2-aminoethyl
) -Aminopropyl-methyl-dimethoxysilane, 3
-Anilinopropyl trimethoxysilane or alkyl
In addition to amine salts and quaternary ammonium salts, epoxy resin
Examples of various modified amines used as curing agents for fats
Preferably, 3-aminopropyl tri
Methoxysilane, 3-aminopropyl triethoxy
Orchid, 3- (2-aminoethyl) -aminopropyl
Liethoxysilane. Examples of the above-mentioned organometallic compounds include, for example,
For example, a compound represented by the following general formula (5) (hereinafter referred to as “organic
Metal compound (5) ”), bonded to the same tin atom
Having 1 to 2 alkyl groups having 1 to 10 carbon atoms
Organometallic compounds of tin (hereinafter also referred to as "organotin compounds"
) Or partial hydrolysates of these compounds
Can be mentioned. [0067]   M (OR⁸)_p(R⁹COCHCOR^Ten)_q... (5) [Wherein M is zirconium, titanium or aluminum
And R⁸And R⁹Are the same or different
Group, n-propyl group, i-propyl group, n-butyl
Group, sec-butyl group, t-butyl group, n-pentyl
Group, n-hexyl group, cyclohexyl group, phenyl group
Which represents a monovalent hydrocarbon group having 1 to 6 carbon atoms;^TenIs
R⁸And R⁹Monovalent hydrocarbon having 1 to 6 carbon atoms as described above
Group, methoxy group, ethoxy group, n-propoxy group
Group, i-propoxy group, n-butoxy group, sec-butoxy
Xyl group, t-butoxy group, lauryloxy group, stearyl
Represents an alkoxyl group having 1 to 16 carbon atoms such as
And p and q are integers from 0 to 4, and (p + q) = (M
Valence). ] Specific examples of the organometallic compound (5) include: (A) tetra-n-butoxyzirconium, tri-n-
Butoxy ethyl acetoacetate zirconium, di-
n-butoxy bis (ethyl acetoacetate) zircon
And n-butoxy tris (ethyl acetoacetate
G) zirconium, tetrakis (n-propylacetoa)
(Cetate) zirconium, tetrakis (acetylacetoacetate)
Acetate) zirconium, tetrakis (ethylacetoacetate)
Organic zirconium compounds such as acetate and zirconium
object; (B) Tetra-i-propoxytitanium
, Di-i-propoxy bis (ethyl acetoacetate)
G) titanium, di-i-propoxy bis (acetyl)
Acetate) titanium, di-i-propoxy bis
Organo-titanium compounds such as (acetylacetone) titanium
object; (C) Tri-i-propoxy aluminum, di-i-prop
Roxy-ethyl acetoacetate aluminum, di-
aluminum i-propoxy acetylacetonate,
i-Propoxy bis (ethyl acetoacetate) al
Minium, i-propoxy bis (acetylacetona
G) Aluminum, tris (ethyl acetoacetate)
Aluminum, tris (acetylacetonate) aluminum
And monoacetylacetonate bis (ethylacetate)
(Acetate) Aluminum and other organic aluminum
Compound; and the like. These organometallic compounds (5) and their
Of the partial hydrolysates, tri-n-butoxy-ethyl
Zirconium acetate, di-i-propoxybi
(Acetylacetonato) titanium, di-i-pro
Poxy ethyl acetoacetate aluminum, Tris
(Ethyl acetoacetate) aluminum, or
Partial hydrolysates of these compounds are preferred. Further, specific examples of the organotin compound include:
(C_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C
_FourH₉)_TwoSn (OCOCH = CHCOOCH_Three)_Two,
(C_FourH₉)_TwoSn (OCOCH = CHCOOC
_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCOC
₈H₁₇)_Two, (C₈H₁₇)_TwoSn (OCOC
₁₁H_{twenty three})_Two, (C₈H₁₇)_TwoSn (OCOCH = CHC
OOCH_Three)_Two, (C₈H₁₇)_TwoSn (OCOCH = C
HCOOC_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCOC
H = CHCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (O
COCH = CHCOOC₁₆H₃₃)_Two, (C₈H₁₇)_TwoS
n (OCOCH = CHCOOC₁₇H₃₅)_Two, (C
₈H₁₇)_TwoSn (OCOCH = CHCOOC
₁₈H₃₇)_Two, (C₈H₁₇)_TwoSn (OCOCH = CHC
OOC₂₀H₄₁)_Two, [0072] (C_FourH₉) Sn (OCOC)₁₁H_{twenty three})_Three, (C_FourH₉)
Sn (OCONa)_ThreeCarboxylic acid type organotin compounds such as
object; (C_FourH₉)_TwoSn (SCH_TwoCOOC₈
H₁₇)_Two, (C_FourH₉)_TwoSn (SCH_TwoCH_TwoCOO
C₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC
₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCH_TwoCO
