JPH08337771A - Anti-fouling agent, coating composition, surface treatment method and outdoor article - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a coating composition, a stain-preventing agent, a surface treatment method, and an outdoor article which are excellent in stain-proofing property and stain-removing property, and also excellent in water resistance and durability. [Structure] (A) Formula (I): Z—X—O—R _f (I) (In the formula, Z is an organic group having or not having a functional group, and X is C═O or SO ₂ , R _f is an organic group in which some or all of hydrogen atoms have been replaced by fluorine atoms and may contain oxygen atoms). Use inhibitors.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stain adhesion preventing agent, a coating composition, a surface treatment method and an outdoor article.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of maintaining aesthetics and emphasizing landscape,
Various analysis and prevention methods for stains on building exteriors and vehicle exteriors have been studied. Especially for dirt carried by rainwater in urban areas, the function of preventing dirt from adhering and accumulating (anti-contamination adhesion), adhering and accumulating Even so, there is a demand for an exterior material having an excellent function (contamination removing property) that can be easily removed by washing.

A method such as increasing the crosslink density of the coating film is effective for improving the stain-removing property, and the surface of the article is made hydrophilic (the contact angle with water is lowered to improve the stain-adhering property). ) Is known to be effective. When improving the stain-adhesion property, if the entire coating film is made hydrophilic, problems occur in water resistance and durability of the coating film. Therefore, a method of efficiently making only the coating film surface hydrophilic is suitable.

A composition comprising a coating resin in which a hydrophilic carboxylate or sulfonate structure is introduced in order to improve stain adhesion is disclosed in, for example, JP-A-6-179790. However, since an ionic hydrophilic group is present almost all over the coating film, the water resistance of the coating film is inferior, and the effect is insufficient because it adversely affects various paint additives and pigments, which adversely affects the curing reactivity. There were drawbacks such as reaching

Further, latent carboxylic compounds are disclosed in Japanese Patent Application Laid-Open Nos. 4-2181561, 5-86297 and 5-86298, but the carboxyl groups are also present in almost the entire coating film. Since it is present, the coating film is inferior in water resistance, and the blocked functional group mainly functions in the cross-linking reaction, so that it has a drawback that the hydrophilicity of the surface is insufficient.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a coating composition which is excellent in antifouling adhesion and stain removability, and also excellent in water resistance and durability, and an antifouling agent used in the composition. Another object of the present invention is to provide a surface treatment method using the composition and an outdoor article obtained by the treatment method using the composition.

[0007]

The present invention provides (A) formula (I): Z-X- _ORf (I) (wherein Z is an organic compound having or not having a functional group). Group, X is C═O or SO ₂ , and R _f is an organic group in which some or all of hydrogen atoms are substituted with fluorine atoms and may contain an oxygen atom). The present invention relates to an anti-contamination agent comprising a compound having a fluorine protecting group.

Further, the present invention comprises 1 to 100 parts by weight of the (A) anti-fouling agent, (B) 100 parts by weight of a cross-linkable functional group-containing coating resin, and (C) a curing agent and / or a curing catalyst. The present invention relates to a coating composition.

The present invention also relates to a coating composition comprising the solvent-soluble fluoroolefin copolymer having the above-mentioned thermally dissociable fluorine-containing protecting group and hydroxyl group, and (C) a curing agent and / or a curing catalyst.

Further, the present invention relates to a method of coating the surface of a coating film with an alkali or an acid after coating any one of the above-mentioned stain-adhesion preventing agents or coating compositions.

Furthermore, the present invention relates to an outdoor article obtained by applying any one of the above-described stain-adhesion preventing agent or coating composition, or treating by the above-mentioned surface treatment method.

[0012]

ACTION AND EXAMPLE In the present invention, antifouling adhesion,
Although it is not clear why the effect of excellent decontamination property is obtained, the following may be considered, for example.

In the formula (I) of the above (A), R _f is thermally dissociable, so that the thermal dissociation causes a hydrophilic group such as a carboxylic acid group, a sulfonic acid group or an amino group to occur, and in particular R _f
When R has a fluorine atom, R _f is concentrated on the surface, so that the hydrophilic group is concentrated on the surface, and it is considered that an excellent effect can be obtained.

Further, R _f is _expressed by the formula (II)

[0015]

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In the case of the organic group represented by, it is considered that the carbon atom to which R ¹ is bonded has an acetal structure and has a high thermal dissociation property, so that an excellent effect can be obtained.

Further, R _f is represented by the formula (III)

[0018]

[Chemical 4]

In the case of the organic group represented by, since the fluorine atom is bonded to the group adjacent to the carbon atom to which R ¹ is bonded, the thermal dissociation property is high due to the electron withdrawing effect of the fluorine atom, which is excellent. It is considered that the effect can be obtained.

Further, in the formula (I) of the above (A), Z
Has no functional group, the surface migration property or surface concentrating property is good, and when Z has a functional group, it is bonded to the coating film by a chemical bond, so that the durability is good. It is considered that the effect can be obtained.

In the formula (I), Z is an organic group having or not having a functional group, and X is C═O or SO.
₂ is shown.

The compound represented by the formula (I) has as a raw material a compound having an organic group represented by Z--X, such as a carboxylic acid compound, a sulfonic acid compound and an isocyanate compound.

Of these, Z is, for example, an alkyl group,
When it does not have a functional group such as an aromatic group, the compound represented by the formula (I) can be regarded as a mere additive.

When Z has a non-double bond functional group such as a hydroxyl group, an amino group, an isocyanate group, an epoxy group and an alkoxysilyl group, the compound represented by the formula (I) is Through this functional group, for example, because it reacts with the coating resin or curing agent described later,
It can be said to be a reactive additive.

Further, when Z has a double-bonding functional group such as a vinyl group, the compound represented by the formula (I) is a monomer containing a thermally dissociable fluorine-containing protecting group described below, that is, a polymer. It can be said that it is a sex additive.

Examples of the carboxylic acid compound include monocarboxylic acid, polycarboxylic acid, hydroxy group-containing monocarboxylic acid, hydroxy group-containing polycarboxylic acid, and the like, from the viewpoint of reactivity with a curing agent and surface concentration. A hydroxy group-containing monocarboxylic acid or the like is preferable.

As the monocarboxylic acid, for example, acetic acid,
Examples of the polycarboxylic acid include propionic acid and the like, and examples of the polycarboxylic acid include succinic acid, a hydroxy group-containing carboxylic acid,
Adipic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, carboxyl group-containing solvent-soluble fluoroolefin copolymer, polyacrylic acid, carboxyl groups at both ends Examples thereof include polyesters, and solvent-soluble fluoroolefin copolymers containing carboxyl groups are preferred from the viewpoint of weather resistance.

Examples of the hydroxy group-containing monocarboxylic acid include 4-hydroxybutanoic acid, 3-hydroxybutanoic acid, 12-hydroxystearic acid and 2,2-
Examples thereof include a reaction product of bis (hydroxymethyl) propionic acid or a dicarboxylic acid anhydride with a diol, and a reaction product of a dicarboxylic acid anhydride with a diol is preferable from the viewpoint of reactivity of a hydroxyl group.

Examples of the dicarboxylic acid anhydride include succinic acid, hydroxy group-containing carboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, and 4-methyl-1,2-cyclohexanedicarboxylic acid anhydride. The cyclic acid anhydride is preferable from the viewpoint of reactivity of the acid anhydride.

Examples of the diol include ethylene glycol, 1,4-butanediol, and 1,4-dihydroxycyclohexane. Among them, 1,4-butanediol is preferable from the viewpoint of reactivity of hydroxyl group.

Examples of the hydroxy group-containing polycarboxylic acid include hydroxyl group- and carboxyl group-containing (meth) acrylic acid ester copolymers.

Further, derivatives of these carboxylic acids, such as chlorides and anhydrides, can also be mentioned.

Examples of the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, and derivatives of these sulfonic acids such as chlorides. , And anhydrides, but chlorides are preferred from the viewpoint of reactivity.

Examples of the isocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate and hexamethylene. Diisocyanate, n-pentane-1,4-diisocyanate, 2-isocyanatoethyl-2,6-diisocyanatecaproate and their trimers, adducts, burettes, and polymers thereof containing two or more isocyanate groups The thing which has is mentioned. Moreover, the thing etc. which modified these with polyethylene oxide or a carboxyl group are also mentioned. Further, among these, from the viewpoint of weather resistance and yellowing resistance, an isocyanate compound containing no aromatic group, such as a hexamethylene diisocyanate derivative or an isophorone diisocyanate derivative, is preferable.

The other raw material for the compound represented by formula (I) may be any compound capable of reacting with the above raw material to introduce R _f into the compound.

In the formula (I), R _f is an organic group in which some or all of hydrogen atoms have been replaced by fluorine atoms and which may contain oxygen atoms.
_It is a fluorine-containing protecting group having a thermal dissociation property such that a fluorine-containing group or the like is eliminated when the _f group decomposes or a part of the bond dissociates.

