JP2001040338A - Coating composition for snow and ice prevention and method for forming coating for snow and ice prevention - Google Patents

Abstract

(57) [Summary] [PROBLEMS] A coating film with high storage stability that has excellent storage stability and does not decrease adhesion, alkali resistance, organic chemical resistance, weather resistance, moisture resistance, (hot) water resistance, etc. An anti-snowing / icing prevention article having a high hardness coating film having excellent anti-snowing / icing ability based on water repellency and oil repellency. 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
Or a coating composition for preventing snow and ice formation, comprising a fluoropolymer having a silyl group having a silicon atom bonded to a hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for preventing snow and ice formation based on water repellency and oil repellency, and more particularly, to an organosilane-based fluoropolymer containing a silyl group. The present invention relates to a coating composition for preventing snow and ice formation.

[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.

According to Japanese Patent Application Laid-Open No. 9-228073, a water-repellent coating made of polytetrafluoroethylene or the like is formed on the surface of an underlayer containing photocatalyst particles such as titanium dioxide and an electron-trapping metal such as silver and copper. Has been proposed. According to this water-repellent member, components that inhibit water repellency such as dirt adhered to the surface of the water-repellent film by the oxidation-reduction reaction of the photocatalyst particles forming the underlayer are decomposed and removed, and water droplets ( By reducing the area of snow, ice), high water repellency is maintained over a long period of time. However, if such photocatalyst particles are used for the underlayer, the substrate itself is severely damaged, and if a water-repellent coating layer is separately provided on the photocatalyst layer, the photocatalytic function is actually sufficient. Does not work. According to the publication, the water-repellent film serving as the surface layer is made of polytetrafluoroethylene or the like, and has not only poor adhesion to the base material and the underlying layer, but also a high temperature when forming the film. There are also disadvantages such as not sintering.

[0004]

The present invention contains a specific organosilane component and a fluoropolymer having a silyl group, has excellent storage stability, and has excellent adhesion, alkali resistance,
Forming a high hardness coating with excellent water and oil repellency and excellent snow and ice prevention properties without reducing organic chemical resistance, weather resistance, moisture resistance, (water) resistance, etc. It is an object of the present invention to provide a coating composition for preventing snow and icing which can be performed.

[0005]

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 kind, and (b) (b-1) the following general formula
The structural unit represented by (2) (hereinafter referred to as “(b-1)
Position)),(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) represented by the following general formula (3).
Constituent unit (hereinafter also referred to as “(b-2) constituent unit”)
U)[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 for preventing snow and ice formation characterized by having
A composition (hereinafter also referred to as “composition (I)”).
It is. Further, the present invention provides the above-mentioned
Forming a coating film composed of a coating composition for preventing icing
A method for forming a coating film for preventing snow and ice formation.
To provide. Further, the present invention provides the following (i)
Or (ii) to form a coating film composed of the composition,
The coating composition for preventing snow and ice formation according to claim 1.
Snow and ice protection, characterized by forming a coating film
It is intended to provide a method for forming a stop coating film. (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) ”).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A coating set for preventing snow and icing
Narubutsu component (a); (a) component to be blended in the coating composition of the present invention (hereinafter also referred to as "organosilane (1)") organosilane represented by the above general formula (1), organosilane It is at least one selected from a hydrolyzate of (1) and a condensate of organosilane (1).
That is, the component (a) may be only one of these three types, or may be a mixture of any two types.
It may be a mixture containing all types. Here, the hydrolyzate of the organosilane (1) does not need to have all of the ² to 4 OR ² groups contained in the organosilane (1) hydrolyzed. For example, only one hydrolyzate is hydrolyzed. Or two or more of them may be hydrolyzed, or a mixture thereof. 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-
Hexyl group, n-heptyl group, n-octyl group, alkyl group such as 2-ethylhexyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, acyl group such as trioil group, vinyl group, allyl group, Examples thereof include a cyclohexyl group, a phenyl group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroalkyl group, a fluoroacetamide group, an 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 isocyanato group, a glycidoxyl group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxyl group. Groups, ureido groups, ammonium bases and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

The alkyl group having 1 to 5 carbon atoms for R ² includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, 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 and tetra-n-butoxysilane. 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, nonafluorohexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 2-hydroxyethyltrimethoxysilane, 2
-Hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 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) atacryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane,
Trialkoxysilanes such as 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, -I-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, Di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-
Heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n
-In addition to dialkoxysilanes such as cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, methyltriacetyloxysilane, dimethyldiacetyloxysilane, etc. Can be mentioned.

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, only trialkoxysilane, 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 alkali resistance of the resulting coating film 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) is When mixing with the remaining components to prepare the composition, 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 weight average molecular weight in terms of polystyrene (hereinafter also referred to as “Mw”) of 800 to 100,000, more preferably 1,
000 to 50,000.