OC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOO
C₁₂H_{twenty five})_Two, (C₈H₁₇)_TwoSn (SCH_TwoCH_TwoC
OOC₁₂H_{twenty five})_Two, (C_FourH₉) Sn (SCOCH = C
HCOOC₈H₁₇)_Three, (C₈H₁₇) Sn (SCOCH
= CHCOOC₈H₁₇)_Three, [0074] Mercaptide-type organotin compounds such as; (C_FourH₉)_TwoSn = S, (C₈H₁₇)_Two
Sn = S, Sulfide-type organotin compounds such as; (C_FourH₉) SnCl_Three, (C_FourH₉)_Two
SnCl_Two, (C₈H₁₇)_TwoSnCl_Two,(C)_FourH₉)_TwoS
nO, (C₈H₁₇)_TwoOrganic tin oxides such as SnO
And these organic tin oxide and ethyl silicate,
Dimethyl maleate, diethyl maleate, diphthalic acid
Reaction products with ester compounds such as octyl;
Can be mentioned. The component (c) may be used alone or in combination of two or more.
Can be used in combination with
It can be used in combination with a reaction retarder. The component (c) is added when the composition is prepared.
May be added to the composition at the stage of forming the coating film.
And furthermore, the preparation of the composition and the formation of the coating film
It may be blended at both stages. The amount of the component (c) used is
In the case other than an organometallic compound or the like, (R) in the component (a)
¹)_nSiO_{(4-n) / 2}100 parts by weight of structural unit represented by
To 100 parts by weight, preferably 0.1 to 100 parts by weight,
01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight
Parts, and in the case of an organometallic compound or the like, the component (a)
Inside (R¹)_nSiO_{(4-n) / 2}Structural unit 10 represented by
0 to 100 parts by weight, preferably 0 to 100 parts by weight, preferably
Is from 0.1 to 80 parts by weight, more preferably from 0.5 to
50 parts by weight. In this case, the amount of the component (c) used is 1
If the amount exceeds 00 parts by weight, the storage stability of the composition is lowered.
And the coating film tends to crack. [0079](D) component;The component (d) has the following general formula
(6) R⁹COCH_TwoCOR^Ten      ... (6) [Wherein, R⁹And R^TenIs an organometallic compound (5)
R of each of the above general formulas⁹And R^TenSynonymous with
Β-diketones and β-ketoesters represented by
, Carboxylic acid compounds, dihydroxy compounds, amination
Compounds and oxyaldehyde compounds.
At least one selected. Such a component (d)
Especially, use of an organometallic compound or the like as the component (c).
When used, it is preferable to use them together. The component (d) is used as a stability improver for the composition.
It works. That is, the component (d) is
The organic metal compound by coordinating to a metal atom such as an organic metal compound.
(A) component and (b) component or (b ') component
Moderately controls the action of accelerating the co-condensation reaction with
The storage stability of the resulting composition.
It is presumed to have the effect of increasing the value. As a specific example of the component (d), acetyl
Setone, methyl acetoacetate, ethyl acetoacetate, acetoacetate
N-propyl acetate, i-propyl acetoacetate, acetoacetate
N-butyl acetoacetate, sec-butyl acetoacetate,
T-butyl cetacetate, hexane-2,4-dione,
Butane-2,4-dione, heptane-3,5-dione,
Octane-2,4-dione, nonane-2,4-dione,
5-methylhexane-2,4-dione, malonic acid,
Uric acid, phthalic acid, glycolic acid, salicylic acid, amino vinegar
Acid, iminoacetic acid, ethylenediaminetetraacetic acid, glyco
Catechol, ethylenediamine, 2,2-bipyridi
, 1,10-phenanthroline, diethylenetriamine
, 2-ethanolamine, dimethylglyoxime, di
List thizone, methionine, salicylaldehyde, etc.
be able to. Of these, acetylacetone,
Ethyl toacetate is preferred. (D) component alone or
Two or more kinds can be used as a mixture. The amount of the component (d) used depends on the amount of the organometallic compound.