The compound represented by the above formula (I) may have only one heat dissociable fluorine-containing protecting group R _f ,
Moreover, you may have two or more. In particular, when only one R _f is included, the compatibility and the solubility are excellent.

Examples of R _f as described above include formula (II):

[0039]

Embedded image

(In the formula, R ¹ , R ² and R ³ are the same or different and each is a hydrogen atom or an organic group having 1 to 18 carbon atoms and optionally containing a fluorine atom, and R ⁴ is 1 to 1 carbon atoms.
18 is an organic group in which some or all of the hydrogen atoms are replaced by fluorine atoms), formula (III):

[0041]

[Chemical 6]

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different, and each is a hydrogen atom or has 1 carbon atom.
To 18 are organic groups in which some or all of hydrogen atoms may be substituted with fluorine atoms, and at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom-containing group. A) or an organic group represented by a fluorine-containing organic group containing a nitrogen atom or a sulfur atom, etc., but from the viewpoint of storage stability, thermal dissociation property, and easy availability, the formula (II) or the formula (III) Organic groups represented by are preferred.

In the formula (II), R ¹ , R ² and R ³
The number of carbon atoms in the is 0 from the viewpoint of ease of synthesis and thermal dissociation.
It is -18, and it is preferable that it is 0-2. The carbon number of R ⁴ is 1 to 1 from the viewpoint of stability, thermal dissociation and desorption.
It is 18 and preferably 2 to 9, and since some or all of hydrogen atoms are replaced with fluorine atoms, the surface concentrating property is excellent.

Examples of the compound which can be the organic group represented by the formula (II) include fluorine-containing vinyl ether,
Examples thereof include a cyclic fluorine-containing vinyl ether and a fluorine-containing isopropenyl ether, but a fluorine-containing vinyl ether is preferable from the viewpoint of stability, thermal dissociation property, and easy availability.

Examples of the fluorine-containing vinyl ether include CH ₂ ═CH—O—R ^* _f [wherein R ^* _f is F (C
_{F 2) q (CH 2)} p, (CF 3) 2 CH, CF 3 CHFCF 2
_{CH 2, H (CF 2)} q (CH 2) p (p is 0 or 1-6
, Q is an integer of 1 to 10, some of the fluorine atoms may be substituted with chlorine atoms, and these fluorine-containing alkyl chains may represent not only straight chains but also branched chains.] Something is included.

Specific examples of the fluorine-containing vinyl ether include 2,2,3,3,3-pentafluoropropyl vinyl ether, 2-perfluorooctylethyl vinyl ether, 2,2,2-trifluoroethyl vinyl ether, and CH ₂ ═. _{CH-O-CH 2 CH 2} C 4 F 9, C
_{H 2 = CH-O-CH} 2 CF 2 CF 2 H, CH 2 = CH-O
_{-CH 2 CF 2 CFHCF 3, CH} 2 = CH-O-CH
₂ (CF ₂ CF ₂ ) ₂ H and the like, surface concentrating properties,
From the viewpoint of easy availability, 2,2,3,3,3-pentafluoropropyl vinyl ether and 2-perfluorooctylethyl vinyl ether are preferable.

In the case of reacting with the compound having an organic group represented by Z-X-, a fluorine-free vinyl ether may be used in combination. Examples of the vinyl ether include ethyl vinyl ether, butyl vinyl ether and isobutyl. Examples thereof include vinyl ether and 3,4-dihydro-2H-pyran.

Examples of the compound which can be the organic group represented by the formula (III) include fluorine-containing alcohol, fluorine-containing oxime, fluorine-containing caprolactam, and fluorine-containing β.
A carbonyl carbonyl compound (eg 1,1,1,
5,5,5-hexafluoro-2,4-pentanedione, etc.) can also be used, and in addition to these fluorine-containing compounds, phenol, caprolactam,
Compounds such as MEK oxime and β-diketone can be used together with the fluorine-containing compound, but the fluorine-containing alcohol is preferable in terms of stability, thermal dissociation property, and easy availability.

Examples of the above-mentioned fluorine-containing alcohol include F (CF ₂ ) _q (CH ₂ ) _q OH, (CF ₃ ) ₂ CHOH,
_{CF 3 CHFCF 2 CH 2 OH,} H (CF 2) q (CH 2) p
OH (in the formula, p is 0 or an integer of 1 to 6, and q is 1 to 10)
And a part of the fluorine atoms may be substituted with chlorine atoms, and these fluorine-containing alkyl chains may be not only straight chains but also branched chains). Of these, secondary and tertiary fluorine-containing alcohols are preferable because they are easily removed as a protective group.

Specific examples of the fluorine-containing alcohol include, for example, 1,1,1,3,3,3-hexafluoro-2-
Propanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoroethanol, C
F ₃ CHFCF ₂ CH (CH ₃ ) OH, C ₄ F ₉ CH ₂ CH ₂
OH, CH ₃ (CF ₃ ) ₂ COH, CF ₃ CFHCF ₂ C
Examples thereof include (CH ₃ ) ₂ OH, but from the viewpoint of thermal dissociation, desorption, and easy availability, 1,1,1,3,3,3-
Hexafluoro-2-propanol is preferred.

In the formula (III), it is preferable that R ¹ is a hydrogen atom and R ⁵ is not a hydrogen atom from the viewpoint of thermal dissociation.

Specific examples of the compound represented by the above formula (I) include, for example,

[0053]

[Chemical 7]

Examples thereof include compound (3) and compound (7) from the viewpoints of thermal dissociation property and sustainability of stability effect.

As a method for obtaining the compound represented by the above formula (I), for example, 1 to 10 mol of the compound having an organic group represented by the above Z--X and the above formula (II) or the formula (I)
1 to 50 mol of a compound represented by II) which can be an organic group is used as a reaction solvent in, for example, an aromatic or aliphatic solvent, more specifically, a ketone, an ester or an ether, and an acid, an alkali, or a catalyst as a catalyst. The metal salt was added to 0.
1 to 5 mol% and a reaction temperature of 20 to 120 ° C. of 1 to 10
Let them react for a time.

A coating resin can be added to the coating composition obtained using the compound having a heat-dissociable fluorine-containing protecting group. As the coating resin, for example, a coating resin containing a crosslinkable functional group is preferable, and for example, a hydroxyl group and / or
Alternatively, a solvent-soluble fluororesin coating resin containing a carboxyl group or an alkoxysilyl group-containing acrylic silicone coating resin may be used.

Examples of the solvent-soluble fluorine coating resin containing a hydroxyl group and / or a carboxyl group include, for example, JP-B-60-21686 and JP-A-3-121107.
JP-A-4-279612, JP-A-4-28707,
Examples thereof include those described in JP-A-2-232221, and commercially available products include, for example, Lumiflon manufactured by Asahi Glass Co., Ltd., Zeffle manufactured by Daikin Industries, Ltd., Cefral coat manufactured by Central Glass Co., Ltd., Dainippon Ink ( Examples thereof include Fluoronate manufactured by Toa Gosei Co., Ltd. and Zaflon.

Examples of the solvent-soluble fluorine coating resin containing a hydroxyl group and / or a carboxyl group include a number average molecular weight (by GPC) of 1,000 to 100,000,
It is more preferably used in the range of 1500 to 30,000, and if the molecular weight is within this range, it is excellent in curability, weather resistance, workability and paintability. Preferred hydroxyl value is 10-2
00 (mgKOH / g), preferable acid value is 0 to 100
(MgKOH / g), and when the hydroxyl value and the acid value are within the ranges, curability and flexibility of the coating film are improved.

Examples of the resin for an acrylic silicone coating containing an alkoxysilyl group include, for example, JP-A-7-48540.
Examples thereof include those described in JP-A-Gazette, and examples of commercially available products include Zemlac manufactured by Kanegafuchi Chemical Co., Ltd. and Clearyama manufactured by Sanyo Kasei Co., Ltd.

Other examples of the coating resin include organosilicone inorganic coating resins, acrylic polyols, polyesters, polyurethanes and the like.

Examples of the solvent-soluble fluoroolefin copolymer having the heat-dissociable fluorine-containing protective group and the hydroxyl group include, for example, vinylic functional group-containing carboxylic acid compounds, vinylic functional group-containing isocyanate compounds and vinylic functional groups. A thermally dissociable fluorine-containing protective group-containing monomer (that is, Z in the formula (I) is a double bond functional group) obtained from the sulfonic acid compound contained therein and the above-mentioned fluorine-containing alcohol or fluorine-containing vinyl ether. Of a carboxylic acid compound containing a carboxylic acid compound containing a vinylic functional group, a carboxylic acid compound containing a vinylic functional group, a carboxylic acid compound containing a vinylic functional group, a monomer containing an ionic group, and the like. To be

Among these monomers, fluoroolefins and hydroxyl group-containing monomers are preferable from the viewpoint of weather resistance.