The commercially available products of component (a) include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicon resin manufactured by Dow Corning Toray, and silicone resin manufactured by Toshiba Silicone Co., Ltd. , Silicon resin manufactured by Shin-Etsu Chemical Co., Ltd., silicon oligomer manufactured by Nippon Yunika Co., Ltd.
Alternatively, they may be used after condensation.

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

(B) a silyl group-containing fluoropolymer; the component (b) in the present invention has the structural unit (b-1) and / or the structural unit (b-2), and is hydrolyzed. Has a silyl group having a silicon atom bonded to a functional group and / or a hydroxyl group (hereinafter, also referred to as “specific silyl group”), and preferably has a specific silyl group at a terminal and / or a side chain of a polymer molecular chain. It is a fluoropolymer. When such a component (b) cures a coating film obtained from the coating composition of the present invention, a hydrolyzable group and / or a hydroxyl group in the silyl group co-condenses 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 from 0.5 to 50 mol%, in the component (b).

The specific silyl group preferably has the following general formula (4) (Wherein, X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an acetoxy group, a phenoxy group, a thioalkoxy group, an amino group or a hydroxyl group, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or And represents an aralkyl group having 1 to 10 carbon atoms, and i is an integer of 1 to 3).

The component (b) is a monomer that constitutes the structural unit (b-1) represented by the general formula (2) (hereinafter also referred to as “(b-1) monomer”). And / or a monomer (hereinafter also referred to as “(b-2) monomer”) constituting the (b-2) structural unit represented by the general formula (3), Obtained by polymerizing (b-3) a monomer containing a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, which constitutes a (b-3) specific silyl group represented by 4), and Optionally, (b-4) another monomer copolymerizable with these monomers (hereinafter referred to as “(b-4)
) May also be obtained by polymerization. The (b-4) monomer is composed of the (b-1) monomer and the (b)
-2) It may have a fluorine atom which is not included in the monomer.

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

(B-1) a monomer; (b-1) a monomer
It is represented by the following general formula (2) ′. (Wherein, R ^{3 to} R ⁵ are C _m Y _{2m + 1} , and 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,
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.
(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
The monomers may be used alone or in combination of two or more.

(B-2) monomer; (b-2) monomer is
It is represented by the following general formula (3) ′. Wherein, Rf represents an alkyl group or an alkoxyalkyl group containing a fluorine atom, R ³ to R ⁵ is a general formula (2) 'interchangeably, within the same meanings, the formula (2)
R ^{3 to} R ⁵ may be different. ]

Examples of the monomer (b-2) include:
Compounds having one polymerizable unsaturated double bond, 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 ethers or (fluoroalkoxyalkyl) vinyl ethers represented by the following formulas: , Perfluoro (isobutyl vinyl ether)
(C) perfluoro (alkoxyalkyl vinyl ethers) 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.

When the monomers (b-1) and (b-2) are used in combination, hexafluoropropylene and perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether are used in combination. It is preferable to use it.

(B-3) Monomer; (b-3) monomer is
A 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 also referred to as "unsaturated silane compound").

Specific examples of the unsaturated silane compound include CH ₂ ＣＨCHSi (CH ₃ ) (OCH ₃ ) ₂ and CH
₂ ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OC
_{2 H 5) 3, CH 2} = CHSi (CH 3) Cl 2, CH
₂ ＣＨCHSiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂
Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO
(CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO
(CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ =
CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ =
CHCOO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂
ＣＨCHCOO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣＨCHC
OO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCH
COO (CH ₂ ) ₃ SiCl ₃ , CH ₂ ＣC (CH ₃ )
COO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C
H ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (OC
H ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ S
i (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) C
OO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣC (C
_{H 3) COO (CH 2)} 2 Si (CH 3) Cl 2, CH
₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ SiCl ₃ , CH
_{2 = C (CH 3) COO} (CH 2) 3 Si (CH 3) C
l ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiC
l ₃ ,

[0028]