2 moles per mole of the organometallic compound
Mol or more, preferably 3 to 20 mol. in this case,
When the amount of the component (e) is less than 2 mol, the composition obtained is
Tend to have insufficient effect of improving the storage stability. [0083](E) component;Component (e) is an inorganic compound
Powder and / or sol or colloid
Formulated according to the desired properties of the membrane. Specific examples of the compound constituting the component (e)
Is SiO_Two, Al_TwoO_Three, AlGaAs, Al (O
H)_Three, Sb_TwoO_Five, Si_ThreeN_Four, SnO_Two, Sn-I
n_TwoO_Three, In_TwoO_Three, Sb-In_TwoO_Three, InP, I
nSb, InAs, InGaAlP, MgF, Ce
F_Three, CeO_Two, 3Al_TwoO_Three・ 2SiO_Two, BeO,
SiC, AlN, Fe, Fe_TwoO_Three, Co, Co-Fe
O_x, CrO_Two, Fe_FourN, BaTiO_Three, BaO-A
l_TwoO_Three-SiO_Two, Ba ferrite, SmCO_Five, Y
CO_Five, CeCO_Five, PrCO_Five, Sm_TwoCO₁₇, Nd
_TwoFe₁₄B, ZrO_Two, Al_FourO_Three, AlN, SiC,
α-Si, SiN_Four, CoO, Sb-SnO_Two, MnO
_Two, MnB, Co_ThreeO_Four, Co_ThreeB, LiTaO_Three, M
gO, MgAl_TwoO_Four, BeAl_TwoO_Four, ZrSi
O_Four, ZnO, ZnS, ZnSe, ZnSb, ZnT
e, PbTe, PbS, PbSe, GeSi, FeSi
_Two, CrSi_Two, CoSi_Two, MnSi_1.73, Mg_TwoS
i, β-B, BaC, BP, TiB_Two, ZrB_Two, Hf
B_Two, Ru_TwoSi_Three, RuO_Two, TiO_Two, TiO_Three,
SrTiO _Three, FeTiO_Three, PbTiO_Three, Al_TwoT
iO_Five, Zn_TwoSiO_Four, Zr_TwoSiO_Four, 2MgO_Two
-Al_TwoO_Three-5SiO_Two, WO_Three, Bi_TwoO_Three, Cd
O, CdS, CdSe, GaP, GaAs, CdFeO
_Three, MoS_Two, LaRhO_Three, GaN, CdP, Nb_Two
O_Five, GaAsP, Li_TwoO-Al_TwoO_Three-4Si
O _Two, Mg ferrite, Ni ferrite, Ni-Zn ferrite
Ferrite, Li ferrite, Sr ferrite, etc.
Can be These components (e) may be used alone or
Seeds or more can be used in combination.
Silica and colloidal alumina. The above colloidal silica was obtained from Snowtech
, Isopropanol silica sol, methanol silica sol
(All made by Nissan Chemical Industry Co., Ltd.); cataloid, male
Cal [produced by Catalyst Chemical Industry Co., Ltd.]; Ludex (US
Syton (Monsanto, USA)
Nalcoag (Nalco Chemical, USA)
It is commercially available under the product name. Also, the above colloidal alumina
Is, for example, synthetic alumina, boehmite, pseudo-boehmite
Etc. can be used. Such colloidal
Lumina is, for example, alumina sol 100, alumina sol
520 [or more, manufactured by Nissan Chemical Industry Co., Ltd.]
Sold. Further, as the component (e), photocatalytic activity
TiO_Two(Including anatase type
Is preferred), and CeO is used in order to provide the ultraviolet absorbing ability.
_Two, ZnO or the like is preferably used. The average particle size of the component (e) is preferably 30
μm or less, more preferably 0.005 to 20 μm,
The thickness is preferably 0.005 to 10 μm. Average particle size
If it exceeds 30 μm, the resulting coating film
The surface may not be smooth. The presence form of component (e) is divided into powder and water.
Sprayed aqueous sol or colloid, isopropyl alcohol
In polar solvents such as coal, and non-polar solvents such as toluene
Solvent-based sols or colloids. solvent
In the case of system sol or colloid, it depends on the dispersibility of the semiconductor.
May be further diluted with water or a solvent,
Surface treatment may be used to improve dispersibility.
(E) the component is an aqueous sol or colloid, or
When it is a sol or colloid in a medium system, the solid content concentration is
It is preferably at most 40% by weight. The method of blending the component (e) into the composition
May be added after preparation of the composition, or
The component (e) is added during the preparation of the product, and the component (e) is added to the component (a).
Co-hydrolysis with component (b) or component (b ')
-It may be condensed. The amount of the component (e) used is based on the above component (a).