Examples of the hydroxyl group-containing monomer include 4-hydroxybutyl vinyl ether, 2- (2-hydroxyethoxy) ethyl vinyl ether, allyl alcohol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether and polyethylene glycol monoallyl ether. However, 4-hydroxybutyl vinyl ether is preferable from the viewpoint of copolymerizability with fluoroolefin, polymerization stability, and easy availability.

Examples of the carboxylic acid compound containing a vinylic functional group include vinyl acetic acid, crotonic acid, 3-allyloxypropionic acid, and a reaction product of the hydroxyl group-containing monomer with the dicarboxylic acid anhydride. From the viewpoint of copolymerizability with olefin and stability of the monomer, 3-allyloxypropionic acid is preferable.

Examples of the above-mentioned vinyl functional group-containing isocyanate compound include a reaction product of the above hydroxyl group-containing monomer and the above diisocyanate.

Examples of the vinyl functional group-containing sulfonic acid compound include vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, C ₄ H ₉ OCO-CH ₂ -CH (SO _{3
H) -CO 2 CH 2 CH =} CH 2, CH 2 = CHCH 2 O
(CH ₂₎ (wherein, n an integer of 1 to 5) _n -SO ₃ H has and the like, CH ₂ = CHCH ₂ from the viewpoint of polymerization reactivity
_{O (CH 2) 3 -SO 3} H is preferred.

Examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and the like.
Tetrafluoroethylene is preferable from the viewpoint of polymerization reactivity.

Examples of the vinyl ethers include ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, but butyl vinyl ether is preferred from the viewpoint of easy availability.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl pivalate,
Examples thereof include vinyl versatate, vinyl benzoate, and vinyl p-t-butylbenzoate, with vinyl pivalate and vinyl benzoate being preferred from the viewpoints of weather resistance, easy availability, and polymerization reactivity.

Examples of the allyl ethers include allyl alcohol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, and glycerol monoallyl ether. From the viewpoint of easy availability, ethylene glycol is used. Monoallyl ether is preferred.

Examples of the ionic group-containing monomer include C ₄ H ₉ OCO-CH ₂ -CH (SO ₃ Na) -CO.
₂ CH ₂ CH = CH _2, commercially available ELEMINOL JS-2
(Manufactured by Sanyo Kasei Co., Ltd.), CH ₂ = CHCH ₂ O (CH
_{2) n} -SO ₃ Na (wherein, n is an integer of from 1 to 5), the general formula ^{_{R * f OCO-CH 2 -CH}} (SO 3 Na) -CO 2 CH 2 C
H = CH ₂ (R ^* _f is the structure) represented by, for example, _{CF 3 CH 2 OCO-CH 2} -CH (SO 3 Na) -CO 2
_{CH 2 CH = CH 2, CF} 3 CF 2 CH 2 OCO-CH 2 -C
_{H (SO 3 Na) -CO 2} CH 2 CH = CH 2, C 8 F 17 C
_{H 2 CH 2 OCO-CH 2} -CH (SO 3 Na) -CO 2 C
Fluorine-containing ionic monomers having H ₂ CH = CH ₂ and the like can be mentioned, but from the viewpoint of easy availability, Eleminol J
S-2 is preferred.

Specific examples of the solvent-soluble fluoroolefin copolymer having the heat-dissociable fluorine-containing protecting group and the hydroxyl group include, for example, the heat-dissociable fluorine-containing monomer, chlorotrifluoroethylene, ethyl vinyl ether, and 4
-Hydroxybutyl vinyl ether copolymer, copolymer of the heat dissociable fluorine-containing monomer and tetrafluoroethylene, vinyl pivalate, vinyl benzoate, 4-hydroxybutyl vinyl ether, the heat dissociable fluorine-containing monomer and chloro Examples thereof include copolymers of trifluoroethylene, vinyl pivalate, vinyl versatate, 4-hydroxybutyl vinyl ether, and the like. From the viewpoint of weather resistance and stain removal, the thermally dissociable fluorine-containing monomer and tetrafluoroethylene, Copolymers with vinyl pivalate, vinyl benzoate and 4-hydroxybutyl vinyl ether are preferred.

The solvent-soluble fluoroolefin copolymer having a heat-dissociable fluorine-containing protective group and a hydroxyl group and the coating resin containing a crosslinkable functional group are mixed with a curing agent and / or a curing catalyst for crosslinking and curing. it can.

Examples of the curing agent include (block) isocyanates, aminoplasts, oxazolines, siloxanes, aziridines, epoxies, hydrazides, carbodiimides and ketimines. Of these, (blocked) isocyanates are preferable from the viewpoint of actual use.

Examples of (blocked) isocyanates are 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, Hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, 2-isocyanate ethyl-2,6-diisocyanate caproate and trimers thereof, adducts, burettes, and two or more isocyanates of these polymers Having a group,
Furthermore, phenol, caprolactam, MEK oxime,
Examples thereof include isocyanates blocked with β-diketone. Moreover, the thing modified with polyethylene oxide or a carboxyl group is also mentioned.
Further, among these, isocyanates containing no aromatic group are preferable from the viewpoints of weather resistance and yellowing resistance. Among these, the hexamethylene diisocyanate derivative and the isophorone diisocyanate derivative are preferable from the viewpoint of easy availability. Examples of commercially available products include Sumitomo Bayer Urethane Co., Ltd. Desmodur, Sumidule, Takeda Pharmaceutical Co., Ltd. Takenate, Nippon Polyurethane Co., Ltd. Coronate, Asahi Kasei Co., Ltd. Duranate.

Examples of the aminoplasts include methylolmelamines, methylolguanamines and methylolureas. As methylol melamines,
Examples thereof include those etherified with lower alcohols such as butylated methylolmelamine and methylated methylolmelamine, and epoxy-modified methylolmelamine. Examples of the methylolureas include alkylated methylolureas such as methylated methylolurea and ethylated methylolurea. Also included are aminoplasts which are water-soluble or water-dispersible by modifying these with polyethylene oxide or a carboxyl group. Of these, methylolmelamine is preferred from the viewpoint of reactivity and compatibility. When using the above aminoplasts, an acidic catalyst or a blocked acidic catalyst can be used.

Examples of the curing catalyst include dibutyltin dilaurate, dibutyltin acetate, dioctyltin maleate, tetraisopropyl titanate, tetrabutyl titanate, tris (acetylacetonate) aluminum, tetrakis (acetylacetonate) zirconium, diisopropoxybis (ethyl). Examples include organic metal compounds such as acetoacetate) titanate and metal salts, and when isocyanate is used, dibutyltin dilaurate is preferable.

The coating composition of the present invention may contain an elimination reaction catalyst in order to accelerate the elimination reaction of the thermally dissociable fluorine-containing protecting group and enhance the hydrophilicity. Examples of the catalyst include sulfonic acids, sulfonates, ammonium salts, carboxylic acid salts, alkali metal halide compounds, alkaline earth metal halide compounds, and combinations thereof, which include an alkali metal from the viewpoint of hydrophilicity. Compounds are preferred.

Examples of the sulfonic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and 3-hydroxy-1-.
Examples thereof include propanesulfonic acid, and p-toluenesulfonic acid is preferable from the viewpoint of catalytic ability.

Examples of the sulfonates include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and 3-hydroxy-1.
-Metals such as propanesulfonic acid (Li, Na, K, C
a, Mg, Zn, etc.) salts and amine (NH ₃ , methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, etc.) salts and the like, but alkali metal salts are preferable from the viewpoint of hydrophilicity.

Examples of ammonium salts include tetramethylammonium hydroxide, tetramethylammonium hydrogen sulfate, tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetrabutylammonium hydroxide, and the like. Tetrabutylammonium hydrogen sulfate,
Examples thereof include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide, with chloride being preferred from the viewpoint of catalytic ability.

Examples of the carboxylic acid salts include F (C
F ₂ ) _q (CH ₂ ) _p CO ₂ H, H (CF ₂ ) _q (CH ₂ ) _p C
O ₂ H (in the formula, p is 0 or an integer of 1 to 6, q is an integer of 0 or 1 to 10, some of the fluorine atoms may be substituted with chlorine atoms, and the fluoroalkyl chain is a straight chain only) Of course, it may be a branched chain) (Li, Na, K, Ca, M)
g, Zn, etc.) salts and amines (NH ₃ , methylamine, methylamine, dimethylamine, diethylamine,
Examples thereof include trimethylamine and triethylamine, but alkali metal salts are preferable from the viewpoint of hydrophilicity.

Examples of the alkali metal halide compound include lithium fluoride, sodium fluoride, potassium fluoride, lithium chloride, sodium chloride, potassium chloride,
Examples thereof include lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide, and the like, and lithium compounds and sodium compounds are preferable from the viewpoint of solubility.