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

(B-4) monomer; (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 2,4-dichlorostyrene, 2,6-dichlorostyrene, 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,
Substituted linear conjugated pentadienes substituted with substituents such as 3-butadiene, 2-cyano-1,3-butadiene, isoprene, an alkyl group, a halogen atom, and a cyano group; linear and side-chain conjugated hexadienes; (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;
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, 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 Other than 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 and 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 at a time and polymerization is performed, a part of the monomer is polymerized, and then the remaining part is continuously processed. Or a method in which the monomer is continuously added 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 total content of the constituent units (b-1) and (b-2) constituting the component (b) is usually 0.5 to 80 mol% in the component (b), preferably Is 1 to 70
Mol%. If the amount is less than 0.5 mol%, it may be difficult to obtain a well-balanced coating film having water repellency and oil repellency, as well as excellent transparency and adhesion. On the other hand, 80 mol%
If it exceeds, the resulting coating film may have poor adhesion to the substrate. Among them, the content of the structural unit (b-1) is preferably 0.5 to 70 mol% in the component (b). Further, the content of the (b-2) structural unit is as follows:
In the component (b), the content is preferably 0.5 to 70 mol%. Further, the content of the structural unit (b-3) is such that the content of the specific silyl group is usually 0.1 to 60 in the component (b).
Mol%, preferably 0.5 to 50 mol%. If it is less than 0.1 mol%, the effect of co-condensation with the component (a) cannot be obtained. On the other hand, if it exceeds 60 mol%, the storage stability of the obtained coating composition tends to be poor. In addition, the structural unit [(b-4) structural unit] composed of the (b-4) monomer which is another copolymerizable monomer,
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) 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:
(R ¹ ) _n SiO _{(4-n ) / 2} in the component (a) [R ¹ and n are the same as in the above formula (1). The same applies to 100 parts by weight of the structural unit represented by the following.], Usually 20 to 800 parts by weight, preferably 25 to 750 parts by weight, more preferably 50 to 700 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, 8
If it exceeds 00 parts by weight, the weather resistance of the coating film tends to decrease.

In the present invention, a vinyl copolymer containing no specific fluorine atom and containing a specific silyl group is used in combination with the component (b) (hereinafter also referred to as "component (b ')").
May be used in a range that does not impair the effects of the present invention. The component (b ′) is composed of the monomer (b-3) and the component (b-4)
It can be obtained by copolymerizing a monomer or by subjecting (b-4) a silane compound to an addition reaction with a polymer obtained by polymerizing the monomer (b-4). The content of the component (b ′) is usually in the range of 100 parts by weight of the component (a).
500 parts by weight or less.

The composition of the present invention and the undercoat composition described below are usually prepared by subjecting water to a hydrolysis / condensation reaction of the organosilane (1) or a particulate component described later, when the composition is prepared. Is added to disperse. In the present invention, the amount of water used is (R ¹ ) _n S in the component (a).
It is generally about 0.5 to 3 mol, preferably about 0.7 to 2 mol, per 1 mol of the structural unit represented by iO _{(4-n) / 2} .

The composition of the present invention and the undercoating composition described below mainly include the component (a) and the components (c) to
An organic solvent is used to uniformly mix the component (e) and the like, adjust the total solid content of the composition, and further improve the dispersion stability and storage stability of the composition.

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, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and 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.

As described above, the coating composition of the present invention has a function of preventing snow and ice formation based on water repellency and oil repellency. It is preferable to apply an undercoat to the surface of the resin. As the undercoating composition for forming the undercoating layer, the above-mentioned composition (i) or composition (ii) can be preferably mentioned.

Hereinafter, the composition (i) and the composition (ii) for the undercoat 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) is preferably prepared by adding an appropriate amount of water to the organosilane (1) to hydrolyze and condense the organosilane (1). As described above, a hydrolyzate and / or condensate of the organosilane (1) can be used as the component (a).

Composition (ii) The undercoating composition (ii) is prepared as described in (a) above.
And (b ') a silyl group-containing polymer.

(B ′) Silyl group-containing polymer; component (b ′) does not contain a fluorine atom and has a specific silyl group, preferably at the terminal and / or side chain of the polymer molecular chain, as described above. Is a polymer. In composition (ii),
The component (b ′) is a component that provides excellent coating performance by curing the coating film by co-condensing the hydrolyzable group and / or hydroxyl group in the silyl group with the component (a). is there. The content of silicon atoms in the component (b ′) is usually 0.001 to 20% by weight, preferably 0.01 to 15% by weight, based on the component (b ′). Preferred specific silyl groups are groups represented by the above general formula (4).

The (b ′) silyl group-containing polymer is used in the production of the above (b) silyl group-containing fluoropolymer,
Without using (b-1) monomer and (b-2) monomer,
(B-4) It is obtained in the same manner as in the method for producing the component (b), except that at least one of the above-mentioned monomers containing no fluorine is used as the monomer.

Other examples of the component (b ') include a specific silyl group-containing epoxy resin and a specific silyl group-containing polyester resin. The specific silyl group-containing epoxy resin is, for example, an epoxy group in an epoxy resin such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, an aliphatic polyglycidyl ether, or an aliphatic polyglycidyl ester. And aminosilanes having specific silyl groups, vinylsilanes, carboxysilanes, glycidylsilanes and the like. The specific silyl group-containing polyester resin is, for example, produced by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with an aminosilane having a specific silyl group, a carboxysilane, a glycidylsilane, or the like. Can be.

The Mw of the component (b ′) is preferably 2,0
00 to 100,000, more preferably 4,000 to
50,000. The amount of the component (b ′) used in the composition (ii) is based on the amount of the component (R ¹ ) _n SiO in the component (a).
It is usually 2 to 900 parts by weight, preferably 10 to 800 parts by weight, more preferably 20 to 700 parts by weight, based on 100 parts by weight of the structural unit represented by _{(4-n) / 2} . In this case, if the amount of the component (b ') is less than 2 parts by weight, the resulting coating film may have poor alkali resistance. Tends to decrease.

