JPH11217540A - Composition for paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, scarcely sticking foulings and useful for outdoor coating excellent in antifoaming properties and coating operating efficiency by including a resin for a coating material, a specific silicate compound and a specified dimethylsilicone oil therein. SOLUTION: This composition is obtained by including (A) a resin for a coating material, (B) a compound represented by formula I [R is a 1-9C organic group containing N, O, F or Cl or H; (n) is 1-100] in an amount of preferably 1-50 pts.wt. based on 100 pts.wt. of the component A, (C) a compound represented by formula II [R<1> is C8 F17 CH2 CH2 , a 1-9C organic group containing N, 0, F or Cl or H; (m) is 1-100] in an amount of preferably 0.1-2 pts.wt. based on 100 pts.wt. of the component A and (D) a dimethylsilicone oil having fluoroalkyl groups in an amount of preferably 0.001-0.3 pt.wt. based on 100 pts.wt. of the component A. Furthermore, the component A is preferably a solvent-soluble fluoroolefin copolymer, an acrylic polyol resin or an acrylic silicone resin having hydroxyl groups and/or carboxyl groups, an inorganic material, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a coating composition suitable for outdoor painting which is hardly adhered with dirt and has excellent defoaming properties and repellency (painting workability).

[0002]

2. Description of the Related Art In recent years, there has been an increasing interest in outdoor dirt, and there is a demand for an exterior material to which dirt is hardly adhered and which is easily removed even if it is adhered. In response to this need, a technology for adding a silicate compound to a paint has been developed as a low-contamination paint. For example, WO 94/06870
No., WO 95/02645, WO 96/2625
No. 4, each publication discloses a coating composition that can hydrophilize the surface of a coating film using a silicate compound (tetrafunctional hydrolyzable silane compound). However, foaming of these coating compositions becomes remarkable by incorporating a silicate compound. Therefore, in order to impart defoaming properties, when a normal defoaming agent is added to the coating composition, the defoaming properties are improved, but the original effect of improving the anti-staining and adhesion properties by hydrophilizing the surface is impaired. . Furthermore, when an ordinary antifoaming agent is used, there remains a problem that repelling of a coating film at the time of coating is remarkable and coating workability is deteriorated.

[0003]

SUMMARY OF THE INVENTION The present inventors have developed a specific method for improving the antifouling property mainly in the outdoors.
When dimethyl silicone oil having a fluoroalkyl group is blended as a defoaming agent when using various types of silicate compounds, the defoaming property can be obtained without lowering the antifouling adhesion, and cissing of the coating film at the time of painting is achieved. And found that the present invention can also be prevented, and completed the present invention.

[0004]

That is, the present invention provides:
(A) paint resin and (B) formula (1):

[0005]

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(Wherein, R is the same or different, and each is an organic group having 1 to 9 carbon atoms or a hydrogen atom which may contain a nitrogen atom, an oxygen atom, a fluorine atom and / or a chlorine atom, and n is A compound represented by the formula (2):

[0007]

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Wherein at least one of R ¹ is C ₈ F ₁₇ C
H ₂ CH ₂ , the rest being the same or different, each of which may be a nitrogen atom, an oxygen atom, a fluorine atom and / or a chlorine atom-containing organic group having 1 to 9 carbon atoms or a hydrogen atom, m is (D represents an integer of 1 to 100) and (D) a dimethyl silicone oil having a fluoroalkyl group.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention having excellent antifouling adhesion and defoaming properties is, as described above, a coating resin (A), a silicate compound (B) of the formula (1), (2)
Silicate compound containing C ₈ F ₁₇ CH ₂ CH ₂ group (C)
And a dimethyl silicone oil (D) having a fluoroalkyl group.

Hereinafter, each component will be described.

Resin for coating (A) Solvent-soluble fluoroolefin copolymer having hydroxyl group and / or carboxyl group, acrylic polyol resin, acrylic silicon resin, inorganic material, vinylidene fluoride having no functional group A polymer or copolymer, a composite aqueous dispersion of a vinylidene fluoride copolymer and an acrylic copolymer, or an aqueous dispersion of a fluoroolefin-vinyl ether copolymer is preferred.

Examples of the fluoroolefin copolymer having a hydroxyl group and / or a carboxyl group include JP-B-60-21686 and JP-A-3-121107.
JP-A-4-279612, JP-A-4-28707
And those described in JP-A-2-232221 and the like. The number average molecular weight (by GPC) of the copolymer is 1000 to 100000
And 1500 to 30000 is preferred. If the molecular weight is less than 1,000, the curability and weather resistance tend to be insufficient, and if it exceeds 100,000, problems tend to occur in workability and coatability.

The hydroxyl value of the copolymer is from 0 to 2
00 (mgKOH / g) and 0 to 150 (mgKO
H / g). When the number of the hydroxyl groups is reduced, curing tends to be poor, and 200 (mgK
OH / g) tends to cause a problem in the flexibility of the coating film.

The acid value is from 0 to 200 (mgKOH /
g), and more preferably 0 to 100 (mgKOH / g). If the acid value is low, curing tends to be poor, and if it exceeds 200 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.

As one of the copolymers, a tetrafluoroethylene copolymer can be used from the viewpoints of anti-staining property, anti-staining property, and anti-rust property.

Examples of the copolymer include Zeffle manufactured by Daikin Industries, Ltd., Lumiflon manufactured by Asahi Glass Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., Fluonate manufactured by Dainippon Ink and Chemicals, Toa Gosei Co., Ltd. Commercial products such as Zaflon manufactured by the company are listed.

Known resins can be used as the acrylic polyol resin. The resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.

The hydroxyl value of the acrylic polyol resin is from 0 to 200 (mgKOH / g).
(MgKOH / g). When the hydroxyl value is low, curing failure tends to occur,
If it exceeds 00 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.

The acid value of the acrylic polyol resin is as follows:
0 to 200 (mg KOH / g) and 0 to 100 (m
gKOH / g). When the acid value is low, curing tends to be poor, and
If it exceeds 0 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.

As the acrylic polyol resin, for example, Dianal manufactured by Mitsubishi Rayon Co., Ltd., Acridic manufactured by Dainippon Ink and Chemicals, Hitachi Chemical Co., Ltd., Hitaloid, and Mitsui Toatsu Chemicals Co., Ltd., Olestar, etc. Commercially available products can be used.

The acrylic silicone resin may be any resin obtained by polymerizing an acrylic silicone monomer together with a hydroxyl group-containing monomer and other polymerizable unsaturated monomers. The acrylic silicone resin may have a hydrolyzable silyl group, a hydroxyl group, or an epoxy group.

As the acrylic silicone resin, for example, Zemurac manufactured by Kanegafuchi Chemical Industry Co., Ltd. and Sanyo Chemical Industry Co., Ltd.
Commercially available products such as Cleamar can be used.

