JP2001329227A - Resin composition for coating excellent in appearance and stain resistance, and method for prolonging stain resistance-imparting performance of resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition capable of giving a coating film excellent in stain resistance, appearance and solvent resistance as well as excellent in persistency enough to hardly suffer from changes in gloss (appearance) and the contact angle after its pot life is over. SOLUTION: The resin composition for a coating comprises (A) a resin for a coating for a production line, (B) a stain resistance-maintaining agent, and (C) a silicon-containing compound represented by the general formula; (R1O)4-a- Si-(R2)a and/or a partial hydrolyzate condensate, and is excellent in external appearance and stain resistance after its pot life is over.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition having excellent appearance and stain resistance, a method for extending the stain resistance imparting performance of the coating resin composition, the resin composition for coating, and a coated article. More specifically, the present invention relates to a low-staining type paint composition, for example, a resin composition for a paint capable of preventing a decrease in stain resistance during storage (particularly after opening (open system)) of a resin composition used for a line paint. . More specifically, for example, in the line painting of metals, ceramics, ceramic moldings, and plastics that can be used for interior and exterior materials of buildings, automobiles, bridges, home appliances, etc., appearance, pot life, closed storage, etc. The present invention relates to a resin composition for a coating material which suppresses a decrease in performance such as stability and reduces the contact angle of a coating film surface with water to make it hydrophilic, thereby imparting stain resistance.

[0002]

2. Description of the Related Art Conventionally, various techniques have been used to impart design effects to industrial products such as metals, ceramics, ceramic moldings, and plastics, and to improve their weather resistance and corrosion resistance. Attempts have been made to coat the surface of the industrial product with a composition comprising a synthetic resin.
In particular, among such compositions, melamine resins, urethane resins and the like are very often used in line applications in terms of the inherent curability, workability, price, etc., and further improve their weather resistance. A composition having a crosslinked structure such as a fluorine resin and an acrylic silicone resin as a composition having excellent weather resistance even when exposed outdoors for a long period of time. It has been used for exterior coating.

However, in recent years, it has been found that dirt adhering to the outside of the structure tends to be difficult to remove. In particular, the tendency is more conspicuous in the case of a light-colored paint, and the appearance is beautiful.
From the viewpoints of ease of cleaning, reduction in the number of times of cleaning, and the like, it is strongly desired that a cured coating film using the composition further improve stain resistance.

[0004] Regarding the method of imparting such stain resistance, a composition comprising a resin and a silicate compound is disclosed in WO94.
/ 06870, and JP-A-6-145453.

[0005] However, these compounds reduce the contact angle immediately after compounding the silicate compound and can sufficiently exhibit stain resistance. However, the compound containing the silicate compound can be stored for a long time, When a product is used in an open system for a long period of time, not only is it not possible to obtain a sufficient contact angle, but also the performance, such as appearance, viscosity, and stain resistance, deteriorates. I was

[0006] The present invention has been made in view of such prior art, and the curability, workability, and the like inherently exhibited by a resin have been developed.
While maintaining weather resistance, corrosion resistance, hardness, stain resistance, etc.
It is an object of the present invention to provide a coating resin composition which can be used for a long period of time by suppressing a change in viscosity and a decrease in appearance after storage.

[0007]

Means for Solving the Problems The resin composition for coatings excellent in appearance and stain resistance according to the present invention does not contain (A) a blend resin of a silyl group-containing resin and another organic resin or a silyl group-containing resin. Organic resin, (B) general formula (I): (R ¹ O) _4-a —Si— (R ² ) _a (I) (wherein, R ¹ and R ² are each independently a hydrogen atom or A monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group (provided that R
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2) and / or a partially hydrolyzed condensate thereof, and (C) a stain resistance maintaining agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A resin composition for a paint of the present invention and a coated article using the same will be described.

One of the major features of the present invention is that
(A) The organic resin as the component (A) is preliminarily blended with the component (C) as the stain resistance maintaining agent to reduce the water content in the system to 2,000 ppm or less, and then the silicon-containing compound and / or its partially hydrolyzed condensate (B ) Is included, whereby a hydrophilic function is sufficiently exhibited even after long-term storage or after pot life, and the contact angle to water is reduced.

The curable composition for paints of the present invention has not only the curability, processability, hardness, stain resistance and appearance but also the stain resistance maintainer (organic resin (A)) inherently exhibits. Since the component (B) is contained at a specific ratio, it has an excellent function of lowering the contact angle with water even after sealed storage or after pot life for a long time, and can impart stain resistance. .

Component (A) The component (A) used in the present invention has the following two embodiments. That is, (A-a): a case where the resin is a blend resin of a silyl group-containing resin and another organic resin. (Ab): When the organic resin does not contain a silyl group.

The component (A) used in the present invention includes:
There is no particular limitation other than the above requirements, and various thermoplastic resins and thermosetting resins can be used. Among these, acrylic resins, fluororesins, melamine resins, and the like, from the viewpoint that the cured product formed from the obtained curable composition for paints has excellent curability, workability, corrosion resistance, hardness, weather resistance, and the like. Epoxy resins and polyester resins which are crosslinked with an acid are preferable, and those containing an acrylic resin and / or a polyester resin as a main component are particularly preferable. Note that such a main component means that the component (A) is contained in an amount of more than 50% by weight.

Component (A): Acrylic Resin As the acrylic resin, for example, a main chain having a main chain of a cured product formed from the obtained curable composition for coatings is excellent in weather resistance, chemical resistance and the like. It consists essentially of a vinyl polymer chain and has the following general formula (2): —Si (R ⁴ ) _b — (R ³ O) _3-b (2) (wherein R ³ and R ⁴ are each independently A hydrogen atom or a monovalent hydrocarbon group selected from an 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, and b represents 0 or 1.) A vinyl polymer having the hydrolyzable silyl group represented 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.