In the present invention, the component (b ') can be used alone or as a mixture of two or more kinds obtained as described above. In the composition (ii), the component (b ′) is preferably co-condensed with the component (a) in the presence of water and / or an organic solvent. In the composition (ii), the type and amount of the component (a) are the same as those of the coating composition of the present invention, and thus the description is omitted.

The following components (c) to (e) are further added to the coating composition of the present invention and the compositions (i) to (ii) for undercoating used as needed. be able to. Hereinafter, these components will be described.

Component (c); component (c) is component (a),
It is a catalyst that promotes the hydrolysis / condensation reaction of component (b), component (b ′) and the like. By using the component (c), the curing speed 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, so that strength, long-term durability, etc. In addition, it is possible to obtain an excellent coating film, and it is easy to increase the thickness of the coating film and to perform a coating operation.

The component (c) includes an acidic compound, an alkaline compound, a metal salt, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter referred to as an organometallic compound and / or a partial hydrolyzate 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. Examples of the metal salt include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.

Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, and the like. -Aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3 -(2-aminoethyl) -aminopropylmethyldimethoxysilane, 3
-Anilinopropyltrimethoxysilane, alkylamine salts, quaternary ammonium salts, and various modified amines used as a curing agent for epoxy resins. Preferred are 3-aminopropyltrimethoxysilane. , 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 also referred to as “organometallic compound (5)”), a compound having 1 carbon atom bonded to the same tin atom. Examples thereof include an organic metal compound of tetravalent tin having 1 to 2 alkyl groups of 10 to 10 (hereinafter, also referred to as “organotin compound”), or a partial hydrolyzate 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 each represents an ethyl group 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. R ¹⁰ represents a divalent hydrocarbon group;
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. An organic zirconium compound;

(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 monoacetylacetonatobis (ethylacetoacetate) aluminum; and the like.

Among these organometallic compounds (5) and their partial hydrolysates, 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 ,

[0068] (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 ,

Mercaptide-type organotin compounds such as (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) | O | (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ );

(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 S
organic tin oxides such as nO and (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; and the like.

The component (c) 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 (c) may be blended when preparing the composition, or may be blended with the composition at the stage of forming a coating film. May be blended in both stages. The amount of the component (c) used is
In the case other than an organometallic compound or the like, (R)
¹⁾ with respect to _{n SiO (4-n) /} 2 in the structural unit 100 parts represented generally 0 to 100 parts by weight, preferably, 0.
01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight. In the case of an organometallic compound or the like, it is represented by (R ¹ ) _n SiO _{(4-n) / 2} in the component (a). Structural unit 10
0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 100 parts by weight, based on 0 parts by weight.
50 parts by weight. In this case, the amount of the component (c) used is 1
If the amount is more than 00 parts by weight, the storage stability of the composition tends to decrease, and cracks tend to occur in the coating film.

Component (d): Component (d) 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 those in the organometallic compound (5). Is the same as R ⁹ and R ^{10 in} each of the above general formulas], which 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 kind. Such a component (d) is particularly preferably used together when an organometallic compound or the like is used as the component (c).

The component (d) acts as a stability improver for the composition. That is, the component (d) coordinates to a metal atom such as the above-mentioned organometallic compound, and promotes the co-condensation reaction of the above-mentioned component (a) with the component (b) or the component (b ′) by the organometallic compound or the like. It is presumed that by appropriately controlling the action of the composition, the action of further improving the storage stability of the obtained composition is achieved.

Specific examples of the component (d) 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 (d) can be used alone or in combination of two or more.

The amount of the component (d) is usually 2 to 1 mol 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 (e) is less than 2 mol, the effect of improving the storage stability of the obtained composition tends to be insufficient.

Component (e): Component (e) is composed of a powder and / or sol or 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 (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-mentioned colloidal silica is snowtex, isopropanol silica sol, methanol silica sol (all manufactured by Nissan Chemical Industry Co., Ltd.); ); Syton (manufactured by Monsanto Co., USA); Nalcoag (manufactured by Nalco Chemical Co., USA). Further, as the above colloidal alumina, for example, synthetic alumina, boehmite, pseudo-boehmite and the like can be used. Such colloidal alumina is, for example, alumina sol 100, alumina sol 5
20 (all manufactured by Nissan Chemical Industries, Ltd.). Further, as the component (e), TiO ₂ (preferably containing an anatase type) is used to impart photocatalytic ability, and Ce is used to impart ultraviolet absorbing ability.
It is preferable to use O ₂ , ZnO, or the like.

The average particle size of component (e) is preferably 30
μm or less, more preferably 0.005 to 20 μm, and still more preferably 0.005 to 10 μm. If the average particle size exceeds 30 μm, the surface of the obtained coating film may not be smooth.