(R¹)_nSiO_{(4-n) / 2}Structural unit 100 represented by
Parts by weight, on a solid basis, usually from 0 to 500 parts by weight,
Preferably, it is 0.1 to 400 parts by weight. [0090]Other additives;Also, the coating of the present invention
The composition and the undercoating composition are coated with the resulting coating film.
To improve color, thickness, paintability, etc.
Separate fillers for additional functions such as abundance and heat shielding
Can also be added and dispersed. With such filler
For example, water-insoluble organic pigments, inorganic pigments, pigments
Other than particulate, fibrous or scaly ceramic
Metals, alloys, and the oxidation of these metals
Substances, hydroxides, carbides, nitrides, sulfides, etc.
Can be. However, as other additives,
(E) Excluding the component. Specific examples of the filler include iron, copper, and iron.
Luminium, nickel, silver, zinc, ferrite, carbo
Black, stainless steel, silicon dioxide, oxidation for pigments
Titanium, aluminum oxide, chromium oxide, manganese oxide
Iron, zirconium oxide, cobalt oxide, synthetic
Light, aluminum hydroxide, iron hydroxide, silicon carbide,
Silicon nitride, boron nitride, clay, diatomaceous earth, sludge
Ash, plaster, talc, barium carbonate, calcium carbonate, charcoal
Magnesium oxide, 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, Navy Blue, Pigment Gris
, Rock ultramarine, cobalt blue, cerulean blue, boric acid
Copper, molybdenum blue, copper sulfide, cobalt purple, mars purple, ma
Ngan purple, Pigment violet, Lead suboxide, Lead acid
Lucium, zinc yellow, lead sulfide, chrome yellow, ocher, mosquito
Domium yellow, strontium yellow, titanium yellow, litharge,
Pigment yellow, cuprous oxide, cadmium red, selenium
Red, chrome vermillion, red iron, zinc white, antimo
White, basic lead sulfate, titanium white, lithopone, lead silicate,
Zircon oxide, tungsten white, lead, zinc white, bunch
White, lead phthalate, manganese white, lead sulfate, graphite, bone
Black, diamond black, thermatomic black, vegetable
Black, potassium titanate whisker, molybdenum disulfide
And so on. These fillers can be used alone.
Alternatively, two or more kinds can be used as a mixture. Filler
The amount used is based on 100 parts by weight of the total solids of the composition.
Usually, it is 300 parts by weight or less. Further, the coating composition of the present invention and
In the composition for undercoating, if necessary, methyl orthoformate may be used.
, Methyl orthoacetate, tetraethoxysilane, etc.
Known dehydrating agent; polyoxyethylene alkyl ether,
Lioxyethylene alkyl phenyl ether, polyoxy
Cyethylene fatty acid ester, polycarboxylic acid type polymer world
Surfactant, polycarboxylate, polyphosphate, polyac
Lylate, polyamide ester, polyethylene glyco
Dispersants such as methyl cellulose, ethyl cellulose
, Hydroxyethylcellulose, hydroxypropyl
Cellulose, hydroxypropyl methylcellulose, etc.
Celluloses, castor oil derivatives, ferrosilicates
Which thickeners: ammonium carbonate, ammonium bicarbonate
, Ammonium nitrite, sodium borohydride,
Inorganic blowing agents such as lucium azide, azobisisobuty
Azo compounds such as lonitrile, diphenylsulfone
Hydrazine compounds such as 3,3'-disulfohydrazine
Compound, semicarbazide compound, triazole compound, N-
In addition to organic blowing agents such as nitroso compounds, surfactants,
Silane coupling agent, titanium coupling agent, dye
Any other additives can be included. Further, the coating property of the composition is further improved.
For this purpose, a leveling agent can be blended. This
Of the leveling agents such as fluorinated leveling agents
(Product name, the same applies hereinafter), for example,
-(BM-CHEMIE) BM1000, BM11
00; Efka 772, Efka 77 of Efka Chemicals
7; Floren series manufactured by Kyoeisha Chemical Co., Ltd .; Sumitomo SU
FC series of LEM Co., Ltd .; full of Toho Chemical Co., Ltd.
Onar TF series, etc.
As a bean-based leveling agent, for example, Big Chemie
BYM series; Shmegma
nn) Shmego Series; Fuka Chemicals
Efka30, Efka31, Efka34, Efka3
5, Efka 36, Efka 39, Efka 83, Efka 8
6, Efka 88, etc.
Or ester leveling agents such as Nisshin.
