JP2000129209A - Method for modifying surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface modification method to make a film hydrophilic by decreasing the contact angle to water, and a product therewith. SOLUTION: This surface modification method and coated product therewith are realized by blending 100 pts.wt. of a resin (A) with 2-70 pts.wt. of a silicon- contg. compd. represented by the formula: (R10)4-a-Si-(R2)a and/or a partially hydrolyzed condensate thereof (B) to prepare a curing type compsn. for coating, forming a film by applying the compsn. to the surface of a substrate, and treating the film in hot water or in a satd. steam at 50 deg.C or above, in order to make the film hydrophilic through decreasing the contact angle to water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for modifying the surface of a coating film formed by using a curable composition for a coating and a method for modifying the surface of a coated product using the same. More specifically, for example, building interior and exterior materials consisting of metals, ceramics, glass, cement, ceramic moldings, plastics, wood, paper, fibers, etc., automobiles, bridges, home appliances,
A method for modifying a surface that reduces the contact angle to water and becomes hydrophilic by treating a coating film formed using a curable composition for coating that can be suitably used for coating of industrial equipment with warm water or steam. And a coated article using the same.

[0002]

2. Description of the Related Art Conventionally, in order to impart a design effect to industrial products such as ceramic materials, iron and steel, building materials for buildings, etc., and to improve the weather resistance and corrosion resistance of the products, the compositions comprising various synthetic resins have been used. Attempts have been made to coat the surface of the product. In particular, among such compositions, a composition composed of a synthetic resin having a cross-linked structure such as a fluororesin, an acrylic urethane resin, a melamine resin, and an acrylic silicone resin is obtained when the cured product is exposed outdoors for a long period of time. Even so, it has excellent weather resistance, and is therefore used as a highly weather-resistant composition for coating the exterior of structures. However, in recent years, improvement in stain resistance outside the structure has been demanded, and therefore, further improvement in stain resistance is strongly desired for a cured product of the high weather resistant composition.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above prior art, and exhibits contamination resistance while maintaining the weather resistance, corrosion resistance, design, hardness, etc. inherently exhibited by a resin. By treating the coating film formed using a curable composition for a coating material capable of simultaneously forming a cured product having the hydrophilicity of the coating film surface with warm water or steam, the film is further hydrophilized, It is an object of the present invention to provide a surface modification method for reducing a contact angle with water and a coated article using the method.

[0004]

According to the present invention, there is provided a compound represented by the following general formula (1): (R ¹ O) _4-a -Si- (R ² ) _a (1) (Wherein, R ¹ and R ² are each independently a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. A silicon-containing compound represented by a hydrocarbon group (wherein R ¹ and R ² are not hydrogen atoms at the same time, a represents 0, 1 or 2) and / or a partial hydrolysis condensate thereof (B) A coating film obtained by applying a curable composition for coating composition containing 70 parts by weight to a substrate at 50 ° C.
A method for modifying the surface to reduce the contact angle with water by making it treated in the above-mentioned warm water or steam at 50 ° C. or more, and to make the surface hydrophilic, and to apply a top surface to the coating surface on which the coating material containing the metallic powder and / or the coloring pigment is applied. The present invention relates to a method for modifying the surface of a painted product to which a coat clear paint is applied.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION A method for modifying a surface obtained by applying the curable composition for a topcoat paint of the present invention and each component used in the curable composition for a topcoat paint will be described.
The surface modification method of applying the curable composition for a topcoat paint of the present invention reduces the contact angle to water in a short time by treating the coating film formed on the substrate surface with steam, thereby reducing the hydrophilicity. It is a method to make it. The method of treatment is not particularly limited as long as it is in warm water of 50 ° C. or higher or steam of 50 ° C. or higher, but it is preferable to perform treatment using steam of 60 ° C. or higher, more preferably 70 ° C. or higher. ,
The contact angle can be reduced in a shorter time.

According to the surface modification method of the present invention, the general formula (1): (R ¹ O) _4-a -Si- (R ² ) _a (1) is used for 100 parts by weight of the resin (A) component. (Wherein, R ¹ and R ² are each independently a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. A silicon-containing compound represented by a hydrocarbon group (wherein R ¹ and R ² are not hydrogen atoms at the same time, a represents 0, 1 or 2) and / or a partial hydrolysis condensate thereof (B) A coating film obtained by applying a curable composition for coating composition containing 70 parts by weight to a substrate at 50 ° C.
A method for modifying the surface to make it hydrophilic and reduce the contact angle with water by treating in hot water or in steam at 50 ° C. or higher, and to apply a coating containing a coating containing a metallic powder and / or a coloring pigment on the coating surface. This is a method for modifying the surface of a painted product to which a coat clear paint is applied.

One of the major features of the present invention is that a coating film formed by using the curable composition for a paint, wherein the specific silicon-containing compound (C) component is blended in a specific amount, is heated or steamed. The treatment is carried out to reduce the contact angle with water.

The curable composition for paints of the present invention has not only the resin (A) component inherently exhibiting, for example, weather resistance, corrosion resistance, design properties, hardness, etc., but also the silicon-containing compound (B) component. Since it is contained in a specific ratio, it can be made hydrophilic by treating it in hot water at 50 ° C. or higher or steam at 50 ° C. or higher, and can reduce the contact angle with water, and can be used outdoors for a long time Excellent stain resistance enough to withstand exposure can be provided.

The resin (A) component used in the present invention is not particularly limited, and various thermoplastic resins and thermosetting resins can be used. Among these, an acrylic resin (hereinafter, referred to as resin (A-1)) is used as the resin (A) component because the cured product formed from the obtained curable composition for paint has excellent weather resistance. , A fluororesin (hereinafter, referred to as resin (A-2)), a melamine resin (hereinafter, referred to as resin (A-3)), and an epoxy resin cross-linked with an acid (hereinafter, referred to as resin (A-4)) are preferable. Those containing the resin (A-1) component and / or the resin (A-2) component as a main component are preferred. Note that such a main component means that the resin (A) component is contained in an amount of more than 50% by weight.

[0010] As the resin (A-1) component, a cured product formed from the curable composition for paint obtained is weather resistant,
From the viewpoint of excellent chemical resistance, for example, the main chain is substantially composed of a vinyl polymer chain, and the general formula (2): (Wherein R ³ and R ⁴ are each independently a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms) A vinyl polymer having a hydrolyzable silyl group represented by a hydrocarbon group (b represents 0 or 1) at the terminal and / or side chain of the main chain (hereinafter referred to as a silyl group-containing vinyl polymer (A)) Component) is preferably used.
In addition, in this specification, a vinyl-based material is derived from a compound containing a group having a polymerizable carbon-carbon unsaturated double bond, such as a vinyl group and a vinylidene group. Since the main chain of the silyl group-containing vinyl polymer (a) component is substantially composed of a vinyl polymer chain, a cured product formed from the curable coating composition containing the component (a) can be used. It is excellent in weather resistance, chemical resistance, etc., and by changing the composition of the monomer constituting the polymer, it is possible to design a wide range of resins from soft to hard. The (a)
In the component, usually, about 50 mol% or more, preferably about 60 mol% or more, and more preferably about 80 mol% or more of units constituting the main chain are composed of units derived from a vinyl monomer. Therefore, the component (a) may contain a urethane bond, a siloxane bond, or the like partially in a main chain or a side chain. In the silyl group-containing vinyl polymer, the hydrolyzable silyl group represented by the general formula (2) is
It is sufficient that at least one is present at the terminal and / or the side chain of the main chain. However, such a water-soluble resin is preferable because the cured product formed from the curable composition for coating obtained has a good balance between the curability and the impact resistance. The number of decomposable silyl groups is 2 to 1 in one molecule.
It is preferable that the number is zero.