The component (e) 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 used after being diluted with water or a solvent, or may be used after surface treatment to improve the dispersibility.
When the component (e) is an aqueous sol or colloid, or a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less.

As a method of blending the component (e) into the composition, the component (e) may be added after the preparation of the composition, or may be added during the preparation of the composition, and the component (e) may be added to the composition (a). It may be co-hydrolyzed / condensed with the component, component (b) or component (b ′).

The amount of the component (e) used is determined by the structural unit 100 (R ¹ ) _n SiO _{(4-n) / 2} in the component (a).
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.

Other additives: The coating composition and undercoat composition of the present invention may be used for coloring, thickening, improving coatability, or imparting functions such as ultraviolet absorption to the resulting coating film. In addition, a filler can be separately added and dispersed. Such fillers include, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, particulate, fibrous or flaky ceramics, metals or alloys, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like. However, as the other additives, the above-mentioned component (e) is excluded.

Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigments, 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 plumbate, 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.

The coating composition and the undercoat composition of the present invention may further include a salicylic acid-based composition, if desired.
Organic ultraviolet absorbers such as benzophenone, benzotriazole, cyanoacrylate, and triazine;
UV stabilizers such as piperidine; methyl orthoformate;
Known dehydrating agents such as methyl orthoacetate and tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphoric acid Dispersants such as salts, polyacrylates, polyamide ester salts, and polyethylene glycol; methylcellulose, ethylcellulose,
Cellulosics such as hydroxyethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose, and thickeners such as castor oil derivatives and ferrosilicates; inorganic foams such as ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrite, sodium borohydride and calcium azide Compounds, azo compounds such as azobisisobutyronitrile, diphenylsulfone-3,3 '
-In addition to organic blowing agents such as hydrazine compounds such as disulfohydrazine, semicarbazide compounds, triazole compounds, N-nitroso compounds, and other additives such as surfactants, silane coupling agents, titanium coupling agents, and dyes You can also.

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 .; and Fluornal TF series manufactured by Toho Chemical Co., Ltd .; BYK series; Shmegma
nn) Shfmego series; Efka Chemicals Efka 30, Efka 31, Efka 34, Efka 3
5, Efka 36, Efka 39, Efka 83, Efka 8
6, Efka 88 and the like, and examples of the ether-based or ester-based leveling agent include Carfinol of Nissin Chemical Industry Co., Ltd .;

By blending 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.

Further, the composition of the present invention may contain an antibacterial agent and an antifungal agent. As antibacterial and antifungal agents,
Carriers such as synthetic zeolite, calcium phosphate, zirconium phosphate, vanadium phosphate, calcium silicate, silica gel, amino acids, metal soaps, ceramics, apatite, activated carbon, montmorinite, and low molecular glass are supported on metals such as silver, copper, and zinc. Metal ion-supported inorganic antibacterial agents; phenol ether derivatives, sulfone derivatives, imidazole derivatives, oxybisphenoxyarsine, organic nitrogen sulfur compounds, nitrile derivatives, benzothiazole derivatives, isothiazole derivatives, thiadiazole derivatives, triazine derivatives, pyrroles Organic antibacterial agents such as derivatives and aliphatic imide derivatives. The amount of antimicrobial agent used is preferably less than 5% by weight, based on the total composition.

The resin used in the present invention, preferably the undercoating compositions (i) to (ii), may be blended with another resin. Other resins include acrylic
Examples include urethane resin, epoxy resin, polyester, acrylic resin, fluorine resin, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion, and polyester emulsion.

In preparing the coating composition and the undercoating composition of the present invention, the components (c) and (d)
When the component is not used, the method of mixing the components is not particularly limited. When the component (c) and the component (d) are used, preferably, (d) of the components (a) to (e) is used. After obtaining a mixture excluding the component (d), a method of adding the component (d) to the mixture is adopted.

Specific examples of the method for preparing the coating composition of the present invention include the following methods. Organosilanes (1), (b) constituting component (a)
A method in which a predetermined amount of water is added to a mixture composed of the component, the component (c), and a required amount of an organic solvent to perform a hydrolysis / condensation reaction, and then the component (d) is added. A predetermined amount of water is added to a mixture of the organosilane (1) constituting the component (a) and a required amount of an organic solvent to carry out a hydrolysis / condensation reaction, and then the components (b) and (c) are mixed. A method of adding, mixing and further performing a condensation reaction, and then adding the component (d).

A predetermined amount of water is added to a mixture of the organosilane (1), the component (c), and the required amount of the organic solvent, which constitute the component (a), to carry out a hydrolysis / condensation reaction. A method in which the components are added and mixed, a partial condensation reaction is further performed, and then the component (d) is added. (A) a part of the organosilane (1) constituting the component,
A predetermined amount of water is added to a mixture composed of the component (b), the component (c), and a required amount of an organic solvent to carry out a hydrolysis / condensation reaction, and then the remainder of the organosilane (1) is added.
After further hydrolysis / partial condensation reaction, (d)
How to add components.