Examples of the alkaline earth metal halide compound include magnesium fluoride, calcium fluoride, magnesium chloride, calcium chloride, magnesium bromide, calcium bromide, magnesium iodide and calcium iodide.

In the coating composition of the present invention, for example, in order to accelerate the elimination reaction of the thermally dissociable fluorine-containing protecting group,
An amide compound, a tertiary amine compound or an ether compound (hereinafter, also referred to as a donor compound) may be blended if necessary to stabilize the catalyst and / or to enhance the hydrophilicity.

Examples of the amide compound include N, N-
Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylformamide, N-methylacetamide, N-methylpyrrolidone, and polyoxazoline, but N-methylformamide is preferable from the viewpoint of stabilizing ability.

Examples of the tertiary amine compound include alkylamines such as trimethylamine, triethylamine and tributylamine, 1,8-diazabicyclo (5.
4.0) Undecene-7 (DBU), alkaloids (similar) such as (−)-sparteine, azacrown compounds, pyridine, and pyridines such as 2,4,6-trimethylpyridine. Pyridines are preferred from the viewpoint of stabilizing ability.

Examples of the ether compound include cyclic ethers such as tetrahydrofuran, 1,4-dioxane and tetrahydropyran, acetic acid esters such as 2-methoxyethyl acetate and 2- (2-methoxyethoxy) ethyl acetate, ethylene glycol, and the like. Diethylene glycol,
Glycols such as triethylene glycol and polyethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, monoalkyl ethers and dialkyl ethers of polyethylene glycol, dicyclohexano-18-crown-6, dicyclohexano-24-crown- 8, dibenzo 18-crown-6, dibenzo-24-crown-8 and other crown ethers, macrolide compounds and the like can be mentioned, but cyclic ethers are preferable from the viewpoint of stabilizing ability.

Further, the coating composition of the present invention includes, for example, pigments, fillers, coating additives, pigment dispersants, thickeners, leveling agents, silane coupling agents, alkyl silicates, colloidal silicas, and ultraviolet rays. Absorbent, HA
Additives such as LSs, fungicides, and surfactants, coating resins other than the above (for example, organosilicone resins,
Acrylic polyols, polyesters, polyurethanes), solvents and the like can be blended.

Examples of the solvent include hydrocarbon solvents such as xylene, toluene, Solvesso 100, Solvesso 150, and hexane, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene acetate. Ester solvents such as glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol acetate, diethylene glycol acetate, dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monobutyl ether, ethylene glycol Dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and other ether solvents, methyl ethyl ketone, methyl isobutyl ketone, acetone, etc. Ketone solvents, sulfonic acid ester solvents such as dimethylsulfoxide, methanol, ethanol, isopropanol, butanol, CF
₃ CH ₂ OH, F (CF ₂ ) ₂ CH ₂ OH, (CF ₃ ) ₂ CH
OH, F (CF ₂ ) ₃ CH ₂ OH, F (CF ₂ ) ₄ C ₂ H ₅ O
H, H (CF ₂ ) ₂ CH ₂ OH, H (CF ₂ ) ₃ CH ₂ OH,
Examples thereof include alcohol solvents such as H (CF ₂ ) ₄ CH ₂ OH.

The compound having a thermally dissociable fluorine-containing protective group of the present invention can be used not only in coating compositions but also in organic resins, inorganic resins, films, adhesives, etc., and their surfaces are modified. However, it is possible to improve the stain adhesion property, stain removal property, charging property, antifogging property, adhesive property, adhesion property and the like.

The antifouling agent of the present invention has the formula (I) above.
And a compound having a heat dissociable fluorine-containing protecting group.

The mixing ratio of each component for obtaining the coating composition of the present invention will be described.

Resin (1) for coating containing crosslinkable functional group (B)
1 part to 100 parts, preferably 10 to 50 parts, of the above-mentioned (A) antifouling agent with respect to 00 parts (parts by weight, the same applies hereinafter), and (A) is mixed in a ratio within this range. As a result, it is excellent in antifouling adhesion, decontamination, and sustainability of effect.

The mixing ratio of (C) the curing agent and / or the curing catalyst to 1 part of (B) is 1 to 100 parts, preferably 10 to 50 parts. By mixing at a ratio within the range, it has excellent curability, solvent resistance, stain removal property, and weather resistance.

The mixing ratio of the solvent-soluble fluoroolefin copolymer having a heat-dissociable fluorine-containing protecting group and a hydroxyl group to the (C) curing agent and / or curing catalyst is
(C) 0.01 to 1 relative to 1 to 100 parts of the copolymer
It is excellent in excellent anti-fouling property, anti-fouling property, weather resistance, water resistance, and chemical resistance by mixing both in a ratio within these ranges.

The copolymerization ratio of the monomer having a heat dissociable fluorine-containing protecting group in the fluoroolefin copolymer is 1 to 20 mol%, and 2 to 8 mol%.
Is preferable, and by setting the copolymerization ratio of the monomer within this range, antifouling adhesiveness, stain removability,
Has excellent weather resistance and water resistance.

The polymerization method may be any ordinary polymerization method.

As a method for mixing the respective components to obtain the coating composition of the present invention, for example, a solution prepared by dissolving a crosslinking functional group-containing coating resin in a solvent is placed in a vessel equipped with a stirrer, and a stain adheres while stirring. The inhibitor may be added, and the curing agent and / or the curing catalyst may be further added.

As another mixing method, a solution prepared by dissolving a solvent-soluble fluoroolefin copolymer having a heat dissociable fluorine-containing protecting group and a hydroxyl group in a solvent is put in the container, and a curing agent and / or Alternatively, a curing catalyst may be added.

Examples of outdoor articles for applying the coating composition of the present invention include outdoor articles coated with a paint, metal panels, films, plastic boards, concrete panels, tiles and the like.

As a method of coating the outdoor article, for example, the coating composition is applied by spray coating and then dried at 50 to 250 ° C. for 1 minute to 2 hours to give a film thickness of 1 to 1.
A 100 μm coating film may be formed.

In the present invention, for example, in this drying step, the protecting group Rf of the compound represented by the above formula (I) is used.
Is desorbed (that is, thermally dissociated) to generate a hydroxyl group,
It is considered that the surface of the coating film becomes moderately hydrophilic, and the antifouling adhesion property and the stain removal property are improved.

In the present invention, after the coating film is formed in this manner, for example, acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, and alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium hydrogencarbonate. 0.
By washing the coating film surface with a 1 to 10% aqueous solution (0 to 30 ° C.), spray coating, or coating with a brush, for example, the remaining protecting group R _f without thermal dissociation is hydrolyzed. It is considered that carboxylic acid groups, sulfonic acid groups, and amino groups become ionic groups by decomposing and further desorbing, and it is considered that the coating becomes more hydrophilic by such treatment. .

[0105] Compounds represented by as described above (A) formula (I) Z-X-O -R f (I) is, R _f is, for example, fluorine-containing vinyl ether (hereinafter, also referred to as FVE) when residues, In each case of a fluorine-containing alcohol (hereinafter, also referred to as FOH) residue, the compound is an additive when Z has no functional group, and the compound when Z has a non-double bond functional group. Is a reactive additive, and when Z has a polymerizable double bond functional group, the compound is a polymerizable additive.

In the coating composition of the present invention, the following are preferred examples of the combination of the anti-staining agent, the coating resin, the curing agent and / or the curing catalyst comprising the above compounds. In the following, the expression means the above expression (I).

(1) In the formula (A1), a stain adhesion preventing agent comprising a compound in which Z has no functional group and R _f is an FVE residue 1 to 100 parts (B) crosslinkable functional group-containing resin for coating 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts This composition has excellent storage stability, and the coating film has antifouling and adhesion properties,
Excellent in removing stains. More preferably, in the formula (A1), Z is a compound having no functional group and R _f is a FVE residue. 1 to 50 parts by weight. 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts by weight This composition has excellent storage stability, and the coating film has excellent weather resistance, antifouling adhesion and decontamination properties.

(2) In the formula (A1), Z is a compound having a non-double bond functional group and R _f is an FVE residue, a stain-adhering agent 1 to 100 parts (B) a crosslinkable functional group Resin for coating material 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film made of this composition is excellent in long-term anti-fouling adhesion property, decontamination property, low electrostatic property and solvent resistance. ing.

More preferably, in the formula (A2), Z is a non-double bond functional group, R _f is an FVE residue, and one non-double bond functional group is contained in one molecule. 1 to 100 parts of (B) crosslinkable functional group-containing coating resin 100 parts (C) curing agent and / or curing catalyst 0.01 to 100 parts (A2) in this composition is 1 molecule Since it has only one non-double bond functional group, it is easily oriented on the coating film surface. Further, a coating film formed from this composition is excellent in long-term anti-fouling adhesion property, stain removal property, low electrification property and solvent resistance.