The silyl group-containing vinyl polymer (a) component has a main chain substantially consisting of a vinyl polymer chain.
A cured product formed from the curable composition for a coating containing the component (a) has excellent weather resistance, chemical resistance, and the like, and is changed from soft to hard by changing the composition of the monomer constituting the polymer. A wide range of resin designs are possible.
In addition, the component (a) usually contains 5 of the units constituting the main chain.
About 0 mol% or more, preferably about 60 mol% or more, more preferably about 80 mol% or more comprises 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 above 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 is independently a hydrogen atom or a monovalent hydrocarbon group selected from an 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. An alkyl group having more than 10 carbon atoms is not preferred because the hydrolyzability of the hydrolyzable silyl group decreases.

The hydrocarbon group represented by R ³ and R ⁴ in the general formula (2) includes, for example, a methyl group, an ethyl group,
an alkyl group having 1 to 4 carbon atoms such as n-propyl group, isopropyl group, n-butyl group, isobutyl group; an aryl group having 6 to 10 carbon atoms such as phenyl group; And the like. In the general formula (2), b
A is 0 or 1, ^(R 3 O) - although present 2 or 3 in the same molecule ^((R 3 _{O) 2} - or ^(R 3 O)
₃ -), such 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 at 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 hydrolyzable silyl group-containing vinyl monomer (α) component represented by the general formula (2): 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,

Embedded image General formula (3) such as:

Embedded image (In the formula, 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);

Embedded image General formula (4) such as:

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ and b represent the above-mentioned general formula (3)
The same as R ³ , R ⁴ , R ⁵ and b in which n is an integer of 1 to 12);

Embedded image General formula (5) such as:

Embedded image(Where R³, R⁴, R⁵, B and n are those of the above general formula
R in (4)³, R⁴, R ⁵, B and n)
Said compound;

Embedded image General formula (6) such as:

Embedded image (In the formula, R ³ , R ⁴ , R ⁵ and b are the same as those in the general formula (2)
And a compound represented by the same formula as R ³ , R ⁴ , R ⁵ and b in the general formula (3), and m represents an integer of 1 to 14);

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

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ and b represent the above-mentioned general formula (3)
The same as R ³ , R ⁴ , R ⁵ and b in the above, p is an integer of 0 to 22), or a (meth) acrylate having an alkoxysilyl group at a terminal via a urethane bond or a siloxane bond. And so on.

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, preferably 5% by weight or more of the total amount of the silyl group-containing vinyl copolymer (a) component from the viewpoint of improving the curability and weather resistance. From the viewpoint of adjusting the internal stress and improving the impact resistance, the content of the component (a) is desirably 60% by weight or less, preferably 50% by weight or less.

Examples of the other copolymerizable vinyl monomer (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):

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 (R ⁶ is a hydrogen atom, q is 1), Placel
FA-4 (R ⁶ is a hydrogen atom, q is 4), Placel
FM-1 (R ⁶ is a methyl group, q is 1), Place
l FM-4 (R ⁶ is a methyl group, q is 4) (all manufactured by Daicel Chemical Industries, Ltd.), TONE M-100 (R ⁶
Is hydrogen atom, q is ^{2), TONEM-201 (R} 6 is a methyl group, q is 1) (more, UCC Co., Ltd.) and the like.

The above-mentioned 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. Is desirable,
From the viewpoint of improvement in curability and weather resistance, it is desirable that the content of the component (a) be 98% by weight or less, preferably 95% by weight or less.

The above-mentioned vinyl polymer (a) containing a silyl machine is described in, for example, JP-A-54-36395, JP-A-57-36109, JP-A-57-55953, and JP-A-58-55953. It can be manufactured by the method described in 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 is as follows:
Any non-reactive material may be used, and there is no particular limitation. 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, ethanol, isopropanol and n-butanol; ethyl cellosolve; Ethers such as butyl cellosolve and cellosolve acetate; ketones such as methyl ethyl ketone, methyl orthoacetate, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone, and acetone. These may be used alone or in combination of two or more. Can be used.

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 S
_{i-S-S-Si (} OCH 3) 3, (CH 3 O) 3 Si
—S ₈ —Si (OCH ₃ ) ₃ , (CH ₃ O) ₃ Si—
_{(CH 2) 3 -S-S-} (CH2) 3 -Si (OC
H ₃ ) _{3 and the} like, and these can be used alone or in combination of two or more. For example, especially γ
When a chain transfer agent having a hydrolyzable silyl group in the molecule such as mercaptopropyltrimethoxysilane is used, a hydrolyzable silyl group is added to the terminal of the main chain of the silyl group-containing vinyl polymer (a) component. 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).

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).

The acrylic resin used in the present invention may be, for example, a urethane bond-containing acrylic resin, in addition to the component (a), because it is inexpensive and hardly affected by temperature during curing. Alternatively, an acrylic resin (b) component which performs urethane crosslinking is preferably used.

The acrylic resin containing a urethane bond includes:
It is a resin having a urethane bond obtained by a reaction between an isocyanate group and a hydroxyl group in the molecule. An example of such a urethane bond-containing acrylic resin is Olestar (manufactured by Mitsui Chemicals, Inc.).

The urethane crosslinkable acrylic resin is a resin having an isocyanate group capable of reacting with a hydroxyl group in its molecule, and a resin capable of forming a urethane crosslinked structure by reacting an isocyanate group with a hydroxyl group. It is. Examples of the acrylic resin having an isocyanate group and performing urethane crosslinking include m-TM
I (manufactured by Takeda Pharmaceutical Co., Ltd., m-isopropenyl-α,
copolymers of isocyanate group-containing monomers such as α-dimethylbenzyl isocyanate); D-150N, D-1
Isocyanurate-type polyisocyanate such as 70N (all manufactured by Takeda Pharmaceutical Co., Ltd.); Duranate 17B-
Block isocyanates such as 60PX, Duranate MF-K60X (all manufactured by Asahi Kasei Kogyo Co., Ltd.), Coronate 2513 (Nippon Polyurethane Co., Ltd.), etc .;
Armatex D-152, Armatex 785-
5, Armatex 748-5M (all manufactured by Mitsui Chemicals, Inc.) and the like.