Carfinol from Chemical Industry Co., Ltd .; Emul from Kao Corporation
And homogenol. When such a leveling agent is blended,
As a result, the finished appearance of the coating film is improved, and
Can be applied all at once. 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. Further, the composition of the present invention contains an antibacterial agent and an antibacterial agent.
A mold may be added. As antibacterial and antifungal agents,
Metals such as silver, copper, zinc, etc.
Lucium, zirconium phosphate, vanadium phosphate, ke
Calcium formate, silica gel, amino acids, metal soaps,
Lamix, apatite, activated carbon, montmorillonite, low
No metal ion supported on a carrier such as molecular glass
Organic antibacterial agent; phenol ether derivative, sulfone derivative
Body, imidazole derivative, oxybisphenoxyarsi
, Organic nitrogen-sulfur compounds, nitrile derivatives, benzothiene
Azole derivatives, isothiazole derivatives, thiadiazo
Derivatives, triazine derivatives, pyrrole derivatives, aliphatic
Organic antibacterial agents such as imide derivatives are exemplified. Antibacterial agent
Is preferably less than 5% by weight based on the total composition.
Is full. The composition used in the present invention is preferably
In other words, the undercoating compositions (i) to (ii) contain other resins.
May be blended. Other resins include acrylic-
Urethane resin, epoxy resin, polyester, acrylic
Resin, fluorine resin, acrylic resin emulsion, epoxy
Resin emulsion, polyurethane emulsion, poly
Ester emulsions and the like can be mentioned. Coating composition of the present invention and primer
In preparing a composition for use, component (c) and component (d)
When components are not used, the method of mixing each component is particularly limited.
Although not specified, when (c) component and (d) component are used
In this case, preferably, the component (d) of the components (a) to (e) is used.
After obtaining the mixture except the components, add the component (d) to this
Is adopted. [0098] The method for preparing the coating composition of the present invention
Examples of the body include the following methods.
Wear. Organosilanes (1), (b) constituting component (a)
Mixing of component, component (c) and required amount of organic solvent
The product was subjected to a hydrolysis / condensation reaction by adding a predetermined amount of water.
Then, a method of adding the component (d). (A) an organosilane (1) constituting the component, and
Add a predetermined amount of water to a mixture consisting of the required amount of organic solvent.
To carry out hydrolysis / condensation reaction, and then the component (b) and
The component (c) was added and mixed, and a condensation reaction was further performed.
Then, a method of adding the component (d). Organosilane constituting component (a)
A mixture comprising components (1) and (c) and a required amount of an organic solvent.
A predetermined amount of water is added to the mixture to carry out hydrolysis and condensation reactions.
Then, the component (b) is added and mixed, and
A method in which a component (d) is added after performing a combined reaction. (A) a part of the organosilane (1) constituting the component,
Component (b), component (c) and the required amount of organic solvent
A predetermined amount of water to the mixture,
And then adding the remainder of the organosilane (1),
After further hydrolysis / partial condensation reaction, (d)
How to add components. In the present invention, (a) to (b)
The components and components other than components (c) to (d) comprise a composition
Can be added at an appropriate stage of preparing the compound. The coating composition of the present invention is storage-stable
Excellent adhesion, adhesion, alkali resistance, organic chemical resistance,
Without deteriorating weather resistance, moisture resistance, water resistance (warm) water resistance, etc.
Forming a coating film with excellent antifouling function with excellent water and oil repellency
Can be achieved. The total solid content of the coating composition of the present invention
The degree is usually 1 to 45% by weight, preferably 2 to 40 weights.
%, Which is appropriately adjusted according to the purpose of use. Composition
If the total solids concentration of the above exceeds 45% by weight, the storage stability
Tends to decrease. [0103] In addition, an undercoating layer sometimes used in the present invention.
The total solid content of the compositions (i) to (ii) for
50% by weight or less, preferably 40% by weight or less,
Appropriately adjusted according to the type of substrate, coating method, coating film thickness
It is. [0104]Sanitary ware The configuration of the sanitary ware of the present invention includes, for example,
Ming coating composition, substrate / composition for undercoat
Any of (i) to (ii) / Coating composition of the present invention
Material or base material / primer / composition for undercoat
Any of the products (i) to (ii) / the coating set of the present invention
And the like. The coating composition of the present invention
And the above compositions (i) to (ii) for undercoating are applied to a substrate
When using any composition, brush, roll core
Coater, flow coater, gravure coater, centrifugal coater
Using a coater, ultrasonic coater, etc.
Coating, spray coating, spraying, screen process, electrodeposition,
Vapor deposition and the like. In the case of the coating composition of the present invention,
As a film thickness, a single coating is about 0.05 to 30 μm thick,
With double coating, a coating film with a thickness of about 0.1 to 60 µm is formed.