More preferably, in the formula (A1), Z is a compound having a non-double bond functional group and R _f is an FVE residue, a stain-adhering agent 1 to 100 parts (B1) a crosslinkable functional group Fluororesin for group-containing paint 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film composed of this composition has a long-term antifouling adhesion property, decontamination property, low electrostatic property, weather resistance, Excellent solvent resistance, chemical resistance, and water resistance.

More preferably, in the formula (A2), Z is a non-double bond functional group, R _f is an FVE residue, and one non-double bond functional group is contained in one molecule. Antifouling agent consisting of 1 to 100 parts (B1) Fluoropolymer for crosslinkable functional group-containing paint 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (A2) in this composition is 1 Since it has only one non-double bond functional group in the molecule, it is easily oriented on the surface of the coating film. A coating film made of this composition is excellent in long-term antifouling adhesion, stain removal property, low chargeability, weather resistance, solvent resistance and water resistance.

(3) In the formula (A1), Z is a compound having a non-double bond functional group and R _f is an FVE residue, a stain-adhering agent 1 to 100 parts (B) a crosslinkable functional group Resin for coating material 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor compound A coating film comprising this composition has long-term antifouling and adhesion properties. It has excellent stain removability, low chargeability and solvent resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A2), Z is a non-double bond functional group, R _f is an FVE residue, and one non-double bond functional group is contained in one molecule. 1 to 100 parts (B) cross-linkable functional group-containing coating resin 100 parts (C) curing agent and / or curing catalyst 0.01 to 100 parts (D) elimination reaction catalyst and / or donor Functional compound (A2) in this composition has only one non-double bond functional group in one molecule and therefore is easily oriented on the surface of the coating film. Further, a coating film formed from this composition is excellent in long-term anti-fouling adhesion property, stain removal property, low electrification property and solvent resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A1), Z is a compound having a double bond and R _f is an FVE residue, a stain-adhering agent 1 to 100 parts (B1) a crosslinkable functional group Fluorine resin for coating containing 100 parts (C) curing agent and / or curing catalyst 0.01 to 100 parts (D) catalyst for elimination reaction and / or donor compound A coating film made of this composition has long-term antifouling and adhesion properties. Excellent in stain removability, low electrostatic property, weather resistance, solvent resistance, chemical resistance, and water resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A2), Z is a non-double bond functional group, R _f is an FVE residue, and one non-double bond functional group is contained in one molecule. 1 to 100 parts (B1) Fluorine resin for coating containing crosslinkable functional group 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or Donor Compound Since (A2) in this composition has only one non-double bond functional group in one molecule, it is easily oriented on the coating film surface. A coating film made of this composition is excellent in long-term anti-fouling adhesion property, stain removability, low electrostatic property, weather resistance, solvent resistance, chemical resistance and water resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

(4) In the formula (A1), Z is a polymerizable double bond functional group and R _f is a FVE residue. Group-containing coating resin 1 to 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film made of this composition has long-term anti-fouling adhesion, anti-staining property, low electrostatic property, solvent resistance. It has excellent properties.

More preferably, in formula (A2), Z is a polymerizable double bond functional group and R _f is a FVE residue. Functional group-containing fluororesin for paint 1 to 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film made of this composition has long-term antifouling adhesion, decontamination, low chargeability, It has excellent weather resistance, solvent resistance, chemical resistance, and water resistance.

(5) In the formula (A1), Z is a compound in which Z has no functional group and Rf is a FOH residue. Antifouling agent 1 to 100 parts (B) Resin for coating containing crosslinkable functional group 100 Parts (C) curing agent and / or curing catalyst 0.01 to 100 parts This composition has excellent storage stability, and the coating film has antifouling and adhesion properties,
Excellent in removing stains.

More preferably, in the formula (A2), Z has no functional group, and R _f is a compound having a secondary or tertiary FOH residue. 1 to 100 parts (B) Crosslinkable functional group-containing coating resin 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (A2) of this composition is ROH of secondary or tertiary FOH.
It is a residue and is more excellent in elimination properties. This composition has excellent storage stability, and the coating film has excellent antifouling adhesion and decontamination properties.

More preferably, in the formula (A1), 1 to 50 parts by weight of a compound in which Z does not have a functional group and R _f is an FOH residue (B1) 100 parts of a fluororesin for a coating composition containing a crosslinkable functional group ( C) Curing agent and / or curing catalyst 0.01 to 100 parts by weight This composition has excellent storage stability, and the coating film has excellent weather resistance, antifouling adhesion and decontamination properties. More preferably, in the formula (A2), Z has no functional group and R _f is a compound having a secondary or tertiary FOH residue. 1 to 100 parts (B1) crosslinkable functional group Fluorine resin for coating containing 100 parts (C) curing agent and / or curing catalyst 0.01 to 100 parts (A2) of this composition is FOH whose Rf is secondary or tertiary.
It is a residue and is more excellent in elimination properties. This composition has excellent storage stability, and the coating film has excellent antifouling adhesion and decontamination properties.

(6) In the formula (A1), Z has a non-double-bonding functional group and R _f is a FOH residue, a stain-adhering agent 1 to 100 parts (B) a crosslinkable functional group Resin for coating material 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film made of this composition is excellent in long-term anti-fouling adhesion property, decontamination property, low electrostatic property and solvent resistance. ing. More preferably, in the formula (A2), Z is a compound having a non-double bond functional group and R _f is a compound having a secondary or tertiary FOH residue 1 to 100 parts (B) Crosslinkable functional group-containing coating resin 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts FOH having a secondary or tertiary R _f of (A2) of this composition.
It is a residue and is more excellent in elimination properties. A coating film made of this composition is excellent in long-term antifouling adhesion, stain removal property, low electrostatic property, and solvent resistance.

More preferably, in the formula (A3), Z is a non-double bond functional group, R _f is a FOH residue, and one non-double bond functional group is contained in one molecule. 1 to 100 parts of (B) cross-linkable functional group-containing coating resin (C) curing agent and / or curing catalyst 0.01 to 100 parts (A2) in this composition is in one molecule Since it has only one non-double bond functional group, it is easily oriented on the surface of the coating film. Further, a coating film formed from this composition is excellent in long-term anti-fouling adhesion property, stain removal property, low electrification property and solvent resistance.

More preferably, in the formula (A4), Z has a non-double bond functional group, R _f is a secondary or tertiary FOH residue, and a non-double bond is present in one molecule. Antifouling agent consisting of a compound having one functional group 1 to 100 parts (B) Resin for paint containing crosslinkable functional group 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts of this composition (A2) is FOH whose R _f is secondary or tertiary
It is a residue and is more excellent in elimination properties. Since (A2) in this composition has only one non-double bond functional group in one molecule, it is easily oriented on the coating film surface. Further, a coating film formed from this composition is excellent in long-term anti-fouling adhesion property, stain removal property, low electrification property and solvent resistance.

More preferably, in the formula (A1), Z is a compound having a non-double bond functional group and R _f is a FOH residue. A stain-adhering agent 1 to 100 parts (B1) a crosslinkable functional group. Fluororesin for group-containing paint 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film composed of this composition has a long-term antifouling adhesion property, decontamination property, low electrostatic property, weather resistance, Excellent solvent resistance, chemical resistance, and water resistance.

More preferably, in the formula (A2), Z is a compound having a non-double bond functional group and R _f is a secondary or tertiary FOH group. B1) Fluororesin for coating containing crosslinkable functional group 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts In this composition (A2), R _f is a secondary or tertiary FOH.
It is a residue and is more excellent in elimination properties. A coating film made of this composition is excellent in long-term anti-fouling adhesion, stain removability, low chargeability, weather resistance, solvent resistance, chemical resistance and water resistance.

More preferably, in the formula (A3), Z is a non-double bond functional group, R _f is a FOH residue, and one non-double bond functional group is contained in one molecule. Antifouling agent consisting of 1 to 100 parts (B1) Fluoropolymer for crosslinkable functional group-containing paint 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (A2) in this composition is 1 Since it has only one non-double bond functional group in the molecule, it is easily oriented on the surface of the coating film. A coating film made of this composition is excellent in long-term anti-fouling adhesion property, stain removability, low electrostatic property, weather resistance, solvent resistance, chemical resistance and water resistance.

More preferably, in the formula (A4), Z has a non-double bond functional group, R _f is a secondary or tertiary FOH residue, and a non-double bond is present in one molecule. Anti-contamination agent consisting of a compound having one functional group 1 to 100 parts (B1) Fluoropolymer for crosslinkable functional group-containing coating 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts This composition (A4) is FOH whose R _f is secondary or tertiary
It is a residue and is more excellent in elimination properties. Since (A4) in this composition has only one non-double bond functional group in one molecule, it is easily oriented on the coating film surface. A coating film made of this composition is excellent in long-term anti-fouling adhesion property, stain removability, low electrostatic property, weather resistance, solvent resistance, chemical resistance and water resistance.