Examples of the inorganic material include a non-fluorinated non-hydrolyzable group-containing metal (Si, Ti, Al, etc.) alkoxide, a non-fluorine-containing non-hydrolyzable group-containing organopolysiloxane, and a non-fluorine-containing metal. (Si, Ti, Al, etc.) alkoxides and the like. Commercially available products include, for example, Ekolton, released by Gunze Sangyo Co., Ltd., Glasca manufactured by Nippon Synthetic Rubber Co., Ltd., porcelain manufactured by Toupe Co., Ltd., and Bellclean manufactured by Nippon Yushi , Bellhard, SH, SR and DC series manufactured by Dow Corning Toray Silicone Co., Ltd., KR series manufactured by Shin-Etsu Chemical Co., Ltd., Plenact manufactured by Ajinomoto Co., Ltd., organic titanate manufactured by Nippon Soda Co., Ltd., Kawaken Fine Chemicals Aluminum alcoholate and aluminum chelate compound manufactured by Co., Ltd., zirconium alcohol manufactured by Hokuko Chemical Industry Co., Ltd. Kisaido, etc. manufactured by Nippon Unicar Company Limited composite modified silicone oil and MMCA the like.

Other examples of the coating resin include fluororesins having no functional group (vinylidene fluoride described in JP-B-43-10363, JP-A-3-28206, JP-A-4-189879, etc.). And a homopolymer or a copolymer of the above), and can be blended with the resin having the above functional group. When a resin having no functional group is used, it is not always necessary to use a curing agent or a curing catalyst in the coating composition of the present invention.

Examples of the composite aqueous dispersion of the vinylidene fluoride copolymer and the acrylic copolymer include those described in JP-A-3-7784 and WO95 / 08582, and commercially available products. Examples thereof include Zeffle manufactured by Daikin Industries, Ltd. and Floren manufactured by Nippon Synthetic Rubber Industry Co., Ltd.

Further, as the aqueous dispersion of the fluoroolefin-vinyl ether copolymer, for example,
And commercially available products such as Lumiflon manufactured by Asahi Glass Co., Ltd., and Fluorate manufactured by Dainippon Ink and Chemicals, Inc.

The silicate compound (B) of the formula (1)
The silicate compound B (hereinafter , referred to as “compound B”) is blended for the purpose of imparting stainproof adhesion to the coating film. That is, when a silicate compound B is formed on the coating film, the silicate compound B is exposed to the surface of the coating film and, when having a hydrolyzable group, undergoes hydrolysis, thereby making the coating film surface hydrophilic and exhibiting antifouling adhesion. You.

In the formula (1), R is a hydrogen atom or an organic group which may contain a nitrogen atom, an oxygen atom, a fluorine atom and / or a chlorine atom as described above.
R may be the same or different.

The organic group has 1 to 9 carbon atoms from the viewpoint of surface concentrating property, hydrolyzing property and desorbability.

As specific examples, for example, H (CH ₂ ) _q ,
(CH ₃ ) ₂ CH, H (CH ₂ ) _q C = O, F (CF ₂ )
_{p (CH 2) q, (} CF 3) 2 CH, H (CF 2) p (CH 2)
_q , F (CF ₂ ) _p (CH ₂ ) _q C = O, H (CF ₂ ) _p (C
H ₂ ) _q C = O, (F (CF ₂ ) _p (CH ₂ ) _q ) ₂ N,
((CF ₃ ) ₂ CH) ₂ N, (H (CF ₂ ) _p (CH ₂ ) _q ) ₂
N, F (CF ₂ ) _p O (CF (CF ₃ ) CF ₂ O) _q CF
_{(CF 3) C = O,} (F (CF 2) p (CH 2) q) 2 C = N,
((CF ₃ ) ₂ CH) ₂ C = N, (H (CF ₂ ) _p (CH ₂ )
_q ) ₂ C = N, F (CF ₂ ) _p (CH ₂ ) _q C = ONR ³ , H
(CF ₂ ) _p (CH ₂ ) _q C = ONR ³ , F (CF ₂ ) _p (C
H ₂ ) _q C = CH ₂ , H (CF ₂ ) _p (CH ₂ ) _q C = CH ₂ ,
F (CF ₂ ) _p (CH ₂ ) _q C = CF ₂ , H (CF ₂ ) _p (C
H ₂ ) _q C = CF ₂ (where q is 0 or an integer of 1 to 6,
p is an integer of 1 to 9, R ³ represents an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear or branched. However, the total number of carbon atoms is up to 9.

Specific examples of these organic groups include, for example, CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH
₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , (CF ₃ ) ₂ CH, H
(CF ₂ ) ₂ CH ₂ , H (CF ₂ ) ₃ CH ₂ , H (CF ₂ ) ₄ C
H ₂ , CF ₃ C = O, CF ₃ CF ₂ C = O, CF ₃ (CF ₂ )
₆ C ＝ O, CF ₃ (CF ₂ ) ₇ C ＝ O and the like.
CF ₃ CH ₂ ,
CF ₃ CF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF
₂ ) ₃ CH ₂ CH ₂ , CF ₃ CＯO and CF ₃ CF ₂ C ＝ O are preferred, and CF ₃ CH ₂ and CF ₃ CF ₂ CH ₂ are more preferred.

In the formula (1), when n is 1, specific examples include the following compounds.

Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OCH ₂ CF ₂ CF ₃ ) ₄ , Si (OCH (C
_{F 3) 2) 4, Si} (OCH 2 CH 2 C 8 F 17) 4, Si (OCH 2 CF 2 CF 2 H) 4, Si (OCH 2 C 4 F 8 H) 4, Si (OCH 2 CF 2 _{CF 3) 2 (OCH 3)} 2, Si (OCH (CF 3) 2) 2 (OCH 3) 2, Si (OCH 2 CH 2 C 8 F 17) 2 (OCH 3) 2, Si (OCH 2 CF 2 CF ₂ H) ₂ (OCH ₃ ) ₂ , Si (OCH ₂ CF ₂ CH ₂ H) ₂ (OC ₄ H ₉ ) ₂ , Si (OCH ₂ CF ₂ CF ₃ ) ₂ (OH) ₂ , Si (OCH (CF ₃ ) ₂ ) ₂ (OH) ₂ , Si (OCH ₂ CF ₂ CF ₂ H) ₂ (ON = CCH ₃ (C ₂ H
₅ )) ₂ , Si (OCOCCF ₃ ) ₄ , Si (OCOC ₂ F ₅ ) ₄ , Si (OCOC ₈ F ₁₇ ) ₄ , Si (OCOCCF ₃ ) ₂ (OCH ₃ ) ₂ , Si (OCOC ₂ F ₅ ) ₂ (OCH ₃ ) ₂ , Si (OCOC ₈ F ₁₇ ) ₂ (OCH ₃ ) ₂ , Si (OCH ₂ CF ₂ CF ₃ ) ₃ (OCH ₂ CH ₂ ) hOCH
_{3, Si (OCH (CF 3} ) 2) 3 (OCH 2 CH 2) hOC
H ₃ , Si (OCH ₂ CF ₂ CF ₃ ) ₂ (OCH ₃ ) (OCH ₂ CH
₂ ) hOCH ₃ , Si (OCH (CF ₃ ) ₂ ) ₂ (OCH ₃ ) (OCH ₂ C
H ₂ ) hOCH ₃ , Si (OCH ₂ CF ₂ CF ₃ ) ₂ (OH) (OCH ₂ CH ₂ )
hOCH ₃ , Si (OCH (CF ₃ ) ₂ ) ₂ (OH) (OCH ₂ CH ₂ )
hOCH ₃ , Si (OCOCF ₃ ) ₃ (OCH ₂ CH ₂ ) hOCH ₃ , Si (OCOC ₂ F ₅ ) ₃ (OCH ₂ CH ₂ ) hOCH ₃ , Si (OCOC ₈ F ₁₇ ) ₃ (OCH ₂ CH ₂ ) hOCH ₃ , Si (OCOCF ₃ ) ₂ (OCH ₃ ) (OCH ₂ CH ₂ ) h
OCH ₃ , Si (OCOC ₂ F ₅ ) ₂ (OCH ₃ ) (OCH ₂ CH ₂ ) h
OCH ₃ , Si (OCOC ₈ F ₁₇ ) ₂ (OCH ₃ ) (OCH ₂ CH ₂ )
hOCH ₃ Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₄ H ₉ ) ₄ , Si (ON = CCH ₃ (C ₂ H ₅ )) ₄ (where h is 1 to 4) Of the above compounds B, those having 1 to 3 carbon atoms in R are preferable.