In the general formula (2), R ³ and R ⁴
Are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 carbon atoms.
It is a monovalent hydrocarbon group selected from aralkyl groups of from 10 to 10. However, if the alkyl group has more than 10 carbon atoms, the hydrolyzability of the hydrolyzable silyl group is undesirably reduced.

The hydrocarbon group represented by R ³ and R ⁴ in the general formula (2) includes, for example, methyl group, ethyl group, n
An alkyl group having 1 to 4 carbon atoms such as -propyl group, isopropyl group, n-butyl group, isobutyl group; an aryl group having 6 to 10 carbon atoms such as phenyl group; An aralkyl group is preferably exemplified. Further, in the general formula (2), b is 0 or 1, and two or three (R ³ O) — are present in the same molecule, but ((R ³ O) ₂ — or (R ³ O)
_3- ), the two or three (R ³ O)-may be the same or different.

As described above, the hydrolyzable silyl group represented by the general formula (2) may be contained in the terminal of the main chain, may be contained in the side chain, and may be contained in the main chain. May be contained in both the terminal and the side chain.

The silyl group-containing vinyl polymer (a) component includes, for example, a unit derived from a vinyl monomer (α) component having a hydrolyzable silyl group represented by the general formula (2), and It is composed of the component (α) and other units derived from the monomer (β) other than the copolymerizable component (α), and is produced using these components (α) and (β). As the component (α), for example,

[0015]

Embedded image General formula (3) such as:

[0016]

Embedded image (Wherein, R ³ , R ⁴ , and b represent R ³ ,
The same as R ⁴ and b, R ⁵ represents a hydrogen atom or a methyl group)
A compound represented by the formula:

[0017]

Embedded image General formula (4) such as:

[0018]

Embedded image (Wherein, R ^3, R ^4, R ⁵ and b is R ³ in the general formula (3), R ^4, identical to R ⁵ and b, n is an integer of 1 to 12) compound represented by the ;

[0019]

Embedded image General formula (5) such as:

[0020]

Embedded image ^{(Wherein, R 3, R 4, R} 5, b and n are the general formula (4) in ^{R 3, R 4, R 5} , the same as b and n) a compound represented by;

[0021]

Embedded image General formula (6) such as:

[0022]

Embedded image (Wherein, R ^3, R ^4, R ⁵ and b is R ³ in the general formula (3), R ^4, identical to R ⁵ and b, m is an integer of 1-14) the compound represented by ;

[0023]

Embedded image (Where p represents an integer of 0 to 20), such as general formula (7):

[0024]

Embedded image (Wherein, R ^3, R ^4, R ⁵ and b is R ³ in the general formula (3), R ^4, identical to R ⁵ and b, p is an integer of 0 to 22) a compound represented by And (meth) acrylates having an alkoxysilyl group at the terminal via a urethane bond or a siloxane bond.

The component (α) can be used alone or in combination of two or more. The amount of the component (α) is 2% by weight or more based on the total amount of the silyl group-containing vinyl copolymer (a) component from the viewpoint of improving curability and weather resistance.
Preferably, the content is 5% by weight or more. From the viewpoint of adjusting internal stress and improving impact resistance,
It is desirable that the content of the component (a) is 60% by weight or less, preferably 50% by weight or less.

Examples of the other copolymerizable vinyl monomers (β) other than the component (α) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-
Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate,
Substituted with a halogen such as cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate; Alkyl (meth) acrylates; aralkyl (meth) acrylates such as benzyl (meth) acrylate; nitrile group-containing vinyl compounds such as (meth) acrylonitrile; epoxy group-containing vinyl compounds such as glycidyl (meth) acrylate; α-
Aromatic hydrocarbon vinyl compounds such as methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; maleic acid, fumaric acid,
Unsaturated carboxylic acids such as itaconic acid, salts thereof such as alkali metal salts, ammonium salts and amine salts; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride; Esters of unsaturated carboxylic acids, such as diesters or half esters with branched alcohols; vinyl acetate, vinyl propionate,
Vinyl esters and allyl compounds such as diallyl phthalate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-methyl (meth) acrylamide, N,
Vinyl compounds containing an amide group such as N-dimethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, itaconic acid diamide, crotonamide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone; methyl vinyl ether, cyclohexyl vinyl ether Other vinyl compounds such as vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, maleimide, fluoroolefin maleimide, N-vinylimidazole, vinylsulfonic acid; 2-hydroxyethyl (meth) acrylate, 1-
Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, 4- Hydroxystyrene, 4-hydroxystyrene vinyltoluene, Aronix 5700 (Toa Gosei Chemical Industry Co., Ltd.)
HE-10, HE-20, HP-1, HP-20
Acrylic ester oligomer having a hydroxyl group at its terminal (Nippon Shokubai Chemical Co., Ltd.), Blenmer PP series, (polypropylene glycol methacrylate), Blenmer PE series (polyethylene glycol monomethacrylate), Blenmer PEP series (polyethylene glycol) Polypropylene glycol methacrylate), Blemmer AP-400 (polypropylene glycol monoacrylate), Blemmer AE-
350 (polyethylene glycol monoacrylate),
Blemmer NKH-5050 (polypropylene glycol polytrimethylene monoacrylate), Blemmer G
Compounds such as LM (glycerol monomethacrylate) (all manufactured by NOF Corporation), ε- obtained by reaction of a hydroxyl group-containing vinyl compound with ε-caprolactone.
Examples include alcoholic hydroxyl group-containing vinyl monomers such as caprolactone-modified hydroxyalkyl vinyl copolymerizable compounds. As a typical example of the ε-caprolactone-modified hydroxyalkylvinyl copolymerizable compound, for example, a compound represented by the following general formula (8):

[0027]