(7) In the formula (A1), Z has a non-double bond functional group and R _f is a FOH residue. Contamination adhesion preventive agent comprising 1 to 100 parts (B) crosslinkable functional group Resin for coating material 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor compound A coating film comprising this composition has long-term antifouling and adhesion properties. It has excellent stain removability, low chargeability and solvent resistance. In addition, this composition contains an elimination reaction catalyst and / or a donor compound, and thus the surface is made more hydrophilic.

More preferably, in the formula (A2), Z is a compound having a non-double bond functional group and R _f is a secondary or tertiary FOH residue. (B) Resin for coating containing crosslinkable functional group 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor compound (A2) of this composition R _f is secondary or tertiary FOH
It is a residue and is more excellent in elimination properties. A coating film made of this composition is excellent in long-term antifouling adhesion, stain removal property, low electrostatic property, and solvent resistance. Further, this composition contains a catalyst for elimination reaction and / or a donor compound,
Surface hydrophilization is further promoted.

More preferably, in the formula (A3), Z is a non-double bond functional group, R _f is a FOH residue, and one non-double bond functional group is contained in one molecule. 1 to 100 parts (B) cross-linkable functional group-containing coating resin 100 parts (C) curing agent and / or curing catalyst 0.01 to 100 parts (D) elimination reaction catalyst and / or donor Functional compound Since (A3) in this composition has only one non-double bond functional group in one molecule, it is easily oriented on the coating film surface. Further, a coating film formed from this composition is excellent in long-term anti-fouling adhesion property, stain removal property, low electrification property and solvent resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A4), Z has a non-double bond functional group, R _f is a secondary or tertiary FOH residue, and a non-double bond is present in one molecule. Anti-contamination agent consisting of a compound having one functional group 1 to 100 parts (B) Resin for paint containing crosslinkable functional group 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Desorption Catalyst for Separation Reaction and / or Donor Compound (A4) of this composition is FOH whose R _f is secondary or tertiary.
It is a residue and is more excellent in elimination properties. Since (A4) in this composition has only one non-double bond functional group in one molecule, it is easily oriented on the coating film surface. Further, a coating film formed from this composition is excellent in long-term anti-fouling adhesion property, stain removal property, low electrification property and solvent resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilization is further promoted.

More preferably, in the formula (A1), Z is a compound having a non-double bond functional group and R _f is a FOH residue. A stain-adhering agent 1 to 100 parts (B1) a crosslinkable functional group. Fluororesin for group-containing paint 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor compound A coating film composed of this composition is used for long-term antifouling adhesion. It has excellent properties, stain removability, low chargeability, weather resistance, solvent resistance, chemical resistance, and water resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A2), Z is a non-double bond functional group, R _f is a FOH residue, and one non-double bond functional group is contained in one molecule. 1 to 100 parts (B1) Fluororesin for coating containing crosslinkable functional group 100 parts (C) Hardener and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor Functional compound (A2) in this composition has only one non-double bond functional group in one molecule and therefore is easily oriented on the surface of the coating film. A coating film made of this composition is excellent in long-term anti-fouling adhesion property, stain removability, low electrostatic property, weather resistance, solvent resistance, chemical resistance and water resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A3), Z is a compound having a non-double bond functional group and R _f is a secondary or tertiary FOH residue. (B1) Fluororesin for coating containing crosslinkable functional group 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor compound (A3) of this composition Is FOH whose R _f is secondary or tertiary
It is a residue and is more excellent in elimination properties. A coating film made of this composition is excellent in long-term anti-fouling adhesion, stain removability, low chargeability, weather resistance, solvent resistance, chemical resistance and water resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

More preferably, in the formula (A4), Z has a non-double bond functional group, R _f is a secondary or tertiary FOH residue, and a non-double bond is present in one molecule. Anti-contamination agent consisting of a compound having one functional group 1 to 100 parts (B1) Fluorine resin for cross-linkable functional group-containing coating 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts (D) Catalyst for elimination reaction and / or donor compound (A4) of this composition is FOH whose R _f is secondary or tertiary.
It is a residue and is more excellent in elimination properties. Since (A4) in this composition has only one non-double bond functional group in one molecule, it is easily oriented on the coating film surface. A coating film made of this composition is excellent in long-term anti-fouling adhesion property, stain removability, low electrostatic property, weather resistance, solvent resistance, chemical resistance and water resistance. In addition, this composition contains a catalyst for elimination reaction and / or a compound having a donor property, so that surface hydrophilicity is further promoted.

(8) In formula (A), Z is a polymerizable double bond functional group and R _f is a FOH residue. Group-containing coating resin 1 to 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film made of this composition has long-term anti-fouling adhesion, anti-staining property, low electrostatic property, solvent resistance. It has excellent properties.

More preferably, in the formula (A2), Z is a polymerizable double bond functional group and R _f is a FOH residue. Functional group-containing fluororesin for paint 1 to 100 parts (C) Curing agent and / or curing catalyst 0.01 to 100 parts A coating film made of this composition has long-term antifouling adhesion, decontamination, low chargeability, Excellent weather resistance, solvent resistance, and chemical resistance.

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these.

Synthesis Example 1 100 g of 1,4-butanediol was placed in a 1 L three-way flask.
(1.1 mol), 4-methylhexahydrophthalic anhydride 186 g (1.1 mol), dissolved in a mixture of 150 g of ethyl acetate and 150 g of xylene, and while maintaining the temperature below 5 ° C, 0.55 g of triethylamine was added. Stirring was continued for hours. The reaction mixture was returned to room temperature, the organic layer was washed with water, and then dried with Molecular Sieve 4A to obtain a monocarboxylic acid compound solution. This solution is hereinafter referred to as Solution A-1.
Say. Further, 213 g of 2,2,3,3,3-pentafluoropropyl vinyl ether (hereinafter referred to as 5FVE) as a compound capable of forming a fluorine-containing protective group
5% hydrochloric acid 0.23g, methyl isobutyl ketone 200g
Was added and stirred at 50 ° C. for 1 hour. The reaction mixture was returned to room temperature, neutralized with an alkali, washed with water, and then dried with a molecular sieve 4A to obtain a compound solution F-1 having a solid content of 49% and having a thermally dissociable fluorine-containing protecting group.

Synthesis Examples 2 to 4 According to Synthesis Example 1, compounds F-2 to F-4 having a thermally dissociable fluorine-containing protecting group were obtained by using the reaction raw materials shown in Table 1.

[0141]

[Table 1]

The abbreviations used in Table 1 indicate the following.

HSA: 12-hydroxystearic acid 17FVE: 2-perfluorooctylethyl vinyl ether MIBK: methyl isobutyl ketone Synthetic example 5 5FVE 213 g, 3 in solution A-1 obtained in Synthetic example 1
5% hydrochloric acid 0.23g, methyl isobutyl ketone 200g
Was added and stirred at 50 ° C. for 1 hour. Further, add 71.5 g of ethyl vinyl ether and 0.1 g of 35% hydrochloric acid, and add 5
Stirred at 0 ° C. for 1 hour. Bring the reaction mixture to room temperature,
After molecular neutralization and washing with water, molecular sieve 4
After drying with A, a compound solution F-5 having a heat dissociable fluorine-containing protecting group having a solid content of 52% was obtained.

Synthesis Example 6 174 g (1.1 mol) of 3-allyloxycarbonylpropionic acid (reaction product of allyl alcohol and succinic anhydride), 213 g of 5FVE, 0.23 g of 35% hydrochloric acid and 400 g of methyl isobutyl ketone were added at 50 ° C. It was stirred for 1 hour. The reaction mixture was returned to room temperature, neutralized with an alkali, washed with water, and then dried with a molecular sieve 4A to obtain a monomer solution M-1 having a heat dissociable fluorine-containing protective group having a solid content of 50%.

Polymerization Example 1 Butyl acetate 2.0 k in a 6 L stainless steel autoclave
g and 680 g (6.8 mol) of tetrafluoroethylene are added, the atmosphere is replaced with nitrogen, and the temperature is raised to 67.5 ° C. Octanoyl peroxide solution (solid content 30%) with stirring
60 g of vinyl pivalate 317 g (2.5 mol) ethyl vinyl ether 134 g (1.9 mol), hydroxybutyl vinyl ether 143 g (1.2 mol), and a monomer solution M- synthesized in the same manner as in Synthesis Example 6 were added.
440 g (about 0.6 mol) of 1 was added over 2 hours. Two hours after the addition of the monomer was completed, 60 g of the same peroxide solution was added, and the mixture was stirred for another 10 hours. The reaction mixture was cooled to room temperature, unreacted monomer was purged, and then the atmosphere was replaced with nitrogen to obtain 3.5 kg of product.
(Solid content 43%) was obtained. Number average molecular weight Mn 8000,
The hydroxyl value was 48 (mgKOH / g). This was concentrated to give a solution with a solid content of 60%. This resin solution having a thermally dissociable fluorine-containing protecting group is called FR-1.

