JPH11279480A - Curable composition for paint and painted object - Google Patents

Abstract

(57) [Problem] To provide a curable composition for an acrylic silicone-based topcoat paint that has excellent adhesion and recoating properties and can suppress odor during coating operation. SOLUTION: This is an acrylic copolymer having at least two hydrolyzable silyl groups bonded to carbon atoms represented by the general formula (1), wherein the alkyl group has 8 carbon atoms.
Acrylic copolymer (A), which is an acrylic copolymer obtained by copolymerizing the above monomer mixture containing 2 to 50% by weight of alkyl (meth) acrylate, saturated hydrocarbon and / or carbon number Is 9 or more aromatic hydrocarbons 50
A solvent composed of at least% by weight and another organic solvent, and / or
Alternatively, a curable composition for a top coat containing the turpentine oil (B), a pigment (C), a hydrolyzable ester compound (D), and a curing catalyst (E) and the curable composition for a top coat are coated. Painted thing. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable composition for a top coat. More specifically, for example, acrylic silicone topcoats that can be suitably used for coating of buildings such as metals, ceramics, glass, cement, ceramic moldings, plastics, wood, paper, fibers, etc., home appliances, industrial equipment, etc. The present invention relates to a curable composition for a paint, and a painted product obtained by applying the curable composition for a top coat.

[0002]

2. Description of the Related Art The surface of industrial products such as ceramic moldings, buildings made of concrete, steel, etc.
BACKGROUND ART The appearance of a building or the like is improved by coating with a top coat such as a fluororesin paint, an acrylic urethane resin paint, or an acrylic silicone resin paint, and the anticorrosion property and weather resistance are improved.

[0003] In order to improve the weather resistance and to further improve the adhesion to the substrate, these top coats are
Furthermore, various measures have been taken to improve the recoating property for the purpose of enhancing the function by laminating multiple layers.

[0004] However, acrylic silicone resin coatings have insufficient adhesion, depending on the object to be coated, as compared with other coatings, and have the disadvantage of causing smearing due to overcoating. In recent years, since environmental problems have become more important in recent years, the odor of conventional strong solvent type paints has been regarded as a problem, and paints with less volatile solvents have been respected. Was.

[0005]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention provides a curable composition for an acrylic silicone top coat which has excellent adhesion and recoating properties and can suppress odor during coating operation. It is intended to provide.

[0006]

Means for Solving the Problems In view of the above-mentioned situation, the present inventors have conducted intensive studies, and as a result, they have a specific hydrolyzable silyl group and the alkyl group has 8 to 20 carbon atoms.
Acrylic copolymer composed of an alkyl (meth) acrylate having an alkyl group of less than 8 and an alkyl (meth) acrylate having an alkyl group of 8 or more, a saturated hydrocarbon in all solvents and / or an aromatic hydrocarbon having 9 or more carbon atoms 50% hydrogen
A composition comprising a solvent and / or turpentine oil, a pigment, a hydrolyzable ester compound, and a curing catalyst occupying a specific ratio occupying the above, has curability at room temperature or high temperature, and a coating film from the composition However, they have found that they have the same excellent weather resistance as a coating film from a conventional acrylic silicone resin coating material, and at the same time have adhesiveness, recoatability and low odor. Further, they have found that when a silicon compound (G) is further added to the above composition, a coating film having additionally excellent stain resistance can be obtained. That is, the present invention relates to the general formula (1)

[0007]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
Represents 10 alkyl groups. R ² is a hydrogen atom, carbon number 1
Represents a monovalent group selected from the group consisting of an alkyl group having 10 to 10, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. When a plurality of R ¹ or R ² are present, they may be the same or different. a is 0 to 2
Represents an integer. A) an acrylic copolymer having at least two hydrolyzable silyl groups bonded to a carbon atom represented by the formula (1), wherein the alkyl group has 8 to less than 20 carbon atoms. 100 parts by weight of an acrylic copolymer (A), which is an acrylic copolymer obtained by copolymerizing a monomer mixture containing 50 to 50% by weight,
A solvent comprising 50% by weight or more of a saturated hydrocarbon and / or an aromatic hydrocarbon having 9 or more carbon atoms and another organic solvent, and / or 5 to 150 parts by weight of turpentine oil (B);
A curable composition for a topcoat containing 5 to 150 parts by weight of a pigment (C), 0.1 to 150 parts by weight of a hydrolyzable ester compound (D), and 0.1 to 20 parts by weight of a curing catalyst (E). is there.