Embedded image (Wherein, R 6 represents a hydrogen atom or a methyl group, and q represents an integer of 1 or more). Specific examples of such compounds include, for example, Placcel F
A-1 (R6 is a hydrogen atom, q is 1), Placel
FA-4 (R6 is a hydrogen atom, q is 4), Placel
FM-1 (R6 is a methyl group, q is 1), Placel
FM-4 (R6 is a methyl group, q is 4) (above, manufactured by Daicel Chemical Industries, Ltd.), TONE M-100 (R6 is a hydrogen atom, q is 2), TONE M-201 (R6 is a methyl group, q is 1) (all made by UCC). The component (β) can be used alone or in combination of two or more. The amount of the component (β) is 40% by weight or more, preferably 50% by weight or more of the total amount of the silyl group-containing vinyl monomer (a) component, from the viewpoint of adjusting the internal stress and improving the impact resistance. In view of improvement in curability and weather resistance, the content of component (a) is preferably 98% by weight or less, more preferably 95% by weight or less. The vinyl polymer (a) component containing a silyl machine is disclosed, for example, in JP-A-54-36395, JP-A-57-36109, JP-A-57-55953, and JP-A-58-157810. And the like. In addition, from the viewpoint of ease of handling, etc., the silyl group-containing compound is prepared by a solution polymerization method using an azo radical polymerization initiator such as azobisisobutyronitrile or a peroxide such as t-butyl peroxyoctoate. It is preferable to produce the vinyl polymer (A) component. The polymerization solvent used in the solution polymerization method may be any non-reactive solvent, and is not particularly limited. Examples of the polymerization solvent include hydrocarbons such as toluene, xylene, n-hexane, and cyclohexane; acetates such as ethyl acetate and butyl acetate; alcohols such as methanol, obtained phenol, isopropanol, and n-butanol; Ethers such as cellosolve, butyl cellosolve, cellosolve acetate; methyl ethyl ketone;
Methyl orthoacetate, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone,
Examples thereof include ketones such as acetone, and these can be used alone or as a mixture of two or more. When the solution polymerization method is employed, the molecular weight of the obtained vinyl polymer (A) component can be adjusted by using a chain transfer agent. Specific examples of the chain transfer agent include, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, (CH ₃ O) ₃ Si-SS-Si
_{(OCH 3) 3, (CH} 3 O) 3 Si-S 8 -Si (OC
_{H 3) 3, (CH 3} O) 3 Si- (CH 2) 3 -S-S- (C
_{H 2) 3 -Si (OCH 3} ) 3 and the like, they can be used alone or in admixture of two or more. For example, when a chain transfer agent having a hydrolyzable silyl group in the molecule such as γ-mercaptopropyltrimethoxysilane is used, the terminal of the main chain of the silyl group-containing vinyl polymer (a) component may be hydrolyzed. A degradable silyl group can be introduced.

The amount of the chain transfer agent is preferably about 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the component (a). The silicon equivalent of the silyl group-containing vinyl polymer (a) component should be 3 to prevent the internal stress from becoming too large and the impact resistance from being reduced.
It is desirably at least 00 g / mol, preferably at least 400 g / mol, more preferably at least 500 g / mol. Further, in order to impart sufficient curability to the obtained curable resin composition for paints, the silicon equivalent is 1500
0 g / mol or less, preferably 10000 g / mol or less,
More preferably, it is desirably 7500 g / mol or less. Further, the solid content concentration of the component (a) is not particularly limited, but is usually preferably about 50 to 70% by weight. In the present invention, in the component (a), a segment formed by a urethane bond or a siloxane bond may be contained in the main chain within a range not exceeding 50% by weight of the component (a).

As the resin (A-1) component used in the present invention, in addition to the above-mentioned component (a), for example, a urethane bond may be used because it is inexpensive and hardly affected by temperature during curing. The contained acrylic resin or the acrylic resin (b) component which performs urethane crosslinking is preferably used. The urethane bond-containing acrylic resin is a resin having a urethane bond obtained by a reaction between an isocyanate group and a hydroxyl group in the molecule. Such an urethane bond-containing acrylic resin is, for example, Olestar (manufactured by Mitsui Toatsu Chemicals, Inc.). The acrylic resin for performing the urethane crosslinking is a resin having an isocyanate group capable of reacting with a hydroxyl group in its molecule,
It is a resin capable of forming a urethane crosslinked structure by reacting an isocyanate group and a hydroxyl group. Examples of the acrylic resin having an isocyanate group and capable of undergoing urethane crosslinking include an isocyanate group-containing acrylic resin such as m-TMI (m-isopropenyl-α, α-dimethylbenzyl isocyanate manufactured by Takeda Pharmaceutical Co., Ltd.). Isocyanurate-type polyisocyanates such as D-150N and D-170N (manufactured by Takeda Pharmaceutical Co., Ltd.); duranate 17B-60PX and duranate MF-K60X (manufactured by Asahi Chemical Industry Co., Ltd.) ),
Block isocyanate such as Coronate 2513 (manufactured by Nippon Polyurethane Co., Ltd.); Acrydic A-801
(Manufactured by Dainippon Ink and Chemicals, Inc.), Armatex D
-152, Almatex 785-5, Almatex 748-5M (all manufactured by Mitsui Toatsu Chemicals, Inc.) and the like. Further, as the component (A-1), a tertiary amino group-containing acrylic polymer (c) component is also preferably used. The tertiary amino group-containing acrylic polymer is usually
It is composed of a unit derived from a tertiary amino group-containing vinyl monomer and a unit derived from another vinyl monomer copolymerizable therewith. Examples of the tertiary amino group-containing vinyl copolymer include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, And diethylaminoethyl (meth) acrylate. The other vinyl monomer copolymerizable with the tertiary amino group-containing vinyl monomer may be, for example, a monomer used for obtaining the silyl group-containing vinyl copolymer (a) component. Body (β)