Further, as the acrylic resin, 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) ) Acrylates, methacrylates, methacrylates and the like. 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 an ordinary method.

The number average molecular weight of the tertiary amino group-containing acrylic polymer is not particularly limited.
It is preferably about 0000.

As the acrylic resin, two or more of the above-mentioned components (a), (b) and (c) can be used as a mixture.

Component (A): Fluororesin Similar to the acrylic resin, the fluororesin preferably used as a main component of the resin (A) is, for example, Lumiflon LF-100 which is a solvent-soluble fluororesin.
-C, Lumiflon LF-400, Lumiflon LFX70
0 (all manufactured by Asahi Glass Co., Ltd.), and these can be used alone or in combination of two or more.

Further, in the present invention, the melamine resin, the epoxy resin and the polyester resin can be selected as the resin (A) component in addition to the acrylic resin and / or the fluorine resin as a main component.

Component (A): Melamine resin As the melamine resin, for example, Euban 20SE
N-butylated modified melamine resin such as -60 (manufactured by Mitsui Chemicals, Inc.); Uban 60 series (manufactured by Mitsui Chemicals, Inc.) isobutylated modified melamine resin; CYMEL235, CYM
EL303 and CYMEL1156 (all manufactured by Mitsui Cytec Co., Ltd.) and the like.
A mixture of more than one species can be used.

Component (A): Epoxy resin The epoxy resin is a resin having two or more epoxy groups in its molecule. As such an epoxy resin, for example, Epicoat 1001 (Yuika Shell Epoxy Co., Ltd.)
Co., Ltd.), Celloxide 2021 (Daicel Chemical Industries, Ltd.)
Manufactured by Nissan TEPIC (manufactured by Nissan Chemical Industries, Ltd.), Epiol NPG-100 (manufactured by NOF Corporation), Epicron (manufactured by Dainippon Ink and Chemicals, 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.

Component (A): Polyester Resin The polyester resin is a polycondensate of an acid component mainly composed of polycarboxylic acid and an alcohol component mainly composed of polyhydric alcohol. The acid component is not particularly limited,
For example, terephthalic acid, isophthalic acid, phthalic acid, 2,
Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid and anhydrides thereof: succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. Group dicarboxylic acids and the like. In addition to the above, lactones such as γ-butyrolactone and ε-caprolactone; hydroxycarboxylic acids corresponding thereto:
A small amount of an aromatic oxymonocarboxylic acid such as P-oxyethoxybenzoic acid; a trivalent or higher valent polycarboxylic acid such as trimellitic acid, trimezic acid, and pyromellitic acid may be contained.

The alcohol component is not particularly restricted but includes, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-dihexaneol, diethylene glycol, triethylene glycol and triethylene glycol. Ethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,2-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexanediol, 2,5-hexanediol, 3-methyl-1,5- Pentanediol, 1,2-dodeca Diols, and aliphatic glycols having a side chain such as 1,2-octadecanediol. In addition to the above, a small amount of a trihydric or higher polyhydric alcohol such as trimethylolpropane, glycerin, and pentaerythritol may be contained.

Examples of the polyester resin include Almatex P645, P646, HMP25 (manufactured by Mitsui Chemicals, Inc.) and the like, and these can be used alone or in combination of two or more.

In the present invention, from the viewpoint that the curability, workability, weather resistance, corrosion resistance, and hardness of the cured product formed from the obtained resin composition for a coating material are further improved, the resin (A) is used as a component. It is preferable to use an acrylic resin or a polyester resin as a main component and a melamine resin and / or an epoxy resin. In particular, it is possible to use a fluororesin for the purpose of improving the weather resistance. As described above, in the present invention, various resins can be used as the resin (A) component, but there is a possibility that the weatherability of a cured product formed from the obtained curable resin composition for a paint may be reduced. In order to eliminate, the number average molecular weight is 2,000 or more, preferably 2500 or more,
More preferably, it is desirable to use a resin having a molecular weight of 3,000 or more, and in order to eliminate the possibility that the viscosity of the curable resin composition for coating material is excessively increased and the coating workability is reduced, the number average molecular weight is preferably 50,000 or less, preferably. Is 400
It is desirable to use a resin of not more than 00, more preferably not more than 30,000.

Component (B) The component (B) is a silicon-containing compound represented by the general formula (1) and / or a hydrolytic condensate thereof. In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group. When the carbon number of the alkyl group represented by R ¹ exceeds 10, the hydrolyzability of the silicon-containing compounds (B) component itself, which is a hydrolyzable compound, deteriorates, which is not preferable. R ¹ in the general formula (1)
And hydrocarbon groups represented by R ² include, for example, methyl, ethyl, n-propyl, isopropyl, n-
Preferable examples include an alkyl group having 1 to 4 carbon atoms such as a butyl group and an isobutyl group; 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 —), two, three or four such (R ¹ O) — may be the same or different. When a is 2, ^two (R ² )-are present in the same molecule ((R ² ) _2- ), and the two (R ² )-may be the same, It may be different.