[0009] The present invention is also a curable composition for topcoat paint, which further comprises a polyester resin (F) having a polymerizable unsaturated group for dispersing a pigment in the curable composition for topcoat paint.

[0010] The present invention further provides the curable composition for a top coat according to the first aspect, or the curable composition for a top coat according to the first aspect, wherein the component (F) is blended. the top coating curable composition, further, the following general formula ^{(2); (R 3 O} ) 4-b -Si- (R 4) b (2) ( wherein, R ³ is a carbon number 1 to 10 A monovalent hydrocarbon group selected from the group consisting of an alkyl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms.
R ⁴ is an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms.
And a monovalent hydrocarbon group selected from the group consisting of an aryl group and an aralkyl group having 7 to 10 carbon atoms. When a plurality of R ³ and / or R ⁴ are present, they may be the same or different. b represents 0 or 1. )) And / or a partially hydrolyzed condensate (G) thereof, which is a curable composition for a topcoat containing 2 to 70 parts by weight based on 100 parts by weight of the acrylic copolymer (A). .

The present invention further provides a curable composition for a topcoat paint according to the first aspect, a curable composition for a topcoat paint according to the second aspect, or the third composition wherein the component (G) is further added thereto. Further, a silane coupling agent (H) comprising at least one compound selected from the group consisting of aminosilanes, epoxysilanes and their reaction products is further added to the curable composition for topcoat paints of the embodiment It is also a curable composition for a topcoat containing 0.1 to 300 parts by weight based on 100 parts by weight of the polymer (A).

The present invention further provides a coated product obtained by applying the curable composition for a top coating material according to any one of the above-mentioned embodiments. Hereinafter, the present invention will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The curable composition for a top coating composition of the present invention is bonded to a carbon atom represented by the above general formula (1) as a base resin having curability at room temperature in the presence of moisture. An acrylic copolymer having at least two hydrolyzable silyl groups, wherein the alkyl group has 8 carbon atoms.
Alkyl (meth) acrylate that is not less than 20 and less than 20
An acrylic copolymer (A) which is obtained by copolymerizing a monomer mixture containing 50 to 50% by weight is contained.

Since the acrylic copolymer (A) consists essentially of a main chain copolymerized with an acrylic monomer,
The resulting coating film formed from the curable composition for a top coating composition of the present invention has excellent weather resistance, chemical resistance and the like. It should be noted that the acrylic copolymer (A) is “substantially composed of a main chain obtained by copolymerizing an acrylic monomer” with a single monomer constituting the main chain of the acrylic copolymer (A). It means that 50% or more, preferably 70% or more of the monomer units are acrylic monomer units.

Further, the acrylic copolymer (A) is
Since the hydrolyzable silyl group is contained in a form bonded to a carbon atom, the coating film has excellent water resistance, alkali resistance, acid resistance and the like. In the acrylic copolymer (A), the number of hydrolyzable silyl groups bonded to carbon atoms represented by the general formula (1) depends on the weather resistance of the coating film, durability such as solvent resistance, and the like. From the viewpoint, the acrylic copolymer (A) 1
2 or more per molecule. More preferably, the number is three or more.

The hydrolyzable silyl group bonded to the carbon atom represented by the general formula (1) may be bonded to the terminal of the main chain of the acrylic copolymer (A), or may be bonded to the side chain. And may be bonded to the terminal and side chains of the main chain.