Ingredients. The tertiary amino group-containing acrylic polymer can be obtained, for example, by polymerizing the tertiary amino group-containing vinyl monomer and other vinyl monomers by a usual method. The number average molecular weight of the tertiary amino group-containing acrylic polymer is not particularly limited, and is preferably about 2,000 to 30,000. As the component (A-1), the component (a)
The component (b) and the component (c) can be used as a mixture of two or more. Similarly to the resin (A-1) component, the resin (A) preferably used as a main component of the resin (A) component
-2) As components, for example, Lumiflon LF-100-C and Lumiflon LF-4 which are solvent-soluble fluororesins
00, Lumiflon LFX700 (above, Asahi Glass Co., Ltd.)
And the like, and these can be used alone or as a mixture of two or more. Further, in the present invention, the resin (A-1) component and / or the resin (A-
The resin (A-3) component and the resin (A-4) component can be selected as the resin (A) component in addition to the component containing the component (2) as a main component. Examples of the resin (A-3) component include n-butylated modified melamine resins such as Uban 20SE-60 (manufactured by Mitsui Toatsu Chemical Co., Ltd.); Modified melamine resin; CYMEL235, CYMEL303,
CYMEL1156 (all made by Mitsui Cytec Co., Ltd.)
And the like, and these can be used alone or in combination of two or more. The resin (A-4) component includes:
It is a resin having two or more epoxy groups in its molecule.
Examples of such resin (A-4) components include Epicoat 1001 (manufactured by Yuka Shell Epoxy), Celloxide 2021 (manufactured by Daicel Chemical Industries, Ltd., bifunctional epoxy resin), and Nissan TEPIC (Nissan Chemical Industries, Ltd.) Co., Ltd.), Epiol NPG-100 (manufactured by Nippon Oil & Fats Co., Ltd.), Epicron (Dainippon Ink Chemical Industry Co., Ltd.)
And bisphenol A type) and denacol (manufactured by Nagase Kasei Kogyo Co., Ltd.), and these can be used alone or in combination of two or more. In the present invention, from the viewpoint that the weather resistance of a cured product formed from the obtained curable resin composition for a paint is further improved,
A resin (A-1) and / or a resin (A-2) as a main component and a resin (A-3) and / or a resin (A-4) as a component. Preferably, it is used. Further, as described above, in the present invention, various resins can be used as the resin (A) component, but the weatherability of a cured product formed from the obtained curable resin composition for a paint decreases. In order to eliminate the fear, the number average molecular weight is 2,000 or more, preferably 25
It is desirable to use a resin having a number average molecular weight of 50,000 or more, in order to eliminate the possibility that the viscosity of the curable resin composition for a coating material is excessively increased and coating workability is reduced. It is desirable to use a resin having a molecular weight of preferably 40,000 or less, more preferably 30,000 or less. The component (B) includes:
A silicon-containing compound represented by the general formula (1) and / or a hydrolytic condensate thereof. The general formula (1)
In, although R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a monovalent hydrocarbon group selected from aryl and aralkyl groups, the alkyl group represented by such R ¹ When the number of carbon atoms exceeds 10, the hydrolyzability of the silicon-containing compounds (B) component itself, which is a hydrolyzable compound, is undesirably reduced. Examples of the hydrocarbon group represented by R ¹ and R ² in the general formula (1) include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. Preferred examples thereof include an aryl group having 6 to 10 carbon atoms such as a phenyl group; and an aralkyl group having 7 to 10 carbon atoms such as a benzyl group. In the general formula (1), a is 0, 1,
Or in the case of 2, (R ¹ O) - but there is 2, 3 or 4 in the same molecule _{^{((R 1 O) 2 -}} , (R 1 O) 3 - or (R ¹ O) ₄ -) , Such two, three or four (R
¹ O)-may be the same or different. Further, when a is 2, (R ² )-is ^{2 in the} same molecule.
Exist ((R ² ) ₂ −), but these two (R ² ) −
May be the same or different. Specific examples of the silicon-containing compound include, for example, tetramethyl silicate, tetraethyl silicate, tetra-n
Tetraalkyl silicates such as -propyl silicate, tetraisopropyl silicate, tetra-n-butyl silicate, tetraisobutyl silicate and tetra-t-butyl silicate; methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-sec- Alkyltrialkoxysilanes such as octyloxysilane, methyltriisopropoxysilane and methyltributoxysilane; aryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; and alkyltriaryloxysilanes such as methyltriphenoxysilane. −
Examples include trialkoxysilanes such as glycidoxytrialkoxysilanes such as glycidoxypropyltrimethoxysilane and triaryloxysilanes.
As the partially hydrolyzed condensate of the silicon-containing compound, for example, water is added to the silicon-containing compound such as the tetraalkyl silicate, trialkoxysilane, and triaryloxysilane in a usual manner, and the resultant is partially hydrolyzed and condensed. What was done is given. Specific examples thereof include, for example, MSi51, ESi40, HAS-
1, HAS-10 (all manufactured by Colcoat Co., Ltd.), MS
56, partial hydrolysis condensate of tetraalkyl silicate such as MS56S (manufactured by Mitsubishi Chemical Corporation) and trialkoxysilane partial hydrolysis condensate such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) And so on. The MSi 51 is a partially hydrolyzed condensate of tetramethyl silicate.
AS-1 is a partially hydrolyzed condensate of tetraethyl silicate. MS56 and MS56S are partially hydrolyzed condensates of tetramethylsilicate.