Examples of the oligomer or cooligomer having n of 2 or more include linear, branched, cyclic, three-dimensional oligomers and cooligomer. The degree of polymerization (n) is preferably from 2 to 100,
More preferably, it is 20. When the degree of polymerization is low, the oligomer or cooligomer tends to have a low boiling point, is easily volatilized during coating, and is hardly taken into the coating film. When the degree of polymerization exceeds 100, it is difficult to control the degree of polymerization during synthesis, and the viscosity of the oligomer or co-oligomer tends to increase, resulting in poor workability. However, when the oligomer or the co-oligomer has a fluorine atom, the polymerization degree is preferably 2 to 40 from the viewpoint of coating film appearance, sag resistance, and alkali resistance.

[0035]

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And the like.

The silicate compound B represented by the above formula (1) is a compound of the compound B, such as a silicon halide, an alkyl metal, a metal alkoxide, or a metal chelate.
One or more kinds of alcohols, carboxylic acids, oximes, β-diketones, β-ketoesters, alkali metal alkoxides, alkali metal salts of carboxylic acids and the like corresponding to the organic group of the silicate compound B; If necessary, in the presence of a catalyst, usually around 1 atm.
It can be synthesized by a method of reacting at a temperature of -100 ° C, preferably 0-80 ° C under stirring, preferably in an atmosphere of a dry inert gas, and a reaction solvent can be used.

In such a synthesis method, the temperature is from 0 to 2
The temperature is set to 00 ° C., preferably 20 to 150 ° C., and water is gradually added to the silicate compound B so that the reaction solution becomes as uniform as possible. Oligomer is obtained. In addition, a co-oligomer can be obtained by using two or more silicate compounds B in such a synthesis method.

In the present invention, the degree of polymerization of the oligomer and the co-oligomer can be controlled by the molar ratio of the water to be reacted and, for example, the silicate compound B. For example, [H
_{When the} reaction is carried out at a molar ratio of ₂ O] / silicate compound B] = 0.4 to 0.95, an oligomer or cooligomer having a degree of polymerization of about 2 to 20 is obtained. Further, by setting the molar ratio in the range of 0.94 to 1.0,
An oligomer or cooligomer having a degree of polymerization of more than 20 and 100 or less is obtained. In addition, as the co-oligomer,
The composition ratio (molar ratio) of the units constituting the co-oligomer obtained by using two kinds of silicate compounds B is from 1/9 to 9
/ 1 is preferred.

Examples of the catalyst include hydrochloric acid, sulfuric acid,
Acetic acid, paratoluenesulfonic acid, ammonia, trimethylamine, triethylamine, tributylamine, 1,
8-diazabicyclo (5,4,0) undecene-7 (D
BU), (−)-sparteine, 4-N, N-dimethylaminopyridine, monoethanolamine, triethanolamine, N, N, N ′, N′-tetramethylethylenediamine, sodium hydroxide, potassium hydroxide, Acids such as sodium hydrogencarbonate, potassium t-butoxide, sodium ethoxide, tetramethylammonium hydroxide, tetramethylammonium hydrogensulfate, tetrabutylammonium hydroxide, tetrabutylammonium hydrogensulfate, etc.
Organic metals / organic metal salts such as alkalis, dibutyltin dilaurate, dibutyltin acetate, dioctyltin maleate, tetraisopropyl titanate, and tetrabutyl titanate are mentioned. However, hydrochloric acid and ammonia are used because catalyst residues are easily removed from the product. And triethylamine are preferred.

Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, t-butanol, octanol, 2,2,2-trifluoroethanol and 2,2,3,3,3-pentafluoroethanol. , Ethers such as tetrahydrofuran, 1,4-dioxane, and tetrahydropyran; ketones / esters such as acetone and 2-methoxyethyl acetate; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylacetamide; Amides such as N-methylpyrrolidone and polyoxazoline; carboxylic acids such as acetic acid, trifluoroacetic acid and F (CF ₂ ) ₈ COOH; and fluorine-containing aromatics such as trifluoromethylbenzene and m-bistrifluoromethylbenzene. But dissolution 2,2,2-trifluoroethanol in terms of high, 2,2,3,3,3-pentafluoro-ethanol, tetrahydrofuran, 1,4-dioxane, tetrahydropyran are preferred.

The silicate compound B is hydrolyzed in the coating film to make the coating film surface hydrophilic, and can give the coating film excellent antifouling adhesion, low electrification and antifogging properties.

In particular, when at least one of Rs in the compound B has a fluorine atom, it is possible to obtain an effect of, for example, excellent surface concentrating property and reproducibility of surface hydrophilicity. The content of the fluorine atom in the compound B is at least 5% by weight, preferably 15 to 60% by weight.
By doing so, it is possible to obtain the effect of being more excellent in surface concentrating property and reproducibility of surface hydrophilicity.

In the formula (1), n is 2 or more and 100
The following oligomers or co-oligomers have the effect of, for example, excellent coating film appearance, sagging resistance and alkali resistance.

The compound B is used in an amount of 0.1 to 80 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the coating resin.
Parts by weight. If the amount is less than 0.1 part by weight, the antifouling property tends to decrease, and if it exceeds 80 parts by weight, the appearance of the coating film tends to be poor, and the compatibility with the resin tends to decrease.

The silicate compound of the formula (2) (hereinafter referred to as
The silicate compound C represented by the formula (2) is represented by the formula (2 ) wherein R ¹ is C ₈
It has at least one long-chain hydrophobic group of H ₁₇ C ₂ H ₅ , and exhibits an antifoaming action by this hydrophobic group. R ¹
Forms a coating film and is then separated by hydrolysis to hydrophilize the coating film surface. Therefore, not only does the hydrophilicity of the coating film surface imparted with the compound B be impaired, but it can be improved.

In the formula (2), R ¹ other than C ₈ F ₁₇ CH ₂ CH ₂ is a hydrogen atom, a nitrogen atom, an oxygen atom,
It is an organic group having 1 to 9 carbon atoms which may contain a fluorine atom and / or a chlorine atom. Such organic groups include
The carbon number 1 described for the silicate compound B of the formula (1)
To 9 organic groups.