In the above general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group,
Examples include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a pentyl group, an octyl group, and a decyl group. Of these, alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group are preferred. If the alkyl group has more than 10 carbon atoms, the reactivity of the hydrolyzable silyl group will decrease. Also, when R ¹ is a group other than an alkyl group such as a phenyl group and a benzyl group, the reactivity of the hydrolyzable silyl group is reduced.

In the above formula (1), R ² is selected from the group consisting of a hydrogen atom, 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. Represents a monovalent group. 1 to 10 carbon atoms
Examples of the alkyl group include the groups exemplified above. As the aryl group having 6 to 10 carbon atoms,
For example, a phenyl group, a tolyl group, a naphthyl group and the like can be mentioned. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint that the composition of the present invention is excellent in curability.

When a plurality of R ¹ and / or R ² are present, they may be the same or different.

In the general formula (1), a is 0 to 2
Represents an integer. That is, in the general formula (1), (R ¹ O)
_3-a of 3-a is selected so that it is 1 or more and 3 or less,
From the viewpoint that the curability of the acrylic copolymer (A) is improved, a is preferably 0 or 1.

Specific examples of the hydrolyzable silyl group bonded to the carbon atom represented by the general formula (1) include, for example,
Examples include groups contained in a monomer containing a hydrolyzable silyl group described below.

As the acrylic copolymer (A), a monomer unit having a hydrolyzable silyl group bonded to a carbon atom represented by the general formula (1) is copolymerized from the viewpoint of ease of synthesis. Polymerized ones are preferred. In addition, the content ratio of the monomer unit in the acrylic copolymer (A) is preferably 3 because the coating film formed using the composition of the present invention is excellent in durability and strength. ~ 90% by weight, furthermore 10 ~
It is preferably 70% by weight, particularly preferably 10 to 50% by weight.

As the monomer unit other than the monomer unit containing a hydrolyzable silyl group bonded to a carbon atom represented by the general formula (1) contained in the acrylic copolymer (A), Is a monomer unit derived from an acrylic monomer described below,
It may be a monomer unit derived from another monomer used as necessary as described later.

The acrylic copolymer (A) has a number average molecular weight of 1000 to 300 from the viewpoint that coating films formed using the composition of the present invention have excellent physical properties such as durability.
00, more preferably 3000 to
25,000.

In the present invention, the acrylic copolymer (A) may be used alone or in combination of two or more.

The production of the acrylic copolymer (A) is as follows:
For example, a monomer containing a polymerizable double bond and a hydrolyzed silyl group bonded to a carbon atom (hereinafter referred to as monomer (A-
1)), a (meth) acrylate having an alkyl group having 8 to less than 20 carbon atoms (hereinafter, also referred to as a long-chain alkyl ester-containing monomer) and / or a derivative thereof (hereinafter, referred to as a monomer (A-2)). , (Meth) acrylic acid and / or a derivative thereof (hereinafter referred to as monomer (A-3)
And other monomers used as necessary.

Specific examples of the monomer (A-1) include, for example, the following compounds (3-1) to (3-11);

[0028]

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The following general formula (3):

[0030]

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(Wherein R ¹ , R ² , and a are the same as above.
R ⁵ represents a hydrogen atom or a methyl group. ), The following compounds (4-1) to (4-9);

[0032]

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The following general formula (4):

[0034]

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(Wherein R ¹ , R ² , R ⁵ and a are the same as above, and n is an integer of 1 to 12), and the following compounds (5-1) to (5-1) 5-2) the compound;

[0036]

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General formula (5) such as:

[0038]

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(Wherein R ¹ , R ² , R ⁵ , a, and n are the same as described above);
A compound of (6-2);

[0040]

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General formula (6) such as:

[0042]

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(Wherein R ¹ , R ² , R ⁵ and a are the same as above, and m is an integer of 1 to 14), and the following (7-1) -A compound of (7-2);

[0044]

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General formula (7) such as:

[0046]

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(Wherein R ¹ , R ² , R ⁵ and a are the same as above, and p is an integer of 0 to 20), or a hydrolyzable compound bonded to a carbon atom. (Meth) acrylates having a silyl group at the terminal via a urethane bond or a siloxane bond are exemplified. Among these, the compound represented by the above general formula (4) is preferable from the viewpoint of excellent copolymerizability and polymerization stability, and excellent curability and storage stability of the obtained composition.