Can be Then dry at room temperature or
Is a temperature of about 30 to 200 ° C., usually about 1 to 60 minutes
By heating and drying to form a coating film
it can. When the undercoat is applied in advance,
Using the above compositions (i) to (ii), a dry film thickness of 1
Thickness of about 0.05 to 30 μm with two coats, thick with two coats
A coating film having a thickness of about 0.1 to 60 μm can be formed.
You. Then, dry at room temperature, or 30 ~ 20
Dry at about 0 ° C for about 1 to 60 minutes
By forming a coating film on various wallpaper base materials
Can be. The total film thickness of the undercoat and topcoat is the dry film
Thick, usually 0.1 to 80 μm, preferably 0.2 to 80 μm
It is about 60 μm. Further, a primer is used depending on the application.
In such cases, the type of primer is not particularly limited, and
Anything that has the effect of improving the adhesion to the composition
It may be selected depending on the type of the base material and the purpose of use. Plastic
Immers may be used alone or as a mixture of two or more.
And contains no coloring components such as pigments and dyes.
May be. As the type of primer, for example,
Kid resin, amino alkyd resin, epoxy resin, polyether
Steal, acrylic resin, urethane resin, fluororesin,
Kuril silicone resin, acrylic melamine resin, acrylic
Resin emulsion, epoxy resin emulsion, polyurethane
Urethane emulsion, polyester emulsion, etc.
Can be mentioned. Also, these primers
If adhesion between the substrate and the coating film under severe conditions is required,
Seed functional groups can also be provided. Such functional groups
Examples include, for example, a hydroxyl group, a carboxyl group,
Group, amide group, amine group, glycidyl group, alkoxy
Examples include silyl groups, ether bonds, and ester bonds.
Can be. Furthermore, the primer has an ultraviolet absorber,
An ultraviolet stabilizer or the like may be blended. The coating composition of the present invention is
The abrasion resistance and gloss of the coating film are further improved on the surface of the formed coating film.
For the purpose of enhancement, see, for example, US Pat.
No. 6,997, U.S. Pat. No. 4,027,073.
Colloidal silica and siloxane described in the specification etc.
Siloxane-based paints such as stable dispersions with resins
Any clear layer can be formed. As the sanitary ware of the present invention, for example,
Tables and toilet members. These sanitary ware of the present invention
As the material of the base material used for the glazing,
And porcelain tiles. these
For base materials, adjustment of base material, improvement of adhesion, sealing of porous base material
Surface treatment for smoothing, patterning, etc.
Can also be applied. [0111] Embodiments of the present invention will now be described with reference to examples.
Will be described more specifically. However, the present invention
The present invention is not limited by the embodiment. Example
Parts and% in Comparative Examples and Comparative Examples are by weight unless otherwise specified.
It is equivalent. In addition, various measurements in Examples and Comparative Examples were performed.
The determination and evaluation were performed by the following methods. (1) Mw Gel permeation chromatography under the following conditions
-(GPC) method. Sample: Olga using tetrahydrofuran as solvent
1 g of condensate of silane or vinyl resin containing silyl group
0.1 g each in 100 cc of tetrahydrofuran
And prepared by dissolving in Standard polystyrene: Mark manufactured by Pressure Chemical Co., USA
Semi-polystyrene was used. Apparatus: High-temperature, high-speed gel permeation chromatograph manufactured by Waters, USA
Togram (Model 150-C ALC / GPC) Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1 cc / min (2) Storage stability A composition without a curing accelerator was added to a polyethylene bottle.
Inside, store sealed at room temperature for 3 months, and visually check for gelation
It was determined by What does not cause gelation
Measures viscosity with a BM viscometer manufactured by Tokyo Keiki Co., Ltd.
The test was performed when the rate of change was within 20%. (3) Adhesion Cross-cut test based on JIS K5400 (Masume 100
), The tape peel test was performed three times, and the average
Relied on. (4) Hardness Based on pencil hardness according to JIS K5400. (5) Alkali resistance The test piece was immersed in a saturated calcium hydroxide aqueous solution for 60 days.
After immersion, the state of the coating film was visually observed. Of change
Those that did not exist were rated "good". (6) Organic chemical resistance 2 cc of isopropyl alcohol is dropped on the coating film, and 5 minutes
After wiping with a cloth later, visually observe the state of the coating film
did. Those that did not change were regarded as “good”. (7) Moisture resistance The test piece was continuously heated in an environment of 50 ° C and 95% humidity.