In the present invention, (a) to (b)
The components and the components other than the components (c) to (d) can be added at an appropriate stage of preparing the composition.

The total solid content of the coating composition of the present invention is usually 50% by weight or less, preferably 2 to 40% by weight, and is appropriately adjusted according to the purpose of use. If the total solid content of the composition exceeds 50% by weight, storage stability tends to decrease.

The total solid content of the undercoating compositions (i) to (ii) which may be used in the present invention is usually
50% by weight or less, preferably 40% by weight or less;
It is appropriately adjusted according to the type of the base material, the coating method, and the coating film thickness.

Method of Forming Snow / Ice Prevention Coating Film The article having a snow / icing prevention coating film may be composed of, for example, a base material / the coating composition of the present invention, a base material / Any of the compositions (i) to (ii) of the present invention / the coating composition of the present invention, or the substrate / primer / any of the above compositions (i) to (ii) for undercoat / the coating composition of the present invention Things. Coating composition of the present invention and composition (i) to undercoat described above
When applying (ii) to a substrate, in the case of any composition, use a brush, a roll coater, a flow coater, a gravure coater, a centrifugal coater, an ultrasonic coater, etc., dip coat, flow coat, spray , Screen process, electrodeposition, vapor deposition and the like.

In the case of the coating composition of the present invention, the dry thickness is about 0.05 to 30 μm in a single application.
In the second coating, a coating film having a thickness of about 0.1 to 60 μm can be formed. Thereafter, the coating film can be formed by drying at normal temperature or by heating and drying at a temperature of about 30 to 200 ° C., usually for about 1 to 60 minutes.

When the undercoat is applied in advance,
Using the above compositions (i) to (ii), a dry film thickness of 1
The second coating can form a coating film having a thickness of about 0.05 to 30 μm and the second coating can have a thickness of about 0.1 to 60 μm. Then, dry at room temperature, or 30 ~ 20
By heating and drying at a temperature of about 0 ° C. for about 1 to 60 minutes, a coating film can be formed on various types of wallpaper base materials. The total film thickness of the undercoat and the top coat is a dry film thickness, usually 0.1 to 80 μm, preferably 0.2 to 80 μm.
It is about 60 μm.

Further, when a primer is used depending on the application, the type of the primer is not particularly limited as long as it has an action of improving the adhesion between the substrate and the composition. Select according to the purpose of use. The primers can be used alone or in combination of two or more, and may contain coloring components such as pigments and dyes.

Examples of the type of primer include alkyd resin, aminoalkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluororesin, acrylic silicone resin, acrylic melamine resin, acrylic resin emulsion, epoxy resin emulsion, and polyurethane emulsion And polyester emulsions. Also, these primers
When the adhesion between the substrate and the coating film under severe conditions is required, various functional groups can be provided. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, an ester bond, and the like. Furthermore, the primer has an ultraviolet absorber,
An ultraviolet stabilizer or the like may be blended.

Further, on the surface of a coating film formed from the coating composition of the present invention, for example, US Pat.
Forming a clear layer composed of a siloxane resin-based coating such as a stable dispersion of colloidal silica and a siloxane resin described in US Pat. No. 6,997, US Pat. No. 4,027,073 and the like. You can also.

Examples of the article substrate to which the composition of the present invention can be applied include articles in which snow and icing are problematic, for example, transmission lines,
Power transmission tower, tower for parabolic antenna, ski lift base material,
Roofing materials, outer walls, antennas, ship exterior materials, aircraft exterior materials,
Examples include tent base materials, solar cells, car windows, road materials, signs, traffic lights, outdoor monitors, various optical equipment lenses, outdoor measurement and observation equipment, and the like. Examples of the material of these substrates include metals such as iron, aluminum and stainless steel; cement, concrete, ALC, flexible board, mortar, slate, enamel, marble, ceramic tile, porcelain tile, gypsum, calcium silicate, Inorganic ceramic materials such as ceramics, brick, wood chip cement board, etc .; phenolic resin, epoxy resin, polyester, polycarbonate, polyethylene, polypropylene, AB
S resin (acrylonitrile-butadiene-styrene resin), fluororesin (PTFE, ETFE, FEP, PF)
A) plastic molded products such as polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, polyimide, fluororesin (PTFE, ETFE, FEP, P
FA, etc.), wood, paper,
Glass etc. can be mentioned. The plastic molded product and the plastic film may contain reinforced glass fiber (FRP). Further, as a substrate for electric materials such as solar cells, a vapor-deposited film such as ITO may be formed on a glass substrate. The composition of the present invention is also useful for repainting a deteriorated coating film. The composition of the present invention can also be applied to a silicon caulking material provided for adhesion and sealing between panels on the outer wall / inner wall and between window panels and the like.