Synthesis Example 7 168 g of 1,1,1,3,3,3-hexafluoro-2-propanol was placed in a 1 L three-way flask and cooled with ice. 90 g of potassium t-butoxide was added to and dissolved therein, and the mixture was stirred. 95 g of p-toluenesulfonic acid chloride dissolved in 500 g of lower diethyl ether was added dropwise over 30 minutes. After completion of the dropping, stirring was continued under ice cooling for 1 hour, and then the reaction was continued at room temperature for 1 hour. The reaction mixture was washed with water, dried over molecular sieve 4A, and the solvent was distilled off to give p-toluenesulfonic acid (1, 1, 1, 3,
129 g of 3,3-hexafluoro-2-propyl) was obtained. The compound having the thermally dissociable fluorine-containing protecting group is hereinafter referred to as F-6.

Polymerization Example 2 Butyl acetate 2.0 k in a 6 L stainless steel autoclave
g and 680 g (6.8 mol) of tetrafluoroethylene are added, the atmosphere is replaced with nitrogen, and the temperature is raised to 67.5 ° C. Octanoyl peroxide solution (solid content 30%) with stirring
The 60g addition, vinyl pivalate 317 g (2.5 mol) of ethyl vinyl ether 134 g (1.9 mol), hydroxybutyl vinyl ether 143 g (1.2 _{mol), C 4 H 9 OCO-} CH 2 -CH (SO 3 -CH (CF
₃₎ represented by _{-CF 3) -CO 2 CH 2 CH} = CH 2 M-
A mixture of 2 monomers-266 g (0.6 mol) was added over 2 hours. Two hours after the addition of the monomer was completed, 60 g of the same peroxide solution as above was added, and another 10
Stirred for hours. The reaction mixture was cooled to room temperature, unreacted monomers were purged, and the atmosphere was further replaced with nitrogen to obtain 3.3 kg of the product (solid content 41%). Number average molecular weight Mn
It was 11,000 and the hydroxyl value was 47 (mgKOH / g). It was concentrated to 60% solids. Hereinafter, the resin solution having the thermally dissociable fluorine-containing protecting group will be referred to as FR-2.

Synthesis Example 8 2-isocyanatoethyl-2,6 was added to a 2 L three-way flask.
-Diisocyanate caproate 267 g, 2,2
675 g of 3,3,3-pentafluoropropanol was added, and the mixture was stirred at 80 ° C. for 5 hours. Then, unreacted alcohol was distilled off under reduced pressure to obtain F-7 as a compound having a thermally dissociable fluorine-containing protecting group.

Synthesis Example 9 To the solution A-1 obtained in Synthesis Example 1, 95 g of ethyl vinyl ether, 0.23 g of 35% hydrochloric acid and 80 g of methyl isobutyl ketone were added, and the mixture was stirred at 50 ° C. for 1 hour. The reaction mixture was returned to room temperature, neutralized with an alkali, washed with water, and then dried with a molecular sieve 4A to obtain a compound solution N-1 having a solid content of 48% and having a thermally dissociable non-fluorine-containing protecting group.

Example 1 Zeffle GK-500 (Fluorine resin polyol solution manufactured by Daikin Industries, Ltd., hydroxyl value 60, solid content 60 wt%)
CR-95 (titanium oxide, Ishihara Sangyo Co., Ltd.) on 208 g
Made) 250 g, butyl acetate 100 g, glass beads 80
Add 0 g and use a tabletop grind mill (three-blade type) to add 1
The mixture was stirred and dispersed at 500 rpm for 1 hour. The glass beads were removed by filtration to obtain 410.5 g of a dispersion liquid. GK-
214.8 g of 500 and 110.3 g of butyl acetate were added and mixed well to obtain a GK-500 white base (pigment / resin = 0.833 weight ratio). 100g of this white base
6.0 g of a compound solution F-1 having a thermally dissociable fluorine-containing protecting group (10 parts by weight based on 100 parts by weight of the fluororesin)
BL-4165 (blocked isophorone diisocyanate curing agent manufactured by Sumitomo Bayer Urethane) was added to 20.
0 g (NCO / OH = 1.2), 0.3% butyl acetate solution of 1% dibutyltin dilaurate, butyl acetate 80
g and mixed well. This coating composition was applied by spray coating to an AM-712-treated aluminum plate (0.5 mm thickness), cured and dried at 180 ° C. for 30 minutes to give a coated film having a coating film thickness of about 40 μm, and the subsequent tests were conducted. .

Example 2 Example 1 was repeated except that 11.9 g of F-2 was used instead of the compound solution F-1 having a thermally dissociable fluorine-containing protecting group.
An experiment was carried out with the same composition.

Example 3 An experiment was conducted in the same formulation as in Example 1 except that 6.0 g of F-3 was used instead of the compound solution F-1 having a thermally dissociable fluorine-containing protecting group.

Example 4 Example 1 was repeated except that 12.3 g of F-4 was used in place of the compound solution F-1 having a thermally dissociable fluorine-containing protecting group.
An experiment was carried out with the same composition.

Example 5 An experiment was conducted in the same manner as in Example 1 except that 6.8 g of F-5 was used instead of the compound solution F-1 having a thermally dissociable fluorine-containing protecting group.

Example 6 Instead of the butyl acetate solution of dibutyltin dilaurate, 0.3% of an ethanol solution of 5% p-toluenesulfonic acid was used.
An experiment was conducted with the same composition as in Example 1 except that g was used.

Example 7 No. 2 of resin solution FR-1 having a heat dissociable fluorine-containing protecting group
CR-95 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) on 08 g
250 g, butyl acetate 100 g, glass beads 800 g
And 150 with a tabletop grind mill (three-blade type)
The mixture was stirred and dispersed at 0 rpm for 1 hour. The glass beads were removed by filtration to obtain 416.3 g of the dispersion liquid. To this, 217.8 g of FR-1 and 111.9 g of butyl acetate were added and mixed well, and this was mixed with FR-1 white base (pigment / resin = 0.833).
Weight ratio). BL-4165 on this white base 100
13.3 g (NCO / O) of (blocked isophorone diisocyanate curing agent manufactured by Sumitomo Bayer Urethane Co., Ltd.)
H = 1.0), tetrabutylammonium chloride 0.
6 g, dimethylformamide 20 g, butyl acetate 60 g
In addition, mixed well. This coating composition was applied by spray coating to an AM-712 treated aluminum plate (0.5 mm thickness), cured and dried at 180 ° C. for 30 minutes, and a coating film thickness of about 40 μm.
The subsequent test was performed using m coated plates.

Example 8 100 g of Zeffle GK-500 white base (face / resin = 0.833 weight ratio) prepared in the same manner as in Example 1 was charged with 1.5 g of the compound F-6 having a heat dissociable fluorine-containing protecting group. And BL
16.6 g of -4165 (blocked isophorone diisocyanate curing agent manufactured by Sumitomo Bayer Urethane Co., Ltd.)
(NCO / OH = 1.0), lithium chloride 0.2 g, dimethylformamide 20 g, and butyl acetate 60 g were mixed well in the mouth. This coating composition was applied by spray coating to an AM-712 treated aluminum plate (0.5 mm thick),
It was cured and dried at 180 ° C for 30 minutes to obtain a coated plate having a coating film thickness of about 40 µm, and the subsequent tests were conducted.

Example 9 No. 2 of resin solution FR-2 having a heat dissociable fluorine-containing protecting group
CR-95 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) on 08 g
250 g, butyl acetate 100 g, glass beads 800 g
And 150 with a tabletop grind mill (three-blade type)
The mixture was stirred and dispersed at 0 rpm for 1 hour. The glass beads were removed by filtration to obtain 421.4 g of a dispersion liquid. To this, 219.7 g of FR-1 and 113.2 g of butyl acetate were added and mixed well, and this was mixed with FR-1 white base (pigment / resin = 0.833).
Weight ratio). BL-4165 on this white base 100
(Sumitomo Bayer Urethane Co., Ltd. blocked isophorone diisocyanate curing agent) 13.0 g (NCO / O
H = 1.0), tetrabutylammonium chloride 0.
6 g, dimethylformamide 20 g, butyl acetate 60 g
In addition, mixed well. This coating composition was applied by spray coating to an AM-712 treated aluminum plate (0.5 mm thickness), cured and dried at 180 ° C. for 30 minutes, and a coating film thickness of about 40 μm.
The subsequent test was performed using m coated plates.