The silicon-containing compounds (B) include:
They can be used alone or in combination of two or more.
Among the components (B), tetramethyl silicate, tetraethyl silicate, a partially hydrolyzed condensate of tetramethyl silicate, and a partial hydrolysis of tetraethyl silicate, from the viewpoint that the curable resin composition for paint obtained is excellent in curability. It is preferable to use at least one selected from the group consisting of condensates or a mixture of two or more thereof. In order to sufficiently improve the stain resistance of a cured product formed from the curable resin composition for a coating material to be obtained, the amount of the component (B) is preferably based on 100 parts by weight of the solid content of the resin (A). It is at least 1 part by weight, preferably at least 2 parts by weight, more preferably at least 5 parts by weight. In order to prevent the appearance of the cured product from deteriorating and to prevent the cured product from cracking, the amount of the component (B) should be 70 parts by weight based on 100 parts by weight of the solid content of the resin (A) component. Or less, preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

The curable resin composition for paints of the present invention comprises a resin (A) compounded with a silicon-containing compound (B) component. In the present invention, the curable resin composition is used for the purpose of further improving curability. Preferably, a curing catalyst (C) component is blended with the curable resin composition for paints.

In the present invention, as the curing catalyst (C) component, the contact angle of the cured product formed from the obtained curable resin composition for paint is made smaller, and the effect of improving the stain resistance is made larger. Acid phosphate, a reaction product of an acid phosphate with a nitrogen-containing organic compound, a carboxylic acid, a sulfonic acid, a reaction product of a sulfonic acid with a nitrogen-containing organic compound, an organic tin It is preferable to use at least one of a compound and an organoaluminum compound. Examples of the curing catalyst (C) include acidic phosphoric acid such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, and didecyl phosphate. Esters; said acidic phosphoric acid ester and, for example, hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, dodecylamine, 1,4-diazabicyclo [2,2,2] octane,
1,8-diazabicyclo [5,4,0] undecene-
7. Reaction products with nitrogen-containing organic compounds such as morpholine and diisopropanolamine; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic Acids, carboxylic acids such as 2-ethylhexanoic acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, 1-
Sulfonic acids such as naphthalenesulfonic acid, 2-naphthalenesulfonic acid; for example, NACURE5225, NAC
Reaction products of the sulfonic acid such as URE5543 and NACURE 5925 (all manufactured by King Industries Co., Ltd.) with the nitrogen-containing e4e4e4e4e4e4e4e4e4dc organic compound; dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, octyltin dimethyl Organotin compounds such as tin oxide;
Organic aluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethyl acetoacetate); propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-glycidoxypropyl trimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, formula: CH ₂
A compound represented by CH ₂ —Si (OCH ₃ ) ₃ , an epoxy compound such as Cardura E, Epicoat 828, Epicoat 1001 (all manufactured by Yuka Shell Epoxy Co., Ltd.), and a phosphoric acid and / or monophosphate ester Addition reaction products: organic titanate compounds such as tetraisopropyl titanate, tetraoctylene glycol titanium, dipropoxy titanium-bis (ethyl acetoacetate), poly (tripropoxy titanium), and isopropyl tristearoyl titanate; Alternatively, two or more kinds can be used as a mixture.
The amount of the curing catalyst (C) component is selected from the group consisting of the resin (A) component and the silicon-containing compound (B) in order to eliminate the possibility that the weatherability of the cured product formed from the obtained curable resin composition for paint is reduced. 10) based on 100 parts by weight of the total solid content of the components
It is desirable that the content be not more than 5 parts by weight, preferably not more than 5 parts by weight. Further, in order to sufficiently improve the curability of the curable resin composition for paints, the amount of the curing catalyst (C) component is preferably 0.05 parts by weight or more based on 100 parts by weight of the total solid content. Is preferably 0.2 parts by weight or more. Further, in the present invention, in order to lower the viscosity of the curable resin composition for paints to such an extent that the workability is further improved, the organopolysiloxane silanol is added to the resin (A) component and the silicon-containing compound (B). ) The component is preferably 50 parts by weight or less based on 100 parts by weight of the total solid content,
More preferably, it may be blended in a range of 30 parts by weight or less. When the amount of the organopolysiloxane silanol is 5
If the amount exceeds 0 parts by weight, the cured product formed from the curable resin composition for a paint may be brittle. further,
When the silyl group-containing vinyl polymer (a) component is used as the resin (A) component, a dehydrating agent or a solvent is added to the curable resin composition for paints of the present invention for the purpose of further improving storage stability. It is preferable to mix them. Examples of the dehydrating agent include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate and the like, and these can be used alone or in combination of two or more. The dehydrating agent may be added to the component (a) during the polymerization of the component (a), or may be added after the polymerization. The amount of the dehydrating agent should be set so that the effect of stabilizing the hydrolyzable silyl group in the component (a) is not so improved and the solidification of the component (a) is rather difficult. 70 parts by weight or less, preferably 50 parts by weight, per 100 parts by weight
It is desirable that the amount is not more than 20 parts by weight, more preferably not more than 20 parts by weight. Examples of the solvent include an alkyl alcohol having an alkyl group having 1 to 10 carbon atoms. Specific examples of such an alkyl alcohol include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, Hexyl alcohol, octyl alcohol and the like can be mentioned, and these can be used alone or in combination of two or more. The amount of the solvent is not particularly limited, but is usually 70 parts by weight or less, preferably 50 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the solid content of the vinyl polymer (a) component. Desirably. Also, without using the dehydrating agent,
When the solvent is used alone, the amount of the solvent is determined in order to sufficiently exhibit the stabilizing effect of the hydrolyzable silyl group in the silyl group-containing vinyl polymer (a) component. It is desirable that the amount be 0.5 part by weight or more, preferably 1 part by weight or more, and more preferably 2 parts by weight or more with respect to 100 parts by weight of the solid content of the component (A). Is 70 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the solid content,
More preferably, the amount is not more than 20 parts by weight. The curable resin composition for a paint in which the dehydrating agent and the solvent are simultaneously blended has extremely excellent storage stability as compared with the curable resin composition for a paint in which the dehydrating agent and the solvent are not blended. As described above, the mixing ratio of the dehydrating agent and the solvent to make the curable resin composition for a coating material exhibit extremely excellent storage stability depends on the ratio of the components (a) and (B), and And it cannot be determined unconditionally, but may be appropriately adjusted so that the curable resin composition for paint obtained has a solid content concentration and a viscosity which are practically required. When the curable resin composition for a paint of the present invention is used by blending it in a top coat clear paint, in particular, by blending an ultraviolet absorber or a light stabilizer into the curable resin composition for a paint, particularly, At the same time, the weatherability of a cured product formed from the curable resin composition for paints can be further improved. Examples of the ultraviolet absorber include a benzophenone-based absorber, a triazole-based absorber,
Phenyl salicylate-based absorbent, diphenyl acrylate-based absorbent, acetophenone-based absorbent, and the like,
These can be used alone or in combination of two or more. The amount of the ultraviolet absorber is usually 0.1 to 100 parts by weight of the total solid content of the curable resin composition for coating.
It is desirably 10 parts by weight, preferably 1 to 5 parts by weight. The light stabilizers can be used alone or in combination of two or more. The amount of the light stabilizer is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total solid content of the curable resin composition for paints. Further, when the curable resin composition for a paint of the present invention is used by being blended with a top coat clear paint, in particular, depending on the use of the top coat clear paint, for example, a diluent, an anti-cissing agent, a leveling agent, etc. Additives: cellulose-based compounds such as nitrocellulose and cellulose acetate butyrate; the resin (A)
In addition to the components, a resin such as an epoxy resin, a melamine resin, a vinyl chloride-based resin, a chlorinated polypropylene-based resin, a chlorinated rubber, and polyvinyl butyral may be further added to the curable resin composition for a paint. The method for obtaining the curable resin composition for paints of the present invention is not particularly limited. For example, optional components such as a resin (A) component, a silicon-containing compound (B) component and, if necessary, a curing catalyst (C) component. Can be adopted by appropriately adjusting and mixing the respective amounts. After applying the curable resin composition for paints of the present invention to a substrate by, for example, a spray coating method or the like, the composition is subjected to room temperature or 60 to 160 ° C.
The composition can be cured by, for example, heating at about the same level to form a cured product (coating film) having particularly excellent stain resistance. As described above, the cured product formed from the curable composition for coating of the present invention has the weather resistance, corrosion resistance, and design properties inherently exhibited by a synthetic resin.