Specific examples of the silicate compound C include, for example, Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH) ₂ , Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₃ (OCH ₂ CH ₂ ) _g OC
H ₃ , Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ ) (OCH ₂ C
H ₂ ) _g OCH ₃ , Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH) (OCH ₂ C
_{H 2) g OCH 3, Si} (OCH 2 CH 2 C 8 F 17) (OCH 3) 3, Si (OCH 2 CH 2 C 8 F 17) (OC 2 H 5) 3 ( wherein, g is 1 And an integer of 4).

The oligomer or co-oligomer of formula (2) wherein m is 2 or more may be a linear or branched oligomer or co-oligomer.
Oligomer or cooligomer such as cyclic or three-dimensional is exemplified. The degree of polymerization (m) is preferably 2 to 100, and more preferably 2 to 40. When the degree of polymerization is low, the oligomer or cooligomer tends to have a low boiling point, is likely to be volatilized at the time of coating, becomes difficult to be taken into the coating film, and has a low defoaming property. Polymerization degree is 10
If it exceeds 0, it is difficult to control the degree of polymerization during the synthesis, or the viscosity of the oligomer or co-oligomer tends to be high, resulting in poor workability. However, when the oligomer or co-oligomer has a fluorine atom, the degree of polymerization is 2 from the viewpoint of coating film appearance, sag resistance and alkali resistance.
~ 40, for example,

[0050]

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And the like.

The silicate compound C can be produced in the same manner as for the compound B.

The compounding amount of the compound C is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the coating resin.
Parts by weight. If the amount is less than 0.01 part by weight, the defoaming property tends to be low. If the amount is more than 5 parts by weight, the hydrophilicity tends to decrease, and the coating film tends to be repelled.

Dimethylsilyl having a fluoroalkyl group
Corn oil (D) Dimethyl silicone oil (D) having a fluoroalkyl group is blended as an antifoaming agent. Although the compound C also has the defoaming property, the addition of the dimethyl silicone oil (D) can further improve the defoaming property and prevent cissing of the coating film at the time of coating.

As the fluoroalkyl group, for example, C
F _3, etc. _{CF 3 CF 2, C 8 F} 17 and the like, the degree of polymerization of dimethyl silicone oil is about 10 to 1000.

Examples of the dimethyl silicone oil (D) having a fluoroalkyl group include FQF501 manufactured by Toshiba Silicone Co., Ltd .; FL100, FA-600, FA-630, and X-50 manufactured by Shin-Etsu Chemical Co., Ltd. −
741, X-70-170C; FS-1265 (10000CS), FS-126 manufactured by Dow Corning Asia Ltd.
5 (1000CS); FZ-3 manufactured by Nippon Unicar Co., Ltd.
108; AO-40H, AO-9 manufactured by Kyoeisha Chemical Co., Ltd.
70H and the like.

The amount of the dimethylsilicone oil (D) having a fluoroalkyl group is 0.001 to 1.0 part by weight, preferably 0.01 part by weight, per 100 parts by weight of the coating resin.
1 to 0.3 parts by weight. If the amount is less than 0.001 part by weight, the defoaming property tends to be insufficient, and if it exceeds 1.0 part by weight, the surface hydrophilicity tends to be alienated.

Other Additives The coating composition of the present invention may contain a curing agent, a curing catalyst, and a chlorofluorocarbon-based solvent as long as the desired antifouling property and antifoaming property of the present invention are not impaired. Good.

Examples of the curing agent include isocyanate compounds, blocked isocyanate compounds, melamine resins, dibasic acids, non-hydrolyzable group-containing silane compounds, epoxy resins and acid anhydrides. Isocyanates, blocked isocyanates and epoxy resins are preferred from the viewpoint of rain.

Examples of the isocyanate compound and the blocked isocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, and trimethylhexamethylene. Diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and burettes thereof, polymers having two or more isocyanate groups, and further blocked Examples include isocyanates, but are not limited thereto.

The mixing ratio of the isocyanate and the coating resin is preferably 0.5 to 5.0, more preferably 0.8 to 1.2, in NCO / OH (molar ratio). When the isocyanate is of a moisture-curable type, it is 1.1 to 1.5.
Is preferred.

Examples of the melamine resin include a melamine resin, a methylolated melamine resin obtained by converting melamine to methylol, an alkyl etherified melamine resin obtained by etherifying methylolated melamine with alcohols such as methanol, ethanol, and butanol. However, the present invention is not limited to these.

As the epoxy compound, for example,

[0064]

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[0065] However, the present invention is not limited thereto.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2-cyclohexyldicarboxylic anhydride, succinic anhydride,
Examples thereof include maleic anhydride, but are not limited thereto.

Further, fumaric acid, succinic acid, adipic acid,
Dibasic acids such as azelaic acid, sebacic acid, dodecanedioic acid and 1,2-cyclohexyldicarboxylic acid are also used as curing agents.

The curing agent is 1 part per 100 parts by weight of the coating resin.
00 parts by weight or less, preferably 5 to 40 parts by weight.

Examples of the curing catalyst include organic tin compounds, organic acid phosphates, organic titanate compounds, and the like.
A reaction product of an acidic phosphoric acid ester and an amine, a saturated or unsaturated polycarboxylic acid or an acid anhydride thereof, an organic sulfonic acid, an amine compound, an aluminum chelate compound,
Titanium chelates, zirconium chelates and the like can be mentioned.

Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate and the like.

Specific examples of the organic acid phosphate include:

[0072]

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And the like.

Examples of the organic titanate compound include titanates such as tetrabutyl titanate, tetraisopropyl titanate and triethanolamine titanate.

Further, specific examples of the amine compound include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
-Methylmorpholine, 1,8-diazabicyclo (5.
4.0) amine compounds such as undecene-7 (DBU), furthermore salts thereof such as carboxylic acids, low-molecular-weight polyamide resins obtained from excess polyamines and polybasic acids,
Examples of the reaction product include an excess of a polyamine and an epoxy compound.

Specific examples of the chelate compound include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), zirconium tetrakis (acetyl acetonate), diisopropoxy bis (ethyl acetoacetate) titanate and the like. .

One curing catalyst may be used, or two or more curing catalysts may be used in combination. Preferred curing catalysts include organotin compounds and aluminum chelate compounds.

In the present invention, the combination of the coating resin and a curing agent and / or a curing catalyst is not particularly limited, but preferred combinations include the following.

In the case of a fluoroolefin copolymer having a hydroxyl group and / or a carboxyl group or an acrylic polyol resin, when these have a hydroxyl group, the curing agent is an isocyanate compound, a blocked isocyanate compound or a melamine resin. As a curing agent when it has, it is a melamine resin or an epoxy compound. In these systems, a curing catalyst can be used in combination.

In the case of acrylic silicone resin, fluorosilicone resin or inorganic material, a curing catalyst may be used.

The curing catalyst is used in an amount of 50 parts by weight or less, preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of the coating resin.