After holding for 1,000 hours, take out and change the state of the coating
Observed visually. If there is no change, "good"
Was. (8) Water resistance After immersing the test piece in tap water at room temperature for 60 days,
The state of the film was visually observed. If there is no change,
"Good." (9) Warm water resistance The test piece was immersed in warm water at 60 ° C for 14 days,
The state of the film was visually observed. If there is no change,
"Good." (10) Stain resistance On the coating, carbon black / kerosene = 1/2 (weight ratio)
Paste for 24 hours at room temperature
After standing, wash with a sponge and stain the coating.
The state was observed and evaluated according to the following criteria. ○: No pollution Δ: Slightly contaminated. X: Contamination is remarkable. (11) Contact angle Ultra-pure water as water or coal tar as oil
(JIS K2439 industrial coal tar) 3μ
The contact angle at the time of mounting is automatically measured by Kyowa Interface Chemical Co., Ltd.
It was measured by a contact angle meter. (12) Friction and wear resistance Wear wheel cs-10, load by Taber abrasion tester
A 0.5 kg load was applied to perform a friction and wear test for 500 revolutions.
The difference between the haze before and after the test, and
evaluated. ；: Haze difference is less than 1 Δ: Haze difference is less than 5 ×: Difference in haze is 5 or more Reference Example 1 [Polymerization of component (b)] A stainless steel autoclave equipped with an electromagnetic stirrer
After sufficient replacement with source gas, the autoclave is
150 parts of butyl isobutyl ketone and ethyl vinyl ether
30 parts and lauroyl peroxide (radical polymerization initiator) 2
And dry ice the solution in the autoclave.
After cooling to −50 ° C. with methanol,
The oxygen in the system was removed again by heat. Hexaph
20 parts of fluoropropylene, perfluoro (methyl vinyl
Ether) and 5 parts of vinyltrimethoxysilane.
And the temperature was raised. The temperature in the autoclave is 60
When the pressure in the autoclave reaches 5 ° C, the pressure is 5k.
gf / cm^TwoMet. Keep the temperature of the reaction system at 60 ° C
The polymerization reaction is continued for 20 hours by stirring while stirring.
And the pressure inside the autoclave is 1.5 kgf · cm^TwoTo
At the time of drop, the reaction was stopped by water cooling, and the solid content
0% of the component (b) (hereinafter also referred to as “(B-1)”)
Obtained. Reference Examples 2 to 5 [Polymerization of component (b)] Same as Reference Example 1 except that the monomer components shown in Table 1 were used
Thus, the components (b) of (B-2) to (B-5) were obtained. [0119] [Table 1]Reference Example 6 [silyl group-containing vinyl polymer]
Synthesis of (b ′)] Methyl methacrylate was added to a reactor equipped with a reflux condenser and stirrer.
Rate 70 parts, n-butyl acrylate 40 parts, γ-meth
20 parts of acryloxypropyltrimethoxysilane,
5 parts of lylic acid, 2-hydroxyethyl methacrylate 13
Part, 1,1,1-trimethylamine methacrylimide 2
Part and i-propyl alcohol 150 parts methyl ethyl
50 parts of ketone and 25 parts of methanol were added and mixed.
Then, the mixture was heated to 80 ° C. while stirring, and
4 parts of isovaleronitrile were dissolved in 10 parts of xylene
After the solution was added dropwise over 30 minutes, the solution was
Silyl group-containing vinyl polymer having a solid concentration of 40%
Solution (b'-1) was obtained. Synthesis Examples 1 to 11 and Comparative Synthesis Examples 1 and 2 Table 2 and Table 3 were added to a reactor equipped with a reflux condenser and a stirrer.
Add each component shown in (excluding water and post-additional components) and mix
After adding water, the mixture was stirred and reacted at 60 ° C. for 5 hours.
Next, post-additional components are added and the mixture is cooled to room temperature,
Coating compositions (A) to (K) of the present invention having a degree of 20%
And compositions (a) and (b) for comparison were obtained. Got
The storage stability of the composition was evaluated. Table 2 shows the evaluation results.