While maintaining hardness and the like, it also has hydrophilicity for expressing excellent stain resistance at the same time. Therefore,
The curable resin composition for paints of the present invention, for example,
It is extremely useful for painting interior and exterior of buildings, automobiles, and industrial equipment. Next, the coated product of the present invention using the curable resin composition for a coating will be described. The coated object of the present invention (hereinafter referred to as coated object (1)) is obtained by applying a coating material containing a metallic powder and / or a coloring pigment to an object to be coated such as a steel plate, a plastic such as polypropylene, polycarbonate or ABS resin, or an FRP. A top coat clear paint containing the curable resin composition for paint of the present invention as a main component is applied to the applied surface. The paint (base coat) containing the metallic powder and / or the coloring pigment is not particularly limited. Examples of the paint (base coat) include an amino alkyd resin, an oil-free alkyd resin, a thermosetting acrylic resin, a thermosetting urethane resin, a nitrified cotton lacquer, a modified acrylic lacquer, a slate acrylic lacquer, a room temperature curable urethane resin, an acrylic enamel resin, and an oxidized resin. Cured alkyd resins, oxidatively cured alkyd resins (such as cellulose acetate butyrate), room-temperature or heat-curable fluororesins, hydrolyzable silyl group-containing resins, curable resin compositions for paints of the present invention, and mixtures thereof As a component, a component containing a metallic powder and / or a coloring pigment can be used. The coating containing the metallic powder and / or the coloring pigment may be any type of solution-type coating using an organic solvent as a medium, non-aqueous dispersion coating, multi-component coating, powder coating, slurry coating, water-based coating, and the like. It may be a paint. There is no particular limitation on the metallic powder and the coloring pigment. Specific examples of the metallic powder include aluminum powder and copper powder. Further, mica powder and the like can be mixed. Specific examples of the coloring pigment include, for example, organic pigments such as phthalocyanine blue, toluidine red, and benzidine yellow, and inorganic pigments such as titanium oxide, carbon black, and red iron. These metallic powders and coloring pigments
Each of them can be used alone or in combination of two or more. In addition, when the said ultraviolet absorber and a light stabilizer are mix | blended with a base coat, the weather resistance of the coating material (1) can be improved further. Further, in order to improve the adhesion between the paint film containing the metallic powder and / or the coloring pigment and the paint film of the top coat clear paint, for example, aminoethylaminopropyltrimethoxysilane, γ-amino Propyltrimethoxysilane,
An aminosilane-based compound such as γ-aminopropyldimethoxysilane, γ-aminopropyltriethoxysilane, and 3-aminopropyldiethoxysilane may be blended. The amount of the aminosilane-based compound is usually 50 parts by weight or less, preferably 20 parts by weight or less, based on 100 parts by weight of the coating material containing the metallic powder and / or the coloring pigment. The coated article (1) of the present invention is obtained by further applying a top coat clear coating on the application surface on which the base coat has been applied. The painted object (1)
Is a two-coat 1 coating method in which, for example, the paint containing the metallic powder and / or the color pigment is applied to an object to be coated and left for a few minutes, and then a top coat clear paint is applied by a wet-on-wet method and heat-cured. It can be manufactured by a method such as a bake method or a two-coat two-bake method in which a paint containing a metallic powder and / or a coloring pigment is applied and cured by heating, and then a top coat clear paint is applied and cured by heating. . The application of the topcoat clear paint can be performed by various methods conventionally used, such as a dipping method, a spraying method, a brush coating method, a method using a roll coater or a flow coater. After such application, 3
By heating the coated surface to 0 ° C. or higher, preferably 55 to 350 ° C., the applied top coat clear coating can be cured. Since the thickness of the coating film of the coated article (1) varies depending on the application, it cannot be determined unconditionally. The thickness of a coating film formed from a paint containing a metallic powder and / or a color pigment is preferably about 10 to 30 μm from the viewpoint of concealing properties and the like, and a coating film formed from a topcoat clear paint. Is preferably about 20 to 50 μm from the viewpoint of durability and the like. Further, as the coated product of the present invention, a coating composition containing a curable resin composition for a coating material of the present invention as a main component and a coating material containing a pigment dispersion as a main component, for example, the above-mentioned coated product (1) There is also a coated article (hereinafter referred to as coated article (2)) which is applied to an object to be coated similar to the object to be coated which can be used in obtaining (1). The coating containing the coating composition and the pigment dispersion as main components is not particularly limited. As the paint, a curable resin composition for a paint of the present invention, a paint composition comprising other compositions used for ordinary paints, and a composition containing a pigment dispersion can be used. The paint containing the dispersion of the paint composition and the pigment as a main component may be any type of paint, similarly to the paint used in the paint (1). The pigment is not particularly limited, and for example, a coloring pigment contained in a paint used for the paint (1) can be used. The coating composition contains the curable resin composition for coating of the present invention as a main component. In addition to the curable resin composition for coating, other compositions used for ordinary coatings are also included. Thing may be contained. In this case,
The ratio of the curable resin composition for paint to the other composition (curable resin composition for paint / other composition (weight ratio)) is 50/50 or more, preferably 60/40 or more,
More preferably, it is desirable to be 65/35 or more. The dispersion contained in the coating material used for the coating product (2) of the present invention can be obtained by dispersing the coating composition and the pigment using a dispersing device such as a paint conditioner using glass beads or the like. When the dispersion is obtained, for example, when the other composition is used, for example, the curable resin composition for paint of the present invention and a pigment are dispersed in advance, and the other composition is added thereto. In addition, it may be dispersed, and conversely, the other composition and the pigment may be dispersed in advance, and the curable resin composition for a paint of the present invention may be added thereto and dispersed.
There is no particular limitation. Incidentally, the coating material contains the dispersion as a main component, in addition to such a dispersion,
For example, a rheology control agent may be contained. The coating (2) of the present invention is a coating to which a coating containing the above-mentioned dispersion as a main component is applied. There is no particular limitation on the method of applying the paint to the object to be coated, for example, and a method similar to the method of applying a top coat clear paint when obtaining the object to be coated (1) can be employed. . After the application, the applied paint can be cured by heating the application surface at room temperature or at 30 ° C. or higher, preferably 55 to 350 ° C. The thickness of the coating film of the coated article (2) varies depending on the application, and cannot be unconditionally determined, but is preferably about 10 to 80 μm, and more preferably about 20 to 50 μm from the viewpoint of durability and the like. This is particularly preferred.
As described above, since the curable resin composition for a paint is used in the paint of the present invention, the paint is maintained while maintaining the original weather resistance, corrosion resistance, design properties, hardness, and the like, and It is extremely excellent in stain resistance. Examples Next, the curable resin composition for a coating material of the present invention and a coated product using the same will be described in more detail based on Examples, but the present invention is not limited to only these Examples. . Resin Production Examples 1 to 7 (silyl group-containing vinyl polymer (a)
Production of Component (Resin (A) Component) Components (1) to (4) having the compositions shown in Table 1 were used. In a nitrogen gas atmosphere, a mixed solution of the component (1) was dropped at a constant speed over 5 hours into a mixed solution of the component (2) heated to 105 ° C. Next, a mixed solution of the component (3) was dropped at a constant speed over 1 hour. This was subsequently stirred at 105 ° C. for 2 hours, and then cooled to room temperature. Next, the component (4) was added thereto and stirred, and the vinyl polymer (a) -1 to vinyl polymer (a) -1 was added.
(A) A solution of -7 was obtained. However, in Production Example 3, the component (4) was not used. The obtained vinyl polymer (a)
The solid concentration, number average molecular weight, amount of active hydrogen and silicon equivalent of -1 to (a) -7 were examined. The results are shown in Table 1. The number average molecular weight was determined according to the following method, and the silicon equivalent was calculated based on the composition of the components shown in Table 1. (Number average molecular weight) Gel permeation chromatography analyzer (manufactured by Toyo Soda Co., Ltd., HLC
The measurement was performed by performing gel permeation chromatography using -8020). The abbreviations in Table 1 indicate the following. St: styrene MMA: methyl methacrylate NBMA: n-butyl methacrylate IBMA: isobutyl methacrylate GMA: glycidyl methacrylate NBA: n-butyl acrylate A-174: γ-trimethoxysilyl propyl methacrylate HEMA: 2-hydroxyethyl methacrylate AAM: acrylamide DMAEMA: Dimethylaminoethyl methacrylate AA: Acrylic acid MEOH: Methanol BUOH: 1-butanol Solvesso 100: Aromatic hydrocarbon (manufactured by Exxon Chemical Co., Ltd.) XY: Xylene TO: Toluene AIBN: 2,2'-azobisisobutyronitrile V-59: 2,2'-azobis (2-methylbutyronitrile MOA: methyl orthoacetate