Specific examples of the silicon-containing compound include, for example, tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetraisopropyl silicate, tetra-n-butyl silicate, tetraisobutyl silicate, tetra-t-butyl silicate and the like. Tetraalkyl silicate; methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-sec-octyloxysilane, methyltriisopropoxysilane,
Alkyltrialkoxysilanes such as methyltributoxysilane, phenyltrimethoxysilane, aryltrialkoxysilanes such as phenyltriethoxysilane,
Examples include alkyltriaryloxysilanes such as methyltriphenoxysilane, trialkoxysilanes such as glycidoxytrialkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, and triaryloxysilanes. As the partially hydrolyzed condensate of the silicon-containing compound, for example, the tetraalkyl silicate, trialkoxysilane,
Examples thereof include those obtained by adding water to a silicon-containing compound such as triaryloxysilane and subjecting it to partial hydrolysis for condensation. Specific examples thereof include, for example, MSi 51, E
Si40, ESi48 (all made by Colcoat Co., Ltd.),
MS56, MS56S, MS57 (all manufactured by Mitsubishi Chemical Corporation), silicate 40, silicate 48 (all,
Examples thereof include partially hydrolyzed condensates of tetraalkyl silicates such as Tama Chemical Co., Ltd., and trialkoxysilane partially hydrolyzed condensates such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.). The MSi 51 is
A partially hydrolyzed condensate of tetramethyl silicate,
ESi40 and HAS-1 are partially hydrolyzed condensates of tetraethylsilicate. MS56, MS
56S is a partially hydrolyzed condensate of tetramethylsilicate.

The silicon-containing compounds (B) include:
They can be used alone or in combination of two or more.
Among the component (B), tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetraisopropyl silicate, tetra-n It is preferable to use at least one selected from the group consisting of -butyl silicate, tetraisobutyl silicate, tetra-t-butyl silicate and partially hydrolyzed condensates thereof, or a mixture of two or more thereof. In particular, in order to suppress the increase in viscosity after pot life or after a long-term closed storage test, tetramethyl silicate, tetraethyl silicate and its partially hydrolyzed condensate and tetra-n
It is preferable to use -propyl silicate, tetraisopropyl silicate, tetra-n-butyl silicate, tetraisobutyl silicate, tetra-t-butyl silicate and a partially hydrolyzed condensate thereof in combination.

The component (B) is used in an amount of 100 parts by weight of the solid content of the resin (A) in order to sufficiently improve the stain resistance of the cured product formed from the obtained resin composition for coatings. 0.5 to 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 2 to 30 parts by weight. If the amount is less than 0.5 parts by weight, stain resistance is not sufficiently exhibited,
If the amount is more than 100 parts by weight, the appearance may be deteriorated or the coating may be cracked, which is not preferable.

Component (C) The stain resistance-maintaining agent (C) is preferably added to the resin composition for coating of the present invention for the purpose of improving the storage stability of the resin (A). Examples of the stain resistance maintaining agent include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthobutyrate, ethyl orthobutyrate, and the like. They can be used alone or in combination of two or more.
The stain resistance maintaining agent may be added during the polymerization of the component (A), or may be added after the polymerization. It is also possible to remove the water content in the pigment by adding it when dispersing the pigment using the component (A), or to add it after dispersing the pigment into a paint. The amount of the stain resistance maintaining agent (C) is not particularly limited as long as the amount of water in the component (A) can be removed. When the component (A) is used as a clear coating, the amount of water is relatively small, so that there is no problem with a small amount. However, when the pigment is dispersed and enameled, it is necessary to remove the water contained in the pigment. The amount of the stain resistance-maintaining agent (C) used is 0.01 to 70 parts by weight, preferably 0.5 to 35 parts by weight, and more preferably 1 to 100 parts by weight based on 100 parts by weight of the resin solids of the component (A). 20 parts by weight. When the amount of the component (C) (dehydrating agent) used is less than 0.01 part by weight, the dewatering effect is insufficient, and the storage stability is reduced. If the amount is more than 70 parts by weight, the coating film is undesirably foamed (foamed). The storage stability is improved by the addition of the stain resistance maintaining agent (C). That is, for example, when the paint is exposed to air (outside air) for a relatively long time (in an open system) as in the case of performing line painting, the paint gradually deteriorates and has the expected physical properties (for example, However, the stain resistance imparting property of imparting stain resistance to the finally obtained coating film is not exhibited, but by adding the stain resistance maintaining agent (C) component as in the present invention. Even when used in an open system for a relatively long time, such as when used in a line coating process, the stain resistance imparting performance does not decrease, and the stain resistance imparting performance can be extended. Not only that, by adding the stain resistance-maintaining agent (C), the appearance of the finally obtained coating film is improved and the effect of maintaining hydrophilicity is exhibited. It can be said that this is a feature of the present invention by blending the component (C) with a stain resistance maintaining agent.

Curing Catalyst The resin composition for a coating material of the present invention comprises a resin (A) component and a silicon-containing compound (B) component and a stain resistance-maintaining agent (C) component. In order to further improve the curability, it is preferable to mix a curing catalyst (D) component with the resin composition for coating.

In the present invention, as the curing catalyst (D) component, the contact angle of a cured product formed from the obtained resin composition for a coating material can be made smaller, and the effect of improving stain resistance can be made larger. In terms of being able to do so, acidic phosphate esters, reaction products of acidic phosphate esters with nitrogen-containing organic compounds, carboxylic acids, sulfonic acids, reaction products of sulfonic acids with nitrogen-containing organic compounds, organotin compounds and It is preferable to use at least one of the organic aluminum compounds.

An explanation will be added. As the curing catalyst (D) component, for example, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate,
Acid phosphates such as dioctyl phosphate and didecyl phosphate; and the acid phosphates, for example, hexylamine, di-2-ethylhexylamine,
N, N-dimethyldodecylamine, dodecylamine,
1,4-diazabicyclo [2,2,2] octane, 1,
Reaction products with nitrogen-containing organic compounds such as 8-diazabicyclo [5,4,0] undecene-7, morpholine, diisopropanolamine; maleic acid, adipic acid,
Azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid,
Carboxylic acids such as 2-ethylhexanoic acid; sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthalenesulfonic acid and 2-naphthalenesulfonic acid; for example, NACURE5225, NACURE
Reaction products of the sulfonic acid and the nitrogen-containing organic compound, such as 5543 and NACURE 5925 (all manufactured by King Industries); dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate 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-glycid Xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, formula: C Compounds represented by _{2 CH 2 -Si (OCH 3)} 3, Kadeyura E, Epikote 828,
Epikote 1001 (above, Yuka Shell Epoxy Co., Ltd.)
Reaction product of an epoxy compound such as a compound of the present invention) and phosphoric acid and / or a monophosphate; tetraisopropyl titanate, tetraoctylene glycol titanium, dipropoxy titanium-bis (ethyl acetoacetate), poly (tripropoxy titanium), Organic titanate compounds such as isopropyl tristearoyl titanate can be used, and these can be used alone or in combination of two or more.