These substrates may be subjected to a surface treatment in advance for the purpose of adjusting the base, improving the adhesion, filling the porous substrate, smoothing, and patterning. Examples of the surface treatment on the metal-based substrate include polishing, degreasing, plating, chromate treatment, flame treatment, and coupling treatment. Examples of the surface treatment on the plastic-based substrate include blasting, 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 The surface treatment for the wood substrate, for example, polishing, filling, insect repellent treatment and the like,
As the surface treatment for the paper base material, for example,
Insect repellent treatment and the like can be mentioned, and as the surface treatment for the degraded coating film, for example, kelenium and the like can be mentioned.

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, if it is necessary to prevent rust, a primer is used in addition to the undercoating coating composition. ), The opacity of the coating film differs depending on the type, and a primer may be used in some cases. In the case of repainting a deteriorated coating film, a primer is used when the old coating film is significantly deteriorated. In the case of other substrates, for example, plastic, wood, paper, glass, etc., a primer may or may not be used depending on the application.

[0108]

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 and evaluations in Examples and Comparative Examples were performed by the following methods.

(1) Mw 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 to which the curing accelerator was not added was sealed and stored 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 with a BM viscometer manufactured by Tokyo Keiki Co., Ltd., and those with a change rate of 20% or less were evaluated as “good”. (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. Those that did not change were regarded as “good”. (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. Those that did not change were regarded as “good”. (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. Those that did not change were regarded as “good”. (8) Weather Resistance According to JIS K5400, an irradiation test was carried out for 3,000 hours with a sunshine weather meter, and the appearance (crack, peeling, etc.) of the coating film was visually observed. Those that did not change were regarded as “good”.

(9) Water Resistance After the test piece was immersed in tap water at room temperature for 60 days, the state of the coating film was visually observed. Those that did not change were regarded as “good”. (10) Warm Water Resistance The test piece was immersed in warm water at 60 ° C. for 14 days, and the state of the coating film was visually observed. Those that did not change were regarded as “good”. (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) Transparency Each composition was applied on a 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. ◎: The transmittance exceeds 80% ○: The transmittance is 60 to 80% △: The transmittance is less than 60% (Fall angle) was measured. ；: Falling angle is less than 50 degrees ○: Falling angle is 50 to 70 degrees △: Falling angle exceeds 70 degrees (14) Contact angle Ultra pure water as water or coal tar as oil on the coating film (JIS K2439 regulation 3μ for coal tar)
The contact angle when l was placed was measured by an automatic contact angle meter manufactured by Kyowa Interface Chemical Co., Ltd.

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, 30 parts of ethyl vinyl ether, and peroxide in the autoclave were added. 2 parts of lauroyl (radical polymerization initiator) was charged, and the solution in the autoclave was dried with dry ice.
After cooling to −50 ° C. with methanol, oxygen in the system was removed again with nitrogen gas. Next, 20 parts of hexafluoropropylene, 45 parts of perfluoro (methyl vinyl ether) and 5 parts of vinyltrimethoxysilane were added, and the temperature was raised. The temperature inside the autoclave is 60 ° C
The pressure in the autoclave at the time of reaching 5 kg
f / cm ² . The polymerization reaction was continued for 20 hours by stirring while maintaining the temperature of the reaction system at 60 ° C. When the pressure in the autoclave dropped to 1.5 kgf · cm ² , the reaction was stopped by water cooling to stop the solid content. Concentration 4
0% of the component (b) (hereinafter, also referred to as “(B-1)”) was obtained.

Reference Examples 2 to 5 <Polymerization of Component (b)> The procedures of (B-2) to (B-5) were carried out in the same manner as in Reference Example 1 except that the monomer components shown in Table 1 were used. (B) The component was obtained.

[0116]

[Table 1]

Reference Example 6 <Synthesis of Silyl Group-Containing Vinyl Polymer (b ′)> In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 40 parts of n-butyl acrylate, and γ-methacryloxypropyl tri 20 parts of methoxysilane, 5 parts of acrylic acid, 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.
The mixture was heated to 80 ° C. with stirring, a solution of 4 parts of azobisisovaleronitrile dissolved in 10 parts of xylene was added dropwise to the mixture over 30 minutes, and the mixture was reacted at 80 ° C. for 5 hours to obtain a solid concentration of 40%. To obtain a silyl group-containing vinyl polymer solution (b′-1).

Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 and 2 Tables 2 and 3 were placed in a reactor equipped with a reflux condenser and a stirrer.
(Excluding water and post-additional components) were added and mixed. After adding water, the mixture was stirred and reacted at 60 ° C. for 5 hours. Next, the post-addition component was added and the mixture was cooled to room temperature to obtain coating compositions (A) to (K) of the present invention and comparative compositions (a) and (b) having a solid content of 20%. The storage stability of the obtained composition was evaluated. The evaluation results are shown in Tables 2 and 3.