[0033]

[Table 1] Production Example 8 (Production of epoxy group-containing acrylic polymer (resin (A) component)) Solvesso 1 heated to 110 ° C. in a nitrogen gas atmosphere
Styrene in a mixed solution of 18 parts of A.00 (Exxon Chemical Co., Ltd., aromatic hydrocarbon) and 9 parts of 1-butanol.
20 parts, glycidyl methacrylate 34 parts, cyclohexyl methacrylate 30 parts, 2-hydroxyethyl methacrylate 34 parts, Solvesso 100 14 parts,
A mixture of 5 parts by weight of 1-butanol and 5.7 parts of Kayaester O (manufactured by Kayaku Akzo Co., Ltd., organic peroxide) was mixed with 4 parts by weight.
It was dropped at a constant speed over time. Next, 10 parts by weight of a xylene solution containing 0.3% by weight of Kayaester O was dropped at a constant speed over 30 minutes. This is followed by 11
After stirring at 0 ° C. for 1.5 hours, the mixture was cooled to room temperature. Next, Solvesso 100 was added thereto and stirred to obtain an epoxy group-containing acrylic polymer (hereinafter, referred to as (A) -1) whose solid content concentration was adjusted to 60% by weight. When the number average molecular weight of the obtained epoxy group-containing acrylic polymer (A) -1 was examined in the same manner as in Production Examples 1 to 7, it was 430.
It was 0. Production Example 9 (Production of Carboxyl Group-Containing Acrylic Polymer (Resin (A))) Xylene 2 heated to 110 ° C. in a nitrogen gas atmosphere
6 parts, 15 parts by weight of styrene, 28 parts of isobutyl methacrylate, 2-ethylhexyl acrylate
A mixture of 5 parts by weight, 20.5 parts by weight of maleic anhydride, 30 parts of 1-methoxy-2-acetoxypropane, 5.7 parts of Kayaester O and 10 parts by weight of xylene was added to 4 parts by weight.
It was dropped at a constant speed over time. Next, 10 parts by weight of a xylene solution containing 0.3% by weight of Kayaester O was dropped at a constant speed over 30 minutes. This is followed by 110
After stirring at 1.5 ° C. for 1.5 hours, the mixture was cooled to room temperature to obtain an acid anhydride group-containing polymer. A mixture of 4 parts of methanol, 0.00.5 part by weight of triethylamine and 8 parts of butyl acetate was reacted at 60 ° C. for 6 hours with respect to 100 parts by weight of the obtained acid anhydride group-containing polymer. Thereafter, it was confirmed by an infrared absorption spectrum that the absorption based on the acid anhydride group (absorption at 1785 cm -1) had disappeared, and xylene was added thereto and stirred to adjust the solid content concentration to 50% by weight. A carboxyl group-containing acrylic polymer (hereinafter referred to as (A) -2) was obtained. When the number average molecular weight of the obtained carboxyl group-containing acrylic polymer (A) -2 was examined in the same manner as in Production Examples 1 to 7, it was 4,300. Examples 1 to 9 and Comparative Examples 1 to 3 The resin (A) component, the silicon-containing compounds (B) component and the curing catalyst (C) were blended so as to have the compositions shown in Tables 2 and 3 (solid content ratio). ), L-1984-50 as a leveling agent with respect to 100 parts by weight of the total solid content.
A mixture was obtained by adding 0.4 parts (manufactured by Kusumoto Kasei Co., Ltd.) and 2 parts of tinuvin 384 (manufactured by Ciba Geigy) as an ultraviolet absorber. This mixture was diluted with xylene.
By adjusting the viscosity with a 4 Ford cup to be about 20 to 25 seconds, a top coat clear paint was obtained. Next, a test piece was prepared by coating an epoxyamide-based cationic electrodeposition primer for automobiles and an intermediately coated surfacer on a soft steel sheet subjected to degreasing and phosphoric acid conversion treatment, and the surface thereof was coated with an acrylic melamine resin paint (white pearl-like). ) Was applied as a base coat. After 5 minutes had passed since the application of the acrylic melamine resin paint, the top coat clear paint was applied to the surface thereof by a wet-on-wet method and left at room temperature for 15 minutes. After this,
This was baked at 140 ° C. for 30 minutes to form a coating film (cured product). With respect to the obtained coating film, the dry film thickness of the base coat was about 15 μm, and the dry film thickness of the top coat clear was about 40 μm. Next, as a physical property of the coating film, a contact angle was examined according to the following method. The results are shown in Tables 2 and 3. (1) Untreated contact angle: A contact angle measuring machine (Kyowa Interface Chemical Co., Ltd.) was applied to the obtained coating film at a temperature of 23 ° C. and a relative humidity of 60%.
Static contact angle of water using CA-S150 type (°)
Was measured, and the hydrophilicity was evaluated. In addition, it shows that a coating film is excellent in hydrophilicity, so that the said contact angle is small. 85 ° C. steam treatment: After the obtained coating film was treated with steam at 85 ° C. for 5 minutes and 20 minutes, the contact angle was measured under the same conditions as in the untreated condition. 50 ° C. steam treatment: 50 ° C. steam treatment of the obtained coating film 6
After treatment for 0 minutes, the contact angle was measured under the same conditions as in the case of no treatment. The abbreviations in the table indicate the following. (A) -3: Acrylic resin capable of cross-linking urethane (Almatex 748-5M, manufactured by Mitsui Toatsu Chemicals, Inc.) (A) -4: n-butylated modified melamine resin (Mitsui Toatsu Chemicals, Inc.) (A) -5: Epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001 (A) -6): Solvent-soluble fluororesin (Asahi Glass Co., Ltd.)
(Lumiflon LF-100-C) (A) -7: Acrylic resin capable of cross-linking urethane (Coronate 2513, block isocyanate, manufactured by Nippon Polyurethane Co., Ltd.) (A) -8: β- (3,4- Epoxycyclohexyl)
Ethyltrimethoxysilane (Nippon Unicar Co., Ltd., A
(-186, epoxy resin) (A) -9: Bifunctional epoxy resin (Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd.) (B) -1: Tetramethylsilicate partial hydrolysis condensate (MSi51 (methylsilicate 51)) (B2): Partial hydrolysis and condensation product of tetraethyl silicate (HAS-1, manufactured by Colcoat Co., Ltd.) (B) -2: Partial hydrolysis and condensation product of tetraethyl silicate (ESi40 (ethyl silicate 40), manufactured by Colcoat Co., Ltd., SiO2 content 40% by weight) (B) -4: Tetramethylsilicate partially hydrolyzed condensate (MS56S manufactured by Mitsubishi Chemical Corporation) (C) -1: Dioctyl Reaction product of phosphate and dodecylamine (dioctyl phosphate / dodecylamine (weight ratio) = 50/50) (C) -2: Reaction product of octyl acid phosphate (AP8, manufactured by Daihachi Chemical Industry Co., Ltd., AP) with 1,8-diazabicyclo [5,4,0] undecene-7 (octyl acid phosphate / 1) , 8-Diazabicyclo [5,4,0] undecene-7 (weight ratio) = 64/3
6) (C) -3: Amine sulfonate salt (NACURE5225, manufactured by King Industries) (C) -4: Dibutyltin dilaurate (C) -5: Tris (ethylacetoacetate) aluminum

[0034]

[Table 2]

[0035]

[Table 3] From the results shown in Tables 2 and 3, the top coat clear paints obtained in Examples 1 to 9 may significantly decrease the contact angle by performing the steam treatment at 85 ° C and the steam treatment at 50 ° C. all right. Examples 10 to 11 The resin (A) component and the silicon-containing compound (B) component were blended so as to have the composition shown in Table 2 (solid content ratio). After adding 0.6 parts of the same leveling agent and 2 parts of the ultraviolet absorber as those used in 1 to 9, the curing catalyst (C) component shown in Table 1 was added to obtain a mixture. This mixture is diluted with xylene,
No. By adjusting the viscosity with a 4 Ford cup to be about 20 to 25 seconds, a top coat clear paint was obtained.
Next, the above-mentioned top coat clear paint was applied to the surface of acrylic urethane white applied on a soft steel plate,
After standing for 30 minutes, it was baked at 70 ° C. for 30 minutes. After this, this is cured at 23 ° C. for 1 day to form a coating film (cured product)
Was formed. The dry film thickness of the obtained coating film is about 40 μm
Met.