The amount of the curing catalyst (D) component is to promote the hydrolysis and condensation of the silicon-containing compound (B) component, and is 0.05% to 100 parts by weight of the solid content of the (B) component.
It is desirable to use 10 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight. If the amount used is 0.01 parts by weight or less, the curability is not sufficient,
When the contact angle is hardly reduced and the amount used exceeds 10 parts by weight, appearance may not be obtained.

In addition , 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, an ultraviolet absorber or a light stabilizer is blended into the resin composition for a paint. In particular, by blending these simultaneously, the weather resistance of a cured product formed from the curable resin composition for a paint can be further improved.

Examples of the ultraviolet absorber include benzophenone-based absorbers, triazole-based absorbers, phenylsalicylate-based absorbers, diphenylacrylate-based absorbers, and acetophenone-based absorbers. A mixture of more than one species can be used.
The amount of the ultraviolet absorber 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 coatings. 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.

When the curable resin composition for a paint of the present invention is used by being mixed with a top coat clear paint, in particular, a diluent, an anti-cissing agent, Additives such as leveling agents; cellulose compounds such as nitrocellulose and cellulose acetate butyrate; in addition to the resin (A) component, in particular, vinyl chloride resins, chlorinated polypropylene resins, chlorinated rubbers, polyvinyl butyral, and the like. A resin or the like may be further blended in the resin composition for coating.

The method for obtaining the curable resin composition for paints of the present invention is not particularly limited. For example, the resin (A) component, the silicon-containing compound (B) component, the stain resistance maintaining agent (C) component, According to the above, a method of appropriately adjusting the amounts of the optional components such as the curing catalyst (D) component and mixing the components and the like can be adopted.

The resin composition for a coating material of the present invention was applied to a substrate by various conventional methods such as a dipping method, a spraying method, a brush coating method, a method using a roll coater or a flow coater. Thereafter, the composition is cured by heating at room temperature or at about 60 to 350 ° C., and a cured product (coating film) having particularly excellent stain resistance can be formed. As described above, the cured product formed from the curable composition for coating of the present invention has excellent stain resistance while maintaining the curability, workability, weather resistance, corrosion resistance, and hardness inherently exhibited by the synthetic resin. It also has hydrophilicity for expressing at the same time, and furthermore, does not cause these performance degradation even after long-term storage. Therefore, the resin composition for coating of the present invention is used for line coating, and is particularly suitable for coating of pre-coated metal (PCM) and the like, and building materials such as roofs and walls, road materials such as fences and guard rails, It is extremely useful for applications such as metal products used outdoors and automobiles, such as vending machines.

[0061]

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 with reference to Examples, but the present invention is not limited to only these Examples. is not.

Synthesis Example 1 (Hydroxy and silyl group-containing vinyl)
Production of System Polymer) 26 parts by weight of xylene was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel, and the temperature was raised to 110 ° C. while introducing nitrogen gas. After that, γ-methacryloxypropyltrimethoxysilane 1
3 parts by weight, styrene 15 parts by weight, butyl methacrylate 29 parts by weight, methyl methacrylate 30 parts by weight, 2-hydroxyethyl methacrylate 13 parts by weight, xylene 2
A mixture consisting of 0 parts by weight and 2.75 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was dropped at a constant rate over 5 hours by a dropping funnel.

After completion of the dropwise addition, 0.25 parts by weight of 2,2'-azobis (2-methylbutyronitrile) and xylene 5
Parts by weight were dropped at a constant speed over 1 hour.
After aging for a period of time, the mixture was cooled, 10 parts by weight of methyl isobutyl ketone was added, and the mixture was diluted with xylene to obtain an acrylic copolymer having a resin solid content of 60%. The number average molecular weight (GPC method) of the obtained acrylic copolymer is 7000
Met.

Synthesis Example 2 (Hydroxy and silyl group-containing vinyl)
Production of polymer) 13 parts by weight of Solvesso 100 and 9 parts by weight of 1-butanol were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, and nitrogen gas was introduced. While heating, the temperature was raised to 110 ° C. Thereafter, 20 parts by weight of γ-methacryloxypropyltrimethoxysilane, 15 parts by weight of styrene, 38 parts by weight of butyl methacrylate, 7 parts by weight of methyl methacrylate, 20 parts by weight of 2-hydroxyethyl methacrylate, 8 parts by weight of Solvesso 100,
5 parts by weight of 1-butanol and 2,2′-azobis (2
-Methylbutyronitrile) 4.7 parts by weight, methanol 2
The mixture consisting of parts by weight was dropped at a constant speed over 5 hours using a dropping funnel.

After completion of the dropwise addition, 0.3 parts by weight of 2,2'-azobis (2-methylbutyronitrile) and 5 parts by weight of xylene were added dropwise at a constant speed over 1 hour, and the mixture was aged at 110 ° C. for 2 hours. , And further diluted with Solvesso 100 to obtain an acrylic copolymer having a resin solid content of 60%. Number average molecular weight (GP) of the obtained acrylic copolymer
C) was 5,100.