The chlorofluorocarbon-based solvent is preferably a liquid at room temperature, and is preferably trichlorofluoroethane, tetrachlorodifluoroethane, trichlorotrifluoroethane, dibromotetrafluoroethane, HCFC-12.
3, HCFC-141b, HCFC-225, dichlorohexafluorocyclobutane, tetrachlorohexafluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, etc., and the compounds 1 and / or 2, Furthermore, in order to dissolve the coating resin and the curing agent well,
It is desirable to simultaneously contain a fluorine atom, a chlorine atom, and a carbon atom, and HCFC-123, HCFC-141b, HC
FC-225 and tetrachlorohexafluorobutane are preferred.

It is also possible to combine two or more of these fluorocarbon solvents, or to combine them with a hydrocarbon organic solvent. The blending ratio of the paint resin and the chlorofluorocarbon solvent was 0.1 to 100 parts by weight of the paint resin.
５０50 parts by weight, and 0.1-20 parts by weight from the viewpoint of coating film appearance.

In the present invention, an organic solvent can be blended in the composition for coating.

Examples of the organic solvent include xylene, toluene, Solvesso 100, Solvesso 150,
Hydrocarbon solvents such as hexane, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
Ester solvents such as ethylene glycol monobutyl ether acetate, 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 mono Ethyl 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,
Ether solvents such as diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and tetrahydrofuran; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone; N, N-dimethylacetamide;
Amide solvents such as methylacetamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, sulfonic acid ester solvents such as dimethylsulfoxide, methanol,
Ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (degree of polymerization: _{3 to} 100), CF ₃ CH ₂ OH, F (C
F ₂ ) ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH, F (CF ₂ ) ₃
CH ₂ OH, F (CF ₂ ) ₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ C
H ₂ OH, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂
Examples thereof include alcoholic solvents such as OH, and alcoholic solvents such as lower alcohols and lower fluoroalcohols are preferable from the viewpoint of compatibility, appearance of the coating film, and storage stability.

The mixing ratio of the coating resin and the alcohol solvent is 1 to 50 parts by weight of alcohol with respect to 100 parts by weight of the coating resin, and 1 to 25 parts by weight in terms of curability and appearance of the coating film. Is more preferable.

When the curing agent has a high reactivity with alcohol such as a room temperature-curable isocyanate,
Further, the amount is preferably 1 to 15 parts by weight, and the type of alcohol is preferably a secondary or tertiary alcohol.

The coating composition of the present invention further includes, for example, a pigment, a pigment dispersant, a thickener, a leveling agent, other defoaming agents other than those described above, a film-forming auxiliary, an ultraviolet absorber, a HALS, a matting agent. Agents, fillers, colloidal silica, fungicides, silane coupling agents, anti-skinning agents, antioxidants, flame retardants, anti-dripping agents, antistatic agents, rust inhibitors, water-soluble resins (polyvinyl alcohol, polyethylene oxide, etc.) ) Can also be blended. However, the other defoaming agents need to be in amounts that do not impair the hydrophilicity of the formed coating film.

Examples of the pigment include titanium oxide,
Examples include iron oxide, aluminum metallic pigment, carbon black, calcined pigment, phthalocyanine pigment, organic pigment, extender pigment and the like.

Examples of the titanium oxide include, for example, Taipaque CR-90, CR-93, and CR-90 manufactured by Ishihara Sangyo Co., Ltd.
95, CR-97 and the like.

Examples of the iron oxide include Todacolor 120ED, 140ED, 160E manufactured by Toda Kogyo Co., Ltd.
D, KN-R, KN-V, Taro manufactured by Titanium Industry Co., Ltd.
LL-XLO, HY-100, HY-200, BL of X
-100 and BL-500.

Examples of the aluminum metallic pigment include Alpaste 0100M manufactured by Toyo Aluminum Co., Ltd.
A, 0700M, 0200M, 0215M, 1950
M, 1900M, 1100M, 1109M, 1200
M, 8820YF, 7080N, MG600, 1700
N and the like.

Examples of the carbon black include MA7, MA11, MA100 and OI manufactured by Mitsubishi Chemical Corporation.
L7B, OIL30B, OIL31B and the like.

Examples of the calcined pigment include Dipoxide # 9510, # 9512, and # 952 manufactured by Dainichi Seika Co., Ltd.
9410 and # 9310.

Examples of the phthalocyanine pigment include # 5195N and # 5370 manufactured by Dainichi Seika Co., Ltd.

Examples of the extender include asbestos, calcium carbonate, precipitated calcium carbonate, clay, kaolin, porcelain, aluminum silicate, diatomaceous earth, white carbon, silica white, hydrous fine silica, bentonite, talc, magnesium silicate, carbonate Examples include magnesium, barite powder, barium sulfate, and precipitated barium sulfate.

Examples of the pigment dispersant include Anti-Terra-P manufactured by Big Chemie Japan, Inc.
Anti-Terra-U, Anti-Terra-2
03/204, Disperbyk, Disperby
k-101, Disperbyk-110, Dispe
rbyk130, Disperbyk161, Disp
erbyk-164, Disperbyk-170, B
ykumen, BYK-P104 / P105, BYK-
104S, BYK-240S, Lactimon and the like.

Examples of the leveling agent include BYK-300 and BYK-300 manufactured by BYK Japan KK
302, BYK-306, BYK-307, BYK-3
35, BYK-310, BYK-320, BYK-32
2, BYK-323, BYK-324, BYK-32
5, BYK-330, BYK-331, BYK-33
3, BYK-344, BYK-370, BYK-35
4, BYK-355, BYK-358 and the like.

Examples of the thickener include Disparon # 6900-20X and # 6900 manufactured by Kusumoto Kasei Co., Ltd.
-10S, # 4200-20, # 4200-10, NL
Benton SD-1, SD-2, SD manufactured by Chemicals Corporation
-3, # 27, # 34, # 38, MPA-2000X and the like.

Examples of the other defoaming agent include those other than the compound C and the silicone oil (D). For example, BYK-051 manufactured by BYK Japan KK,
BYK-052, BYK-053, BYK-055, B
YK-057, BYK-065, BYK-066, BY
K-070, BYK-077, BYK-080, BYK
-088, BYK-141, Paintat 54, Dow Corning Asia Co., Ltd., Paintat S, DB-
100, OC-2 compound, FS544, FS01
1, FS80, FS81, DKQ1-071, DKQ1
-1086, paintat 7, etc., but as described above, it is necessary to use an amount that does not impair the hydrophilicity of the formed coating film.

As the ultraviolet absorber, for example, benzophenone-based and benzotriazole-based ones are preferable.
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methyoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone are the same as those of 2- (2'
-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole), 2-
(2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-
5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tertbutylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3 ', 5'-ditertbutylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tertoctylphenyl) benzotriazole are effective.

A particularly suitable ultraviolet absorber is represented by the formula (3):

[0103]

Embedded image

(Wherein R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, a lower alkyl group, particularly a branched lower alkyl group or an aryl group, particularly a phenyl group, and X represents hydrogen. Atom or halogen atom, especially chlorine atom).

Examples of the HALS include Tinuvin-770, 292, and 62212 manufactured by Ciba-Geigy Corporation.
3, 440 and the like.