Next, the physical properties of the coating film were examined in the same manner as in Examples 1 to 9. Table 2 shows the results. From the results shown in Table 2, the contact angles of the topcoat clear paints obtained in Examples 10 to 11 were significantly reduced by the steam treatment and the 50 ° C steam treatment as in Examples 1 to 9. Example 12 A resin (A) component and a silicon-containing compound (B) component were blended so as to have the composition shown in Table 2 (solid content ratio), and the pigment concentration (the ratio of the pigment to the total solid content) was 40% by weight. Using glass beads, titanium oxide (CR-90, manufactured by Ishihara Sangyo Co., Ltd.) was dispersed for 2 hours by a paint conditioner so that the solid content concentration was 60% by weight, to prepare a white enamel. The curing catalyst (C) shown in Table 1 was added to this white enamel.
The components were added to obtain a mixture. This mixture was diluted with xylene. Viscosity by 4 Ford cup is about 20 ~
It was adjusted to 25 seconds to obtain a paint. Next, the coating material was applied to the surface of an aluminum plate (A5052P) and cured at 23 ° C. for 14 days to form a coating film (cured product). The dry film thickness of the obtained coating film was about 30 μm.

Next, the physical properties of the coating film were examined in the same manner as in Examples 1 to 9. Table 2 shows the results. Example 13 A resin (A) component and a silicon-containing compound (B) component were blended so as to have a composition shown in Table 2 (solid content ratio), and a white enamel was prepared in the same manner as in Example 12. An isocyanate compound (Takenate D17 manufactured by Takeda Pharmaceutical Co., Ltd.) is added to the obtained white enamel so that the equivalent ratio of the isocyanate group to the hydroxyl group (isocyanate group / hydroxyl group) becomes 1.
0N) and a curing catalyst were added, and a coating film was obtained in the same manner as in Example 12. The coating film properties were examined in the same manner as in Examples 1 to 12. Table 1 shows the results. Abbreviations in the table indicate the following. (A) -10: Hydroxyl group-containing acrylic copolymer (Acrydic A801 manufactured by Dainippon Ink and Chemicals, Inc.) Based on the results shown in Table 5, the paints obtained in Examples 12 to 13 were coated in Examples 1 to 8. 85 ° C steam treatment and 50
The contact angle was significantly reduced by steam treatment at ℃.

[0038]

According to the present invention, a coating film obtained by applying the curable resin composition for a coating material of the present invention to the surface of a substrate is heated to 50 ° C. or
It can be seen that this method is a surface modification method capable of reducing the contact angle with water and making the surface hydrophilic by treating in steam at a temperature of not less than ° C. While maintaining the inherent weather resistance, corrosion resistance, designability, hardness, etc. of the resin, it forms a cured product based on excellent hydrophilicity and also has excellent stain resistance that can withstand long-term outdoor exposure. Is what you can do. Therefore, the curable resin composition for paints of the present invention can be suitably used for coating interior and exterior of buildings, automobiles, industrial equipment, and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CG131 CH201 CL011 DA161 DB001 DL052 GA15 HA156 JA35 JC13 JC24 JC32 JC38 JC39 KA03 KA04 NA03 NA05 NA06 PC02 PC03 PC04 PC05 PC08 PC10

Claims (13)

[Claims] Claims: 1. A resin (A) component (100 parts by weight)
Formula ^{(1): (R 1 O} ) 4-a -Si- (R 2) a (1) ( wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms A monovalent hydrocarbon group selected from an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms (provided that R ¹ and R ² are not hydrogen atoms at the same time), a is 0, 1 or 2) and 1 to 70 parts by weight of a component (B) of a silicon-containing compound represented by the formula (1) and / or a partially hydrolyzed condensate thereof. 5 membranes
A surface modification method in which the surface is treated in hot water at 0 ° C. or higher or steam at 50 ° C. or higher to reduce the contact angle with water to make the surface hydrophilic. 2. The resin (A) component is an acrylic resin (A-
2. The method for modifying a surface according to claim 1, wherein the composition mainly comprises 1) a component and / or a fluororesin (A-2) component. 3. The acrylic resin (A-1) component has a main chain substantially consisting of a vinyl polymer chain, and has a general formula (2): (Wherein R ³ and R ⁴ are each independently a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms) The surface modification method according to claim 2, which is a vinyl polymer having a hydrolyzable silyl group represented by a hydrocarbon group (b represents 0 or 1) at the terminal and / or side chain of the main chain. 4. The method for modifying a surface according to claim 2, wherein the acrylic resin (A-1) is a urethane bond-containing acrylic resin or an acrylic resin capable of performing urethane crosslinking. 5. The surface modification method according to claim 2, wherein the acrylic resin (A-1) component is a tertiary amino group-containing acrylic polymer. 6. The resin (A) is a melamine resin (A-
3) epoxy resin (A) which is crosslinked with a component and / or an acid
-4) The method for modifying a surface according to any one of claims 2 to 5, wherein the method comprises a component. 7. A group in which the silicon-containing compound and / or the partially hydrolyzed condensate thereof (B) comprises tetramethyl silicate, tetraethyl silicate, a partially hydrolyzed condensate of tetramethyl silicate and a partially hydrolyzed condensate of tetraethyl silicate. And at least one selected from the group consisting of: and a mixture of two or more thereof.
7. The method for modifying a surface according to any one of claims 6 to 6. 8. The method for modifying a surface according to claim 1, further comprising a curing catalyst (C) component. 9. The curing catalyst (C) is composed of an acid phosphate, a reaction product of an acid phosphate with a nitrogen-containing organic compound, a carboxylic acid, a sulfonic acid, and a reaction of a sulfonic acid with a nitrogen-containing organic compound. The method for modifying a surface according to any one of claims 1 to 8, wherein the method is at least one selected from the group consisting of a product, an organotin compound, and an organoaluminum compound, or a mixture of two or more thereof. 10. A coated product obtained by applying a topcoat clear coating to a coating surface to which a coating containing a metallic powder and / or a coloring pigment has been applied, wherein the topcoat clear coating is defined in any one of claims 1 to 9. A method for modifying the surface of a painted product containing the curable composition for paints according to any one of the above as a main component. 11. A coated article to which a coating composition containing a coating composition and a pigment dispersion as a main component is applied, wherein the coating composition is any one of claims 1 to 9. A method for modifying the surface of a painted product containing the curable composition for paints as a main component. 12. The method for modifying a surface according to claim 1, wherein the treatment is performed using steam at 70 ° C. or higher. 13. A coating film obtained by the method for modifying a surface according to claim 1.