Synthesis Example 3 (Production of Epoxy Resin) 17 parts by weight of Solvesso 100 and 10 parts by weight of n-butanol were charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. The temperature was raised to 110 ° C. while introducing nitrogen gas. After that, styrene 2
0 parts by weight, glycidyl methacrylate 34 parts by weight, cyclohexyl methacrylate 30 parts by weight, 2-hydroxyethyl methacrylate 16 parts by weight, Solvesso 100
, A mixture consisting of 13 parts by weight of n-butanol and 5.7 parts by weight of Kayaester O was dropped at a constant rate over 4 hours by a dropping funnel.

After completion of the dropping, 0.3 parts by weight of Kayaester O and 10 parts by weight of xylene were added dropwise at a constant speed over 30 minutes, and the mixture was aged at 110 ° C. for 1 hour and 30 minutes, and then cooled.
After dilution with Solvesso 100, an epoxy group-containing polymer having a resin solid content of 60% was obtained. The number average molecular weight (GPC method) of the obtained acrylic copolymer was 5,400.

Synthesis Example 4 (Acrylic Tree Containing Carboxyl Group)
Production of Fat) 26 parts by weight of Solvesso 100 was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, and the temperature was raised to 110 ° C. while introducing nitrogen gas. Thereafter, 15 parts by weight of styrene, 28 parts by weight of isobutyl methacrylate, 36.5 parts by weight of 2-ethylhexyl acrylate, 20.5 parts by weight of maleic anhydride, 1-
A mixture of 30 parts by weight of methoxy-2-acetoxypropane, 5.7 parts by weight of Kayaester O, and 10 parts by weight of xylene was dropped at a constant rate over 4 hours by a dropping funnel.

After the completion of the dropwise addition, 0.3 parts by weight of Kayaester O and 10 parts by weight of xylene were added dropwise at a constant speed over 30 minutes, then aged at 110 ° C. for 1 hour and 30 minutes, cooled, and diluted with Solvesso 100. As a result, an acid anhydride group-containing polymer having a resin solid content of 50% was obtained. The number average molecular weight (GPC method) of the obtained acid anhydride group-containing polymer was 5,600.

Synthesis Example 5 (Production of Hydroxyl-Containing Polymer) 26 parts by weight of xylene was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel, and nitrogen gas was introduced. The temperature was raised to 110 ° C. Thereafter, 15 parts by weight of methyl methacrylate, 57 parts by weight of isobutyl methacrylate, 8 parts by weight of n-butyl acrylate, 20 parts by weight of 2-hydroxyethyl methacrylate,
14.5 parts by weight of xylene and 2,2′-azobis (2
A mixture consisting of 5.6 parts by weight of (-methylbutyronitrile) was dropped at a constant rate over 5 hours by a dropping funnel.

After completion of the dropwise addition, 0.4 parts by weight of 2,2'-azobis (2-methylbutyronitrile) and Solvesso 1
After dripping 6.8 parts by weight of 00 at a constant speed over 1 hour,
After aging at 110 ° C. for 2 hours, the mixture was cooled, 10 parts by weight of methyl isobutyl ketone was added, and the mixture was diluted with xylene to obtain an acrylic copolymer having a resin solid content of 60%.
The number average molecular weight of the obtained acrylic copolymer (GPC
Method) was 6,900.

Preparation of Component B (B-1) 100 parts by weight of ethyl silicate 48 (partial hydrolysis condensate of ethyl silicate manufactured by Colcoat Co., Ltd.) was added to 100 parts by weight (solid content) of the resin obtained in Synthesis Example 2. Was previously mixed and diluted with Solvesso 100 to adjust the solid content concentration to 60%. This solution was aged at 50 ° C for 4 hours (B-
1) Components were obtained.

(Preparation of white enamel paint ) White enamel paint-A Commercially available Armatex HMP25 (polyester resin,
Titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.) 72 with respect to 54 parts by weight of a nonvolatile content of 60% (Mitsui Chemicals, Inc.)
1 part by weight of xylene and 10.8 parts by weight of xylene were mixed and dispersed for 2 hours by a paint conditioner using glass beads.

Thereafter, 90 parts by weight of the above Armatex HMP25 was added to Cymel 303 (Mitsui Cytec Co., Ltd.).
21.6 parts by weight of melamine resin) and xylene.
6 parts by weight, and paint conditioner
Dispersion was performed for 0 minutes to prepare white enamel paint-A (solid content: 60%, pigment concentration: 40%).

White enamel paint-B The epoxy resin (nonvolatile content 60%) obtained in Synthesis Example 3 was added to 54
With respect to parts by weight, 72 parts by weight of titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.) and 10.8 parts by weight of xylene were blended, and the mixture was dispersed for 2 hours by a paint conditioner using glass beads.

Then, 36 parts by weight of the resin obtained in Synthesis Example 3 and 90 parts by weight of the resin obtained in Synthesis Example 4 were mixed with xylene 3
7.2 parts by weight were blended, and further dispersed for 30 minutes with a paint conditioner to prepare a white enamel paint-B (solid content concentration 60%, pigment concentration 40%).

White enamel paint-C The hydroxyl group-containing acrylic resin obtained in Synthesis Example 5 (nonvolatile content 60
%) With respect to 54 parts by weight, 72 parts by weight of titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.) and 10.8 parts by weight of xylene were blended, and dispersed with a paint conditioner using glass beads for 2 hours. Was. Thereafter, 126 parts by weight of the hydroxyl group-containing acrylic resin obtained in Synthesis Example 5 and 37.2 parts by weight of xylene were blended, and further dispersed for 30 minutes with a paint conditioner to obtain white enamel paint-C (solid content: 60%, (Pigment concentration: 40%).

White enamel paint-D The hydroxyl group-containing acrylic resin obtained in Synthesis Example 5 (nonvolatile content 60
%) With respect to 54 parts by weight, 72 parts by weight of titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.) and 10.8 parts by weight of xylene were blended, and dispersed with a paint conditioner using glass beads for 2 hours. Was.