Examples of the matting agent include Seridust # 3620 and # 96 manufactured by Hoechst Industry Co., Ltd.
15A, # 9612A, # 3715, # 3910, etc.
Hoechst wax PE520, white carbon, and the like.

Examples of the silane coupling agent include methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylisocyanate, 3-triethoxysilylpropylisocyanate, methyltris (ethylmethylketoxime)
Examples thereof include silanes, and those containing an alkylketoxime group or an isocyanate group are preferred.

The coating composition of the present invention is excellent in solvent solubility and leveling property, and the formed coating film has a high degree of weather resistance, stain resistance, chemical resistance, optical properties, and mechanical properties. Excellent in properties, adhesion to base material, heat-resistant yellowing, etc., as well as ordinary curing compositions, for indoor use such as building materials and interior materials, or for outdoor use such as automobiles, aircraft, ships, trains, etc. Can be applied directly to metals, concrete, plastics, etc. as a paint, or overlaid on an undercoat such as wash primer, rust preventive paint, epoxy resin, acrylic resin paint, polyester resin paint. Further, it can be used as a sealing agent or a film forming agent.

The coating composition can take various forms such as clear, solid, and compounding of a filler.

As for the coating method, various methods such as spray, brush, roller, curtain flow, roll, and dipping are used.

The coating composition of the present invention can be applied to various substrates. Examples of the substrate to be applied include a metal substrate, a cement substrate, and a plastic substrate.

Examples of the metal base include iron and its chemical conversion products or plating products, aluminum and its chemical conversion products, stainless steel and its chemical conversion products, and the like.

Examples of the cement-based material include cements, limes, gypsum, concrete, cement mortar, asbestos slate, gypsum board and the like.

Examples of the plastic base material include polyvinyl chlorides, polyesters, polycarbonates, acrylics, polyolefins, polystyrenes, polyurethanes, polyamides, nylons, natural rubbers, urethane rubbers, and ABS. Resins.

When the base material is a metal base material, for example, after applying the following undercoat paint and intermediate paint,
It is preferable to apply the coating composition of the present invention from the viewpoint of anticorrosion properties and interphase adhesion.

In this case, a zinc-rich paint is preferred as the undercoat.

Examples of the vehicle of the organic zinc-rich paint include a combination of an epoxy resin and a polyamide resin, a chlorinated rubber, a polystyrene resin, and a silicone resin. Examples of the vehicle of the inorganic zinc-rich paint include ethyl silicate, Examples include sodium silicate, lithium silicate, potassium silicate, and ammonium silicate. Particularly preferred vehicles for purposes such as the present invention are epoxy resin-polyamide resin combinations, ethyl silicate, potassium silicate, and lithium silicate.

Other examples of the undercoat paint and the intermediate paint are preferably epoxy resins (including tar-modified and urethane-modified), vinyl resins (including tar-modified and acrylic resins), chlorinated rubbers, polyurethane resins, and phenols. At least one kind of synthetic resin selected from resins, a commonly used coloring pigment, extender pigment, suspending agent, dispersant,
It is a paint obtained by kneading a curing agent, a curing accelerator, a diluent, a solvent and the like.

The epoxy resin is a resin having two or more epoxy groups in a molecule and usually used for paint.

As the epoxy resin, for example, bisphenol type epoxy resin is commercially available under the trade names of Epicoat 828, 834, 836, 1001, 1004, and DX-X (trade names, manufactured by Shell Chemical Co., Ltd.).
255, trade name Araldite G manufactured by Ciba Geigy Co., Ltd.
Y-260, trade name DER3 manufactured by Dow Chemical Co., Ltd.
30, 331, 337: DEN431, 43 manufactured by Dow Chemical Co., Ltd., which are generally marketed as phenol novolak type epoxy resins, such as Epicron 800 manufactured by Dainippon Ink and Chemicals, Inc.
8. As a polyglycol type epoxy resin, Araldite CT-trade name, commercially available from Ciba-Geigy Co., Ltd.
508, trade name DER-73 manufactured by Dow Chemical Co., Ltd.
2, 736, as an ester type epoxy resin, for example, Epicron 2 manufactured by Dainippon Ink and Chemicals, Inc.
Examples of the linear aliphatic epoxy resin include epoxidized polybutadiene such as BF-1000 (trade name, manufactured by Nippon Soda Co., Ltd.).

Further, epoxy compounds easily deduced from these resins, and derivatives of the epoxy resins, can also be used, and are included in the technical scope of the present invention.

For example, polyol type epoxy resins, alicyclic epoxy resins, halogen-containing epoxy resins and the like are included.

The epoxy resin includes natural asphalt,
Asphaltite, asphalt-based pyrobitumen,
Bituminous substances such as tar, coal tar, artificial asphalt and pitch can be mixed.

As the curing agent for the epoxy resin, those usually used for coating materials, such as amine adducts and polyamide resins, can be used.

Examples of the curing agent include Toamide Y-25, 245, 2400, and 2500 manufactured by Fuji Kasei Kogyo Co., Ltd., which are generally commercially available as polyamide resin, and trade names manufactured by Daiichi General Co., Ltd. Zenamide 200
0, Versamide 115, 125, manufactured by Sanwa Chemical Co., Ltd., Sunmide 320, 330, X2000, manufactured by Shell Chemical Co., Ltd., Epicure 3255, 425
5. Tomide 238 and Fuji Cure 202 manufactured by Fuji Chemical Industry Co., Ltd., Adeka Hardener EH-531 manufactured by Asahi Denka Co., Ltd., and Sunmide T manufactured by Sanwa Chemical Co., Ltd. as an aliphatic polyamine, as amine adduct resins.
-100, D-100, P-100, Epomate B-00 manufactured by Ajinomoto Co. as a heterocyclic diamine derivative
2, C-002 and S-005.

The amount of the curing agent to be added to the epoxy resin is around the equivalent, that is, 0.1 to 1 equivalent of the epoxy resin.
It is in the range of about 7 to 1.3 equivalents.

Further, a polyisocyanate can be used as a curing agent for the epoxy resin.

The vinyl resins used in the present invention include, for example, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, styrene, vinyl toluene,
It is a copolymer of one or more monomers such as vinyl alcohol, acrylic acid, methacrylic acid, maleic anhydride, alkyl acrylate, alkyl methacrylate, and is a copolymer of vinyl chloride resin and vinyl chloride-vinyl acetate copolymer. A coalescing resin, an acrylic resin and the like can be mentioned.

The chlorinated rubber resin used in the present invention is a chlorinated product of natural rubber and usually has a chlorine content of 65 to 68%.

The chlorinated rubber can be used by mixing with rosin, coumarone-indene resin, phenol resin, vinyl chloride resin, petroleum resin, nitrile rubber, chloroprene rubber, and alkyd resin.

Further, paraffin chloride, diphenyl chloride,
It is used by mixing with a plasticizer such as dioctyl phthalate and tricresyl phosphate.

Further, the polyurethane resin used in the present invention is a compound having two or more active hydrogens in a molecule, for example, a polyester polyol, a polyether polyol, a polyoxyalkylene obtained from a polybasic acid and a polyhydric alcohol. This is a composition using glycol, acrylic polyol, or the like as a main agent, and using a polyisocyanate having two or more isocyanate groups in the molecule described above as a curing agent.