These monomers (A-1) may be used alone or in combination of two or more. As described above, the monomer (A-1) contains 3 to 3 monomer units containing the hydrolyzable silyl group represented by the general formula (1) in the obtained acrylic copolymer (A). 90% by weight, even 8
It is preferably used so that it is contained in an amount of up to 70% by weight, particularly 11 to 50% by weight.

Specific examples of the monomer (A-2) include, for example, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, palmitoyl (meth) acrylate, Examples thereof include (meth) acrylates having an alkyl group having 8 to 20 carbon atoms, such as stearyl (meth) acrylate, octadecanoyl (meth) acrylate, oleyl (meth) acrylate, and icosanoyl (meth) acrylate. Above all, 2-ethylhexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, palmitoyl (meth) acrylate from the viewpoint of good weather resistance and solvent solubility And stearyl (meth) acrylate are preferred. Particularly preferably, lauryl (meth) acrylate,
Stearyl (meth) acrylate and isobornyl (meth) acrylate. The monomer (A-2) is
Two or more types may be used in combination.

Specific examples of the monomer (A-3) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (Meth) acrylonitrile, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide (meth) acryloylmorpholine, AS-6 which is a macromonomer,
Compounds such as AN-6, AA-6, AB-6, and AK-6 (trade names) (all manufactured by Toa Gosei Chemical Industry Co., Ltd.), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-
Methylol (meth) acrylamide, 4-hydroxystyrene vinyl toluene, Alonix 5700 (trade name) manufactured by Toa Gosei Chemical Industry Co., Ltd., 4-hydroxystyrene, HE-10, HE-20, HP- manufactured by Nippon Shokubai Chemical Co., Ltd.
1 and HP-20 (trade names) (all of which are acrylate oligomers having a hydroxyl group at the terminal), Blemmer-PP series (trade name) (polypropylene glycol methacrylate), Blemmer PE series (trade name) manufactured by NOF Corporation ) (Polyethylene glycol monomethacrylate), Blemmer PEP series (trade name) (polyethylene glycol polypropylene glycol methacrylate), Blemmer AP-400 (trade name) (polypropylene glycol monoacrylate), Blemmer AE-350 (trade name) (polyethylene glycol mono) Acrylate) and Blemmer GLM (trade name) (glycerol monomethacrylate), hydroxyalkyl esters of (meth) acrylic acid such as N-methylol (meth) acrylamide ; An ε- caprolactone-modified hydroxyalkyl vinyl copolymer compound obtained by reaction of a hydroxyl group-containing compound and ε- caprolactone P
lacel FA-1 (trade name), Placel
FA-4 (trade name), Placel FM-1 (trade name), Placel FM-4 (trade name) (all manufactured by Daicel Chemical Industries, Ltd.), TONE M-201 (trade name)
(UCC); polycarbonate-containing vinyl compound (specific examples include HEAC-1 (trade name) (manufactured by Daicel Chemical Industries, Ltd.)), hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid Or (meth) acrylic compounds containing a phosphoric ester group such as condensation products with phosphoric esters, and (meth) acrylates containing a urethane bond or a siloxane bond. These monomers (A-2) may be used alone or in combination of two or more.

The acrylic copolymer (A) contains 3-90% by weight of a monomer unit having a reactive silyl group bonded to a carbon atom represented by the general formula (1) in the molecule. In the case where n-butyl methacrylate units are contained, any effect obtained when these are contained can be obtained.

The total amount of the monomers (A-2) and (A-3) used may be appropriately adjusted according to the type and the amount of the monomer (A-1) used. 5 to 90% by weight of the total amount, further 30 to 85% by weight,
Particularly, it is preferably 50 to 85% by weight. The amount of the monomer (A-1) used is 3 to 5 of the total amount of the polymerization components.
0% by weight, preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight.