Example 10 100 g of Zeffle GK-500 white base (pigment / resin = 0.833 weight ratio) prepared in the same manner as in Example 1 was charged with 1.5 g of the compound F-7 having a thermally dissociable fluorine-containing protecting group. And B
14.9 g of L-4165 (blocked isophorone diisocyanate curing agent manufactured by Sumitomo Bayer Urethane Co., Ltd.)
(NCO / OH = 0.9) 0.3 g of butyl acetate solution of 1% dibutyltin dilaurate, 0.3 g of lithium chloride
g, dimethylformamide 20 g, and butyl acetate 60 g were mixed well in the mouth. This coating composition is applied by spray coating to an AM-712-treated aluminum plate (0.5 mm thickness), cured and dried at 180 ° C. for 30 minutes, and a coating film thickness of about 40 μm.
The following test was performed as the coated plate.

Example 11 250 g of CR-95 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) and 100 g of butyl acetate were added to 250 g of Zemlac YC3623 (acrylic silicone manufactured by Kanegafuchi Chemical Co., Ltd., solid content: 50%).
g, 10.0 g of HC (OCH ₃ ) ₃ as a dehydrating agent and 800 g of glass beads were added, and the mixture was stirred and dispersed at 1500 rpm for 1 hour by a tabletop grind mill (three blade type). The glass beads were removed by filtration to obtain 444.5 g of a dispersion liquid.
To this, 259.3 g of YC3623, butyl acetate solution 3
7.1 g was added and mixed well to obtain YC3623 white base (pigment / resin-0.833 weight ratio). To 100 g of the white base, 1.5 g of F-7 was added, 0.15 g of a 1% butyl acetate solution of dibutyltin dilaurate and 80 g of butyl acetate were mixed well in the mouth. This coating composition is applied to a dull steel plate (0.5 mm thickness) by spray coating and cured and dried at 180 ° C. for 30 minutes to obtain a coating film thickness of about 40 μm.
The following test was performed as the coated plate.

Comparative Example 1 Example 1 was repeated except that 4.7 g of N-1 was used instead of the compound solution F-1 having a thermally dissociable fluorine-containing protecting group.
An experiment was carried out with the same composition.

Comparative Example 2 100 g of Zeffle GK-500 white base (pigment / resin = 0.833 weight ratio) prepared in the same manner as in Example 1 was added with BL-.
1165 g of 4165 (blocked isophorone diisocyanate curing agent manufactured by Sumitomo Bayer Urethane Co., Ltd.) (N
(CO / OH = 1.0) 0.3 g of a 1% dibutyltin dilaurate butyl acetate solution and 80 g of butyl acetate were mixed well in the mouth. This coating composition was applied by spray coating to an AM-712-treated aluminum plate (0.5 mm thickness), cured and dried at 180 ° C. for 30 minutes to give a coated plate having a coating film thickness of about 40 μm, and the subsequent tests were conducted.

The following tests were conducted on the coated plates prepared in Examples 1-11 and Comparative Examples 1-2.

Mitsuzawa: According to JIS K-5400, a specular gloss of 60 degrees was measured. Pencil hardness: Measured according to JIS K-5400. Contamination Adhesion: Each coated plate was placed on the roof of a three-story building in Osaka Prefecture on an outdoor exposure table with a 30 ° slope on the south side, and the brightness (L * value) after 3 and 6 months was measured to determine the initial brightness. Difference with (-
ΔL *) was used as an index of stain adhesion, and the following judgment was made. A was evaluated as A when ΔL * was 0 to less than 2 and B as 4 to less than 4 and C as 4 to less than 6 and D as 10 to less than 10. . Decontamination property: The surface of the coated plate used for evaluating the contamination adhesion property was washed with a brush to remove the adhered dirt. The difference between the lightness (L * value) after removal and the initial lightness (-△
L *) was evaluated as an index of stain removability (the meanings of symbols A to E are the same as above). Accelerated weather resistance: Ice Par UV tester (Iwasaki Electric Co., Ltd.)
It was tested with a weather resistance tester, and the weather resistance was evaluated by a 60-degree specular gloss retention rate (%) of about 1000 hours.

For the weather resistance test, the following conditions were adopted. (1) Cycle LIGHT, black panel temperature 63
° C, relative humidity 70%, time 11h, shower 10 seconds / 1
Time (2) Cycle DEW, black panel temperature 30 ° C, relative humidity 100%, (3) Cycle REST, black panel temperature 63 ° C,
The relative humidity is 85%, and the results are shown in Table 2.

[0166]

[Table 2]

[0167]

As is clear from the above results, the anti-staining agent of the present invention has excellent anti-staining and adhesion properties.

Further, the coating composition of the present invention comprising the anti-staining agent, the cross-linkable functional group-containing coating resin, the curing agent and / or the curing catalyst is excellent in storage stability and thermosetting property.

Further, the coating composition comprising the solvent-soluble fluoroolefin copolymer having a heat-dissociable fluorine-containing protective group and a hydroxyl group of the present invention and a curing agent and / or a curing catalyst has antifouling adhesion and stain resistance. It has excellent removability and weather resistance.

The surface treatment method of the present invention is excellent in surface hydrophilicity.

Further, the outdoor article of the present invention is excellent in antifouling adhesion.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yoshiki Shimizu, 1-1 Nishiichitsuya, Settsu City, Osaka Prefecture Daikin Industries, Ltd. Yodogawa Works (72) Inventor, Hiroo Mitsuhata, Nishiichitsuya, Settsu City, Osaka Prefecture Daikin Yodogawa Manufacturing Co., Ltd.

Claims (14)

[Claims] 1. (A) Formula (I): Z—X—O—R _f (I) (In the formula, Z is an organic group having or not having a functional group, and X is C═O or SO ₂ and R _f each are a compound having a thermally dissociable fluorine-containing protecting group represented by (a hydrogen atom is partially or entirely substituted with a fluorine atom and is an organic group which may contain an oxygen atom). Anti-fouling agent. 2. (A) -Rf is represented by the formula (II): (In the formula, R ¹ , R ² and R ³ are the same or different and each is a hydrogen atom or an organic group having 1 to 18 carbon atoms and optionally containing a fluorine atom; R ⁴ is a hydrogen atom having 1 to 18 carbon atoms; The anti-fouling agent according to claim 1, which is a thermally dissociable fluorine-containing protecting group represented by an organic group in which some or all of the atoms are substituted with fluorine atoms. 3. The (A) stain adhesion preventing agent 1 according to claim 2.
~ 100 parts by weight and (B) crosslinkable functional group-containing coating resin 1
A coating composition comprising 00 parts by weight and (C) a curing agent and / or a curing catalyst. 4. A coating composition comprising the solvent-soluble fluoroolefin copolymer having a heat-dissociable fluorine-containing protective group and a hydroxyl group according to claim 2 and (C) a curing agent and / or a curing catalyst. 5. (A) -Rf is represented by the formula (III): (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and each is a hydrogen atom or has 1 to 18 carbon atoms and part or all of the hydrogen atoms are substituted with a fluorine atom. Is a heat-dissociable fluorine-containing protecting group represented by the formula (3), wherein at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorine atom-containing group. Anti-fouling agent. 6. The (A) stain adhesion preventing agent 1 according to claim 5.
~ 100 parts by weight and (B) crosslinkable functional group-containing coating resin 1
A coating composition comprising 00 parts by weight and (C) a curing agent and / or a curing catalyst. 7. A coating composition comprising the solvent-soluble fluoroolefin copolymer having a thermally dissociable fluorine-containing protecting group and a hydroxyl group according to claim 5, and (C) a curing agent and / or a curing catalyst. 8. The anti-staining agent or coating composition according to claim 2, wherein the compound having a heat-dissociable fluorine-containing protecting group is a compound having only one protecting group. 9. The antifouling agent or coating composition according to claim 5, 6 or 7, wherein in the formula (III), R ¹ is a hydrogen atom and R ⁵ is not a hydrogen atom. 10. The method according to claim 3, 6, 8 or 9, wherein the resin (B) for cross-linkable functional group-containing coating material is a solvent-soluble resin for fluorine coating material containing a hydroxyl group and / or a carboxyl group. Agent or paint composition. 11. The anti-fouling agent or coating composition according to claim 3, wherein the (B) resin for coating material containing a crosslinkable functional group is a resin for acrylic silicon coating material having an alkoxysilyl group. . 12. A catalyst for removing a thermally dissociative fluorine-containing protecting group is selected from the group consisting of sulfonic acids, sulfonates, ammonium salts, carboxylates, alkali metal halide compounds and alkaline earth metal halide compounds. The anti-fouling agent or coating composition according to any one of claims 2 to 11, which comprises at least one selected from the group consisting of amide compounds, tertiary amine compounds and ether compounds as stabilizers thereof. . 13. A method of coating the surface of a coating composition with the anti-staining agent or the coating composition according to claim 1, and then treating the surface of the coating film with an alkali or an acid. 14. An outdoor article obtained by coating the anti-staining agent or coating composition according to any one of claims 1 to 12 or treating by the method according to claim 13.