Thereafter, 90 parts by weight of the hydroxyl-containing acrylic resin obtained in Synthesis Example 5, 21.6 parts by weight of Cymel 303 (melamine resin manufactured by Mitsui Cytec Co., Ltd.), and 48.6 parts by weight of xylene were added. The mixture was dispersed with a paint conditioner for 30 minutes to prepare white enamel paint-D (solid content: 60%, pigment concentration: 40%).

White Enamel Paint-E Titanium oxide (CR-97, Ishihara Sangyo Co., Ltd.) was used with respect to 54 parts by weight of the acrylic resin containing a hydrolyzable silyl group and hydroxyl group (nonvolatile content: 60%) obtained in Synthesis Example 1. Was mixed with 10.8 parts by weight of xylene and dispersed for 2 hours with a paint conditioner using glass beads.

Thereafter, 126 parts by weight of the resin obtained in the above Synthesis Example 1 and 37.2 parts by weight of xylene were blended, and further dispersed for 30 minutes with a paint conditioner to obtain white enamel paint-E (solid content: 60%, pigment: (Concentration: 40%).

White Enamel Paint-F Commercially available Armatex HMP25 (polyester resin,
Titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.) 72 with respect to 54 parts by weight of a nonvolatile content of 60% (Mitsui Chemicals, Inc.)
1 part by weight of xylene and 10.8 parts by weight of xylene were mixed and dispersed for 2 hours by a paint conditioner using glass beads.

Thereafter, 99 parts by weight of the above Armatex HMP25 was added to Cymel 303 (Mitsui Cytec Co., Ltd.).
Melamine resin) and 48 parts by weight of xylene, and further dispersed with a paint conditioner for 30 minutes to obtain white enamel paint-F (solid content: 60%).
%, Pigment concentration 40%).

Examples and Comparative Examples White enamel (white enamel paints A to F) 100 obtained
The silicon-containing compound (B) component, the stain resistance-maintaining agent (C), and, if necessary, the crosslinking agent (D) and / or the curing catalyst are blended with respect to parts by weight so as to have a composition shown in [Table 1]. ,
This mixture was diluted with Solvesso 100 to prepare a viscosity of about 30 seconds by Ford Cup # 4 to obtain a resin composition for coating.

After the obtained paint was left at room temperature for 24 hours, the water content was measured by the Karl Fischer method. As a result, Example 1 was 430 ppm, Example 8 was 820 ppm and Comparative Example 1
Was 3600 ppm.

Next, the above-mentioned resin composition for a coating was applied to a soft steel sheet which had been subjected to a degreasing and phosphoric acid conversion treatment and coated with an epoxyamide-based cation electrodeposition primer and an intermediately coated surfacer as test pieces.

After leaving at room temperature for 10 minutes,
It was baked for 1 minute at ℃ to form a coating film (cured product). The dry film thickness of the white enamel was about 30 μm.

(1) Appearance of the obtained coating film,
(2) solvent resistance, (3) flexibility, (4) pencil hardness,
(5) Stain resistance, (6) hydrophilicity, and (7) pot life were evaluated by the following methods. The results are also shown in [Table 1].

(1) Appearance (gloss) Gloss at 60 ° was measured according to JIS K5400.

(2) Solvent Resistance Xylene was impregnated into absorbent cotton, and a 20-way rubbing test was performed.

(3) Flexibility A 180 ° bending test was performed using a round bar having a diameter of 6 mm.

(4) Hardness (pencil hardness) Evaluated according to JIS K5400.

(5) Stain resistance The lightness represented by the L * a * b * color system at the initial stage of exposure was measured by a colorimeter (CR300, manufactured by Minolta Co., Ltd.). ° outdoor exposure for 3 months. The absolute value (ΔL value) of the difference between the lightness after exposure and the lightness before exposure was used as a measure of contamination. In addition, the smaller the numerical value, the more excellent the stain resistance, and the larger the numerical value, the more dirty.

(6) Hydrophilicity (contact angle) Contact angle measuring instrument (CA-S150, manufactured by Kyowa Interface Science Co., Ltd.)
Before exposure, 3 months after outdoor exposure at 30 ° south side in Settsu City, Osaka Prefecture, and 50 ° C, 98% RH as an accelerated evaluation method.
Evaluation was made by measuring the contact angle with water after treatment in an atmosphere for 3 days. The smaller the value, the higher the hydrophilicity.

(7) Pot life The paint to be tested was weighed in a 450 ml mayonnaise bottle in an amount of about 300 g, stirred with a stirrer at a temperature of 23 ° C. and in an atmosphere of 55 RH%, and gloss and contact angle after 2, 4, and 6 hours had passed. Was examined for changes.

[0096]

[Table 1]

From the results shown in Table 1, all of the coating films formed using the coating materials obtained in the examples maintain the appearance, solvent resistance, and flexibility, which are conventionally required, while maintaining the stain resistance. It can be seen that the resin composition of the present invention is excellent in the durability and the durability is excellent without lowering the gloss and the contact angle after the pot life test under the stirring condition.

[0098]

According to the present invention, it is understood that the contamination resistance and the pot life can be made compatible by blending a stain resistance maintaining agent and a silicon compound with a conventionally used organic resin. The appearance, solvent resistance, originally exhibited by the composition,
It is possible to form a cured product based on excellent hydrophilicity and having excellent contamination resistance that can withstand long-term outdoor exposure while maintaining flexibility.
Therefore, the curable resin composition for paints of the present invention is used continuously for metals, ceramics, ceramic moldings, plastics and the like which can be used for building interior and exterior materials, automobiles, bridges, home appliances and the like. It can be suitably used for painting.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 163/00 C09D 163/00 175/14 175/14 183/02 183/02 183/04 183/04 201 / 00 201/00 (72) Inventor Naoto Ando 3-130-1, Nozoe, Harima-cho, Kako-gun, Hyogo F-term (reference) 4J038 CC021 CD001 CG001 DA191 DB001 DD001 DG221 DL022 DL031 DL042 GA03 GA08 GA09 GA15 JA29 JC24 KA04 KA09 MA07 NA01 NA05 NA26 PA19 PB05 PB07 PB09 PC02 PC03 PC08