When the base material is a cement base material, it is preferable to apply the coating composition of the present invention after applying, for example, the following undercoat paint and intermediate paint.

Examples of the undercoat paint include a multi-layer finish paint such as an uncured synthetic resin emulsion-based multi-layer finish paint, a reaction-curable water-soluble epoxy resin multi-layer pattern finish paint, and a reaction-curable solvent-based epoxy resin multi-layer finish paint. It is particularly preferred to use The resin components of the uncured synthetic resin emulsion include, for example, acrylic resins, vinyl acetate resins, and modified resins thereof. Examples of the curing system of the reaction-curable aqueous or solvent-based epoxy resin include an epoxy-polyamine system, an epoxy-polyamide system, and an epoxy-polyamine polyamide system.

The method of applying the undercoat paint to the cement-based substrate can be performed by, for example, spray coating, roller coating, or the like. The coating amount is usually 0.5 to 2.0 kg / m
² seems sufficient. The drying is generally performed for 1 to 3 days.

Before the undercoat paint is applied to the cement base material, a conventionally known primer, surfacer sealer, or the like generally used for an architectural foundation treatment can be applied. In addition to the above-mentioned undercoat paints, there are included those obtained by directly applying or applying the sealer to a sealer such as a solvent type epoxy resin and then performing a smooth finish with an isocyanate curable resin paint.

The method of applying the coating composition of the present invention to an undercoat film can be performed by, for example, roller coating, brush coating, spray coating, or the like. Coating amount is 0.05 ~
0.5 kg / m ² , preferably 0.1 to 0.3 kg / m ²
It is. Drying can form a cured coating in one day or more at room temperature.

[0138] As a refurbishment coating method, an old top coat of an architectural exterior coat applied to a cement base material is subjected to a base treatment if necessary, and then the paint composition of the present invention is applied and renovated. There is a way.

[0139] In the above method, the old topcoat film includes:
Although not particularly limited, a curable fluorine paint, a curable acrylic paint, an acrylic silicone paint, a carbonyl-hydrazide curable water-based paint, a vinyl acetate-modified acrylic resin paint, and the like, as used in the paint composition of the present invention described above. A coating film formed by a non-crosslinked aqueous coating such as a non-crosslinked solvent-based coating and an acrylic resin-based aqueous coating is particularly preferred.

The carbonyl-hydrazide-curable water-based paint is prepared by blending a water-dispersible carbonyl group-containing copolymer with a dihydrazide crosslinking agent and an aqueous polyurethane resin having a hydrazine residue (for example, Japanese Patent Application No. Hei 10 (1994) -108,197). 171683). A primer and a surfacer may be coated between the old top coat and the cement base material, or a multi-layer coating material may be coated on this.

The undercoat treatment, if necessary, performed on the old top coat can be carried out, for example, by applying the following undercoat agent. Preferred examples of the base treating agent include cement-based (eg, cement / synthetic resin emulsion-based) fillers or surfacers, and reaction-curable resin-based (eg, epoxy polyamine-based, epoxy polyamide-based) penetrating sealers, and the like. Can be

The undercoating method can be carried out by applying the undercoating agent with, for example, a roller or a brush. The coating amount of the surface treatment agent, for example those of the filler 0.3~2.0kg / m ^2, the surfacer 0.1~1.0kg / m ^2, the penetration-type sealer 0.0
It is considered that 1 to 0.5 kg / m ² is sufficient.

[0143] After the application of these undercoating agents, a polyisocyanate-curable solvent-based paint can be further applied. This coating method can be performed by, for example, a roller, a brush, or spraying. Also, it is considered that an application amount of 0.05 to 0.5 kg / m ² is sufficient. Drying of the undercoating agent and the polyisocyanate-curable solvent-based paint is usually performed 1 to 3 times. The coating and drying of the coating composition of the present invention can be carried out in the same manner as the above-mentioned coating composition of the present invention.

When the base material is a plastic base material, the undercoat paint and the intermediate paint used for the metal base material and the cement base material are applied, and then the coating composition of the present invention is applied. You can also.

When the base material is a film or sheet among plastic base materials, examples of the coating method include a gravure coating method, a doctor blade method, a roll coating method, a reverse roll method, and an air knife coating method. In the case of these coating methods, the coating film thickness is suitably from 1 to 20 μm, preferably from 1 to 10 μm, from the viewpoint of coating film appearance and coatability.

Examples of uses of the article coated with the coating composition of the present invention include a waterproof sheet for construction, a waterproof sheet for tunnel, a vinyl sheet for agriculture, a vinyl film for agriculture, a curing sheet, a protective sheet for a building and a vehicle. For protection sheet, mesh sheet, mesh screen, polycarbonate roof, acrylic board wall, polycarbonate wall, guardrail, traffic signal, tunnel inner wall, tunnel interior board, road sign, information board, highway side wall, highway soundproof wall, road light, bridge , Bridge girders, piers, chimneys, wallpapers, tatami mats, mats, tablecloths, ventilation fans, marking films, geomembranes, billboards, post boxes, telephone poles, tents, automobiles, aircraft, ships, trains and the like.

[0147]

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

Synthesis Example 1 (Synthesis of Compound B) In a 20-liter glass flask, 2.6 kg of methyl silicate 51 (tetramethoxysilane oligomer (about tetramer) manufactured by Colcoat Co., Ltd.) was charged. , 2,3,3,3-pentafluoropropanol (5
FP) 10.0 kg. Then 5FP 2.4kg
Was added over 30 minutes. After the mixture was stirred at 40 ° C. for 1 hour, the temperature was raised and the volatile components methanol, 5FP and triethylamine were distilled off. When 10.5 kg was distilled off, the distillation was stopped, and the content was cooled to room temperature. 4.49 kg of the product remained in the flask. As a result of analysis by 1H-NMR, CF ₃ CF ₂ CH ₂ O groups and CH ₃ O
The molar ratio of the groups was 0.71 to 1.

Synthesis Example 2 (Synthesis of Compound C) Methyl silicate 5 was placed in a 3 liter glass flask.
500 g of 1, and then 1500 g of 2-perfluorooctylethanol heated to 50 ° C were charged, and the reaction mixture was heated at 150 to 170 ° C for 10 hours. During this time, methanol and the like generated by the transesterification flowed out.
Upon cooling the contents to room temperature, 1850 g of product was obtained. When analyzed by 1H-NMR, the product C
The molar ratio of ₈ F ₁₇ CH ₂ CH ₂ O groups to CH ₃ O groups was 0.50 to 1.