[0119]

[Table 2]

[0120]

[Table 3]

(* 1): Zinc oxide dispersed in toluene (solid content 30%) (* 2): Water-dispersed (pH 4) anatase type titanium oxide (solid content 30%) (* 3): Particle diameter 0.1 μm

Reference Example 7 <Synthesis of Undercoating Coating Composition> In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyltrimethoxysilane, 30 parts of glycidoxypropyltrimethoxysilane, 20 parts of water, i -Propyl alcohol 15
0 parts and 20 parts of a 10 ^-2 mol / l hydrochloric acid aqueous solution were added, and the mixture was stirred well and reacted at 60 ° C for 4 hours. Then, the mixture was cooled to room temperature, and zinc oxide dispersed in toluene (solid content concentration 30%) 2
By adding 0 parts, a composition having a solid content of 20% was obtained. 100 parts of the obtained composition was mixed with i-propyl alcohol 10
After 0 parts were added and mixed well, 10 parts of an i-propyl alcohol solution (solid content: 15%) of a reaction product composed of dibutyltin diacetate and a silicate oligomer was added, and the mixture was stirred well, and the undercoating coating composition (i-1) was added. ) Got.

Reference Examples 8 to 10 <Synthesis of Undercoating Coating Composition> To a reactor equipped with a reflux condenser and a stirrer, the components (types and parts) shown in Table 4 (other than the components added later) were added. The mixture was stirred well and reacted at 60 ° C. for 4 hours. Next, the mixture was cooled to room temperature, and post-additional components were added to obtain a composition having a solid content of 20%. After 100 parts of i-propyl alcohol was added to 100 parts of the obtained composition and mixed well, 10 parts of an i-propyl alcohol solution (solid content: 15%) of a reactant composed of dibutyltin diacetate and a silicate oligomer was added. After stirring well, the undercoating coating composition (ii-
1) to (ii-3) were obtained.

[0124]

[Table 4]

(* 1) Polyester resin manufactured by Takamatsu Yushi Co., Ltd. (solid content: 20%)

Reference Example 11 <Preparation of Undercoat Coating Composition> 100 parts by weight of the solution (b′-1) obtained in Reference Example 6 was
80 parts by weight of methyl ethyl ketone and 20 parts by weight of i-propyl alcohol were added and stirred well, and
% Undercoat coating composition (p-1).

Examples 1 to 15 and Comparative Examples 1 and 2 A coating material for undercoating and a coating composition of the present invention, if necessary, were dried on a ceramic substrate having a thickness of 1.5 cm to a dry film thickness of 2 μm. And dried to obtain a sample. Various evaluations were performed on the obtained samples. The results are shown in Tables 5 to 7.

[0128]

[Table 5]

[0129]

[Table 6]

[0130]

[Table 7]

Examples 14 to 20 The undercoating coating composition shown in Table 8 was applied to each of the substrates shown in Table 8 as required so that the dry film thickness became 10 μm, and dried. The coating composition of the present invention described in (1) was applied to a dry film thickness of 2 μm and dried to obtain a sample. The obtained sample was evaluated for adhesion and weather resistance. The results are also shown in Table 8.

[0132]

[Table 8]

[0133]

The coating composition for preventing snow and ice formation according to the present invention contains a specific organosilane component and a fluoropolymer having a silyl group, so that it has excellent storage stability and adhesion. It has a function of preventing snow and ice formation by water repellency and oil repellency without deteriorating alkali resistance, organic chemical resistance, weather resistance, moisture resistance, water resistance (warm) water resistance and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H020 AA03 AA04 AB01 4J002 CP031 CP061 EX046 FD146 GH00 4J038 CD092 CE052 DL021 DL031 GA12 JC32 NA06

Claims (3)

[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
At least one kind, and (b) (b-1) the following general formula
Structural unit represented by (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) represented by the following general formula (3).
Constituent units[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 a silicon source bonded to a hydrolyzable group and / or a hydroxyl group.
Selected from the group of polymers containing silyl groups
Prevention of snow and icing, characterized by containing at least one species
Coating composition. 2. A method for forming a coating film for preventing snow and ice formation, comprising forming a coating film comprising the coating composition for preventing snow and ice formation according to claim 1 on the surface of an article. . 3. A coating film comprising the composition of the following (i) or (ii) is formed, and a coating film comprising the coating composition for preventing snow and ice formation according to claim 1 is formed thereon. A method for forming a coating film for preventing snow and icing, comprising: (I) (a) The following general formula (1) (R ¹ ) _n Si (OR ² ) _4-n ... (1) (wherein, when two R ¹ are present, they are the same or different. Represents a monovalent organic group having 1 to 8 carbon atoms, R ² represents the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 2 Is.)
A coating composition comprising at least one selected from the group consisting of an organosilane represented by the following formula, a hydrolyzate of the organosilane, and a condensate of the organosilane. (Ii) A coating composition containing the component (a) and (b ′) a polymer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group.