Claims (18)

[Claims] (A) a blend resin of a silyl group-containing resin and another organic resin; (B) a general formula (I): (R ¹ O) _4-a —Si— (R ² ) _a (I) (Wherein R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group (provided that R ¹ and R ² are
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2) which is blended with a silicon-containing compound and / or a partially hydrolyzed condensate thereof, and (C) a stain resistance-maintaining agent, which is excellent in appearance and stain resistance. Resin composition. (A) an organic resin containing no silyl group, (B) a general formula (I): (R ¹ O) _4-a -Si- (R ² ) _a (I) R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group (provided that
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2) which is blended with a silicon-containing compound and / or a partially hydrolyzed condensate thereof, and (C) a stain resistance-maintaining agent, which is excellent in appearance and stain resistance. Resin composition. 3. The composition according to claim 1, wherein the organic resin in the component (A) is an acrylic resin. 4. The composition according to claim 1, wherein the organic resin in the component (A) is a hydroxyl group-containing acrylic resin and an amino resin. 5. The composition according to claim 1, wherein the organic resin in component (A) is a hydroxyl group-containing acrylic resin and contains a polyisocyanate compound and / or a blocked polyisocyanate compound. object. 6. The composition according to claim 1, wherein the organic resin in the component (A) is an acrylic resin which forms a crosslink between a carboxyl group and an epoxy group. 7. The composition according to claim 1, wherein the organic resin in the component (A) is an acrylic resin that forms a silicon crosslink. 8. The composition according to claim 1, wherein the organic resin (A) is a polyester melamine resin. 9. The composition according to claim 1, wherein the organic resin (A) is an epoxy resin. 10. The component (B) is at least one selected from the group consisting of tetramethyl silicate, a partially hydrolyzed condensate of tetramethyl silicate, tetraethyl silicate, and a partially hydrolyzed condensate of tetraethyl silicate. Item 10. The composition according to any one of Items 1 to 9. (11) the component (B) is tetramethylsilicate, a hydrolytic condensate of tetramethylsilicate, tetraethylsilicate, a hydrolytic condensate of tetraethylsilicate, tetrapropylsilicate, a hydrolytic condensate of tetrapropylsilicate, tetrabutyl silicate, Silicate,
The composition according to any one of claims 1 to 9, wherein the composition is a mixture of two or more kinds selected from the group consisting of hydrolytic condensates of tetrabutyl silicate. 12. The composition according to any one of claims 1 to 11, wherein the stain resistance maintaining agent of the component (C) is a hydrolyzable ester compound. 13. The composition according to claim 1, wherein 0.5 to 100 parts by weight of (B) is mixed with 100 parts by weight of (A). . 14. The composition according to claim 1, wherein 0.1 to 35 parts by weight of (C) is mixed with 100 parts by weight of (A). . 15. A coating resin composition capable of imparting stain resistance to a cured coating film so as to exhibit excellent stain resistance, even if it is an open system. A method for maintaining stain resistance imparting performance that cannot be performed, wherein (A) a blend resin of a silyl group-containing resin and another organic resin, (B) a general formula (I): (R ¹ O) _4-a- Si — (R ² ) _a (I) (wherein, R ¹ and R ² are each independently a hydrogen atom or a monovalent carbon selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group) Hydrogen group (however, R
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2) is blended with a silicon-containing compound represented by the formula (1) and / or a partial hydrolysis-condensation product thereof, and the resin composition thus obtained is further added with (C) a stain resistance-maintaining agent. A method for extending the stain resistance imparting performance of a resin composition for coatings, which is characterized by the following. 16. A coating resin composition capable of imparting excellent stain resistance to a cured coating film by imparting the stain resistance imparting performance, thereby reducing the stain resistance imparting performance even in an open system. A method for maintaining stain resistance imparting performance which cannot be performed, wherein (A) an organic resin containing no silyl group is added to (B) a general formula (I): (R ¹ O) _4-a -Si- (R ² ) _a (I) (wherein, R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms (provided that R
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2) is blended with a silicon-containing compound represented by the formula (1) and / or a partial hydrolysis-condensation product thereof, and the resin composition thus obtained is further added with (C) a stain resistance-maintaining agent. A method for extending the stain resistance imparting performance of a resin composition for coatings, which is characterized by the following. 17. The following (C)
Ingredients are blended to reduce the water content in the system to 2000 ppm
A method for preparing a resin composition for a coating, comprising the following step (B): (A) A blend resin of a silyl group-containing resin and another organic resin, or an organic resin containing no silyl group. (B) General formula (I): (R ¹ O) _4-a —Si— (R ² ) _a (I) (wherein, R ¹ and R ² each independently represent a hydrogen atom or a carbon atom of 1) To 10 monovalent hydrocarbon groups selected from alkyl groups, aryl groups and aralkyl groups (provided that R
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2)) and / or a partially hydrolyzed condensate thereof. (C) A stain resistance maintaining agent. 18. The following component (A) is applied to the surface to which the paint containing metallic powder and / or color pigment is applied.
A coated product obtained by applying a coating resin composition comprising the component (B) and the component (C) as a top coat clear coating and curing the coating. (A) A blend resin of a silyl group-containing resin and another organic resin, or an organic resin containing no silyl group. (B) General formula (I): (R ¹ O) _4-a —Si— (R ² ) _a (I) (wherein, R ¹ and R ² each independently represent a hydrogen atom or a carbon atom of 1) To 10 monovalent hydrocarbon groups selected from alkyl groups, aryl groups and aralkyl groups (provided that R
¹ and R ² are not simultaneously hydrogen atoms), a is 0, 1
Or 2)) and / or a partially hydrolyzed condensate thereof. (C) A stain resistance maintaining agent.