Example 1 Zeffle GK-500 / Zeffle GK-510 white paint (GK-500 / GK-510 = 7/3 (weight ratio), hydroxyl value = 60, acid value = 2.7, pigment / resin = 0.833
(Weight ratio), pigment CR-95, fluororesin solid content 30% by weight) and 100 g of the compound obtained in Synthesis Example 1 were added in an amount of 4.5 g.
(15 parts by weight with respect to 100 parts by weight of fluororesin), 0.9 g of the compound obtained in Synthesis Example 2 (3 parts by weight with respect to 100 parts by weight of fluororesin), and FZ-3108 which is a dimethyl silicone oil D having a fluoroalkyl group. 0.06 g
(0.2 parts by weight based on 100 parts by weight of the solid content of fluororesin), 7.0 g of Takenate D-140N, 3.5 g of Coronate HX (NCO / OH = 1.1) and 30 g of butyl acetate were added. added. This coating composition was applied to an AM-712 treated aluminum plate (7 ×
(15 × 0.5 cm), and cured and dried at room temperature for 1 week to obtain a coated plate having a coating thickness of about 40 μm, and the subsequent tests were performed.

(Defoaming property) A composition for a paint was prepared to be 20 cm × 30
cm tinplate with a roller (Small roller SY11M manufactured by Yoshikawa Sangyo Co., Ltd.) while applying a breeze, drying at room temperature for 1 hour (touch drying), and the remaining foam on the coating film surface The degree is visually observed.

Evaluation A: No residual foam B: 1 to 9 residual foam C: 10 to 30 residual foam D: 31 or more residual foam (Repelling property) 70 g of butyl acetate was further added to the coating composition obtained in Example. In addition, the state of the coating film is visually determined by spray coating.

A: No abnormality B: Some cissing occurred C: Extremely cissing occurred (Anti-contamination adhesion) The coated plate prepared in the defoaming test was inclined on the 3rd floor rooftop of a building in Osaka Prefecture at a slope of 30 ° on the south side. After 3 months and 6 months of outdoor exposure, the antifouling property and appearance are evaluated. Stain adhesion prevention measures the difference (ΔL *) between the initial lightness of the coated plate and the lightness after exposure.

Evaluation A: ΔL * is less than 0 to 2 B: ΔL * is less than 2 to 4 C: ΔL * is less than 4 to 7 D: ΔL * is less than 7 to 10 E: ΔL * is 10 or more (appearance) As in the defoaming test, the coating is left for one week after the roller coating, and the appearance of the coating film is visually observed.

Evaluation A: No abnormality B: There is some dullness.

C: There is an abnormality (contents are described).

(Gloss) According to JIS K-5400,
Measure the specular gloss at 60 degrees.

(Pencil hardness) Measured according to JIS K-5400.

As a result, the defoaming property was B, the repelling property was A, the antifouling property was B for 3 months and 6 months, the appearance was A for 3 months and 6 months, the gloss was 81, and the pencil hardness was 81. Is 2H
Met.

Examples 2 to 19 Coatings were formed in the same manner as in Example 1 except that the coating resin, compound B, compound C and dimethyl silicone oil D were used in the types and amounts shown in Table 1. Done. Table 1 shows the results.

Comparative Examples 1-2 When dimethyl silicone oil having a fluoroalkyl group (FZ-3108) was not used in Example 1 (Comparative Example 1), and dimethyl silicone oil having a fluoroalkyl group in Example 2 was used. (AO-4
0H) (Comparative Example 2)
The same test as in Example 1 was performed. Table 1 shows the results.

The abbreviations used in Examples and Comparative Examples (Table 1) indicate the following.

Coating resin GK-500: Zeffle GK- manufactured by Daikin Industries, Ltd.
500 (product name). A tetrafluoroolefin copolymer having a hydroxyl group and being soluble in a solvent.

GK-510: Zeffle GK-510 (trade name) manufactured by Daikin Industries, Ltd. Solvent-soluble tetrafluoroolefin copolymer having a hydroxyl group and a carboxyl group.

LC-941: Zeffle LC-941 (trade name) manufactured by Daikin Industries, Ltd. A composite aqueous dispersion of a vinylidene fluoride copolymer and an acrylic polymer.

A-801: Acridic A-801 (trade name) manufactured by Dainippon Ink and Chemicals, Inc. Acrylic polyol resin.

YC3623: trade name. Acrylic silicone resin manufactured by Kanegabuchi Chemical Industry Co., Ltd.

A-3: Ekolton A-3 (trade name) available from Gunze Sangyo Co., Ltd. Inorganic material (resin for inorganic paint).

1750: Couponil 1750 (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

High silicon acrylic resin (acrylic silicon / silicate graft resin).

Compound B Me51: Methylsilicate 51 (trade name) manufactured by Colcoat. Oligomer of tetramethoxysilane (about tetramer).

Et48: Ethylsilicate 48 (trade name) manufactured by Colcoat. Oligomers of tetraethoxysilane (about 10-mers).

Dimethyl silicone oil D FZ-3108: trade name. Fluorosilicone manufactured by Nippon Unicar Co., Ltd.

AO-40H: Trade name. Kyoeisha Chemical Co., Ltd.
Fluorosilicone.

FA-600: Product name. Fluorosilicone manufactured by Shin-Etsu Chemical Co., Ltd.

Pigment CR-95: trade name. Titanium oxide white pigment manufactured by Ishihara Sangyo Co., Ltd.

Curing agent or curing accelerator D-140N: Takenate D- manufactured by Takeda Pharmaceutical Co., Ltd.
140N (product name). Isophorone diisocyanate curing agent.

HX: Coronate HX (trade name) manufactured by Nippon Polyurethane Co., Ltd. Hexamethylene diisocyanate curing agent.

[0179]

[Table 1]

[0180]

According to the coating composition of the present invention, it is possible to provide a coating which has excellent defoaming properties and does not deteriorate coating workability. The obtained coating film can prevent the adhesion of pollutants outdoors and has less repelling. Things.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 133/14 C09D 133/14 143/04 143/04 // (C09D 201/02 183: 06 183: 08) (72) Invention Person Yasushi Yonei 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd.Yodogawa Works (72) Inventor Tsuyoshi Nagai 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd.Yodogawa Works (72) Inventor Nagata Junichiro 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Yoshikazu Ishimoda 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (3)

[Claims] 1. A resin for paint (A), and (B) a formula (1): (In the formula, R is the same or different, and all are a nitrogen atom, an oxygen atom, an organic group having 1 to 9 carbon atoms which may contain a fluorine atom and / or a chlorine atom or a hydrogen atom, n is 1 to 100 And (C) a compound represented by the formula (2): (Wherein at least one of R ¹ is C ₈ F ₁₇ CH ₂ CH ₂ and the rest are the same or different, all of which are nitrogen atoms,
An organic group having 1 to 9 carbon atoms or a hydrogen atom which may contain an oxygen atom, a fluorine atom and / or a chlorine atom, m
Represents an integer of 1 to 100), and (D)
A coating composition comprising dimethyl silicone oil having a fluoroalkyl group. 2. The composition according to claim 1, wherein R in the formula (1) is an organic group containing a fluorine atom. 3. The coating resin is a solvent-soluble fluoroolefin copolymer having a hydroxyl group and / or a carboxyl group, an acrylic polyol resin, an acrylic silicon resin, an inorganic material, and a vinylidene fluoride having no functional group. Homopolymer or copolymer, a composite aqueous dispersion of a vinylidene fluoride copolymer and an acrylic copolymer,
The composition according to claim 1, wherein the composition is an aqueous dispersion of a fluoroolefin-vinyl ether copolymer.