Also shown in Table 3. [0122] [Table 2][0123] [Table 3](* 1): Zinc oxide dispersed in toluene (solid content)
(Concentration 30%) (* 2): Water-dispersed (pH 4) anatase type titanium oxide
(Solid content 30%) (* 3): particle size 0.1 μm Reference Example 7 [Coating composition for undercoating]
Synthesis) In a reactor equipped with a reflux condenser and stirrer,
70 parts of xysilane, glycidoxypropyltrimethoxy
30 parts of silane, 20 parts of water, i-propyl alcohol 15
0 parts and 10^-2Add 20 parts of mol / l hydrochloric acid aqueous solution
The mixture was stirred and reacted at 60 ° C. for 4 hours. Then to room temperature
After cooling, toluene dispersed zinc oxide (solid content concentration 30%) 2
By adding 0 parts, a composition having a solid content of 20% was obtained. Profit
100 parts of the obtained composition were mixed with i-propyl alcohol 10
Add 0 parts and mix well, then dibutyltin diacetate.
I-prote of reactant consisting of silicate and silicate oligomer
Add 10 parts of pill alcohol solution (15% solids)
Stir well to obtain undercoating coating composition (i-1)
Was. Reference materials 8 to 10 [undercoating coating
Synthesis of composition) Table 4 shows a reactor equipped with a reflux condenser and a stirrer.
Add each type and number of components (excluding post-additional components) and mix well.
The mixture was stirred and reacted at 60 ° C. for 4 hours. Then cool to room temperature
And a composition with a solid content of 20%
I got In 100 parts of the obtained composition, i-propyl al
After adding 100 parts of coal and mixing well, dibutyls
Reactant consisting of diacetate and silicate oligomer
Of i-propyl alcohol solution (solid content 15%) of 10
Part of the mixture, stirred well, and prepared the undercoating coating composition (ii
-1) to (ii-3) were obtained. [0127] [Table 4](* 1) Polyester tree manufactured by Takamatsu Yushi Co., Ltd.
Fat (solid content 20%) Reference Example 11 [Preparation of undercoat coating composition] To 100 parts of the solution (b'-1) obtained in Reference Example 6,
80 parts of ethyl ketone and i-propyl alcohol 2
Add 0 parts and stir well, for undercoating with a solid content of 20%
A coating composition (p-1) was obtained. Examples 1 to 15 and Comparative Examples 1 and 2 Undercoat as needed on 1cm thick ceramic tile surface
Coating material and the coating composition of the present invention
Apply and dry to a dry film thickness of 2μm, sanitary ware
Sample. Various evaluations on the obtained sample
Was done. The results are shown in Tables 5 to 7. [0130] [Table 5] [0131] [Table 6][0132] [Table 7] [0133] Industrial Applicability The coating composition for sanitary ware of the present invention
Is a fluorine containing a specific organosilane component and a silyl group.
Because it contains an elemental polymer, it has excellent storage stability.
Adhesion, alkali resistance, organic chemical resistance, weather resistance, moisture resistance
Without reducing the water resistance and (hot) water resistance.
An improved coating can be formed. Moreover, the coating
The membrane has high hardness, excellent durability and abrasion resistance,
It has an antifouling function due to its oil repellency. Therefore, long term
Maintenance-free sanitary ware without compromising the beauty
And useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) E03D 9/00 E03D 9/00 11/02 11/02 Z // C08L 27/12 C08L 27/12 29 / 10 29/10 83/04 83/04 F-term (reference) 2D038 ZA00 2D039 AA00 BA03 DB04 4G059 AA04 AC22 FA05 FA11 4J002 BD12X BE04X BF04X BG07X BQ00X CD20X CF00X CP03W GH01 4J038 CD092 DL021 DL0307 JC32 NA05

Claims (1)

[Claims] (1) 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, and (B) (b-1) a structural unit represented by the following general formula (2) (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. ) And / or (B-2) Structural unit represented by the following general formula (3) [In the formula, Rf represents an alkyl group containing a fluorine atom or an alkyl group.
A oxyalkyl group;^Three~ R^FiveIs the general formula (2)
It is synonymous and, within the same meaning, R in general formula (2) ^Three~ R
^FiveAnd may be different. ] And hydrolyzable
Having a silicon atom bonded to a group and / or a hydroxyl group
At least one selected from the group of polymers containing a silyl group
Coating set for sanitary ware characterized by containing
Adult. 2. The coating for sanitary ware according to claim 1.
Sanitary ware having a coating film composed of the composition. 3. A composition comprising the following composition (i) or (ii):
The sanitary ware core according to claim 1, further comprising:
Characterized by having a coating film composed of a coating composition.
Sanitary ware. (I) (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 of decomposed products and condensates of the organosilane
A coating composition containing at least one. (Ii) component (a), and (b ′) a hydrolyzable group
And / or silicon compounds having a silicon atom bonded to a hydroxyl group.
Coating composition containing a polymer containing a ril group
object.