The amount of the monomer (A-2) used is 2 to 50 parts by weight based on the total amount of the polymerization components. When the amount of the monomer (A-2) is less than 2 parts by weight, the saturated hydrocarbon and / or the aromatic hydrocarbon having 9 or more carbon atoms may be used.
A solvent composed of at least% by weight and another organic solvent, and / or
Alternatively, the solubility in the turpentine oil (B) becomes insufficient, and if it exceeds 50 parts by weight, the resulting coating film will exhibit remarkable tackiness, so that it is limited to the above range. Preferably 3 to
It is 40 parts by weight, particularly preferably 5 to 30 parts by weight.

When n-butyl methacrylate is used as the monomer (A-3), the amount used is 20 to 50% of the monomer used, which is represented by the following general formula (2). This is preferred because it has excellent compatibility with the silicone compound and / or its hydrolysis-condensation product (G), and also has an excellent balance of various properties of a coating film formed from the obtained curable composition.

In the present invention, for the purpose of further improving the weather resistance of a coating film formed from the obtained composition of the present invention, for example, a segment bonded to the main chain by a urethane bond or a siloxane bond; A-1), a monomer (A-2), a segment derived from a monomer other than the monomer (A-3), and the like are introduced into the acrylic copolymer (A) in a range not exceeding 50% by weight. May be.

The above monomer (A-1) and monomer (A-
2) Specific examples of the monomer other than the monomer (A-3) are not particularly limited, and examples thereof include aromatic substances such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene. Aromatic hydrocarbon vinyl compounds; maleic acid, fumaric acid, itaconic acid,
Unsaturated carboxylic acids such as (meth) acrylic 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 20 linear or branched alcohols or amines; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl pyridine, aminoethyl Amino group-containing vinyl compounds such as vinyl ether;
Amide group-containing vinyl compounds such as itaconic acid diamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene , Butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, and other vinyl compounds such as vinylsulfonic acid. These may be used alone or in combination of two or more.

The acrylic copolymer (A) may contain a group such as a carboxyl group or an amino group, and in that case, the curability and adhesion are improved. However, in the case of a carboxyl group or an amino group bonded to a polymer chain, the activity is weak, and a cured product having good characteristics cannot be obtained even if the curing is performed by using these instead of a curing catalyst.

In the coating composition of the present invention, the acrylic copolymer (A) as a main component further has an alkoxysilyl having a lower molecular weight than an acrylic copolymer obtained by non-aqueous dispersion polymerization described below. Adding non-aqueous polymer particles (NAD) obtained by non-aqueous dispersion polymerization of a monomer used for an acrylic copolymer (A) using a group-containing copolymer as a dispersion stabilizer resin; Can be. By adding this component in a very small amount, the viscosity of the coating composition can be reduced and the solid composition can be made high, and the impact resistance of the cured coating film can be further improved.

Next, an example of a method for producing the acrylic copolymer (A) will be described. The acrylic copolymer (A) is, for example, a hydrosilylation method described in JP-A-54-36395, JP-A-57-55954, or the like, or a monomer containing a reactive silyl group. However, from the viewpoint of ease of synthesis and the like, a monomer containing a reactive silyl group is used, and an azo radical polymerization initiator such as azobisisobutyronitrile is used. It is particularly preferred to produce by the solution polymerization method used.

The solvent used in the above solution polymerization method is not particularly limited as long as it is a non-aqueous solvent, and examples thereof include hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; and acetic acids such as ethyl acetate and butyl acetate. Esters;
Cellosolves such as ethyl cellosolve and butyl cellosorb; ether esters such as cellosolve acetate; ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone and acetone;
Examples include alcohols such as methanol, isopropyl alcohol, n-butanol, isobutanol, hexanol, octanol and the like.

In the above-mentioned solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, (CH ₃ O) ₃ Si-SS-
_{Si (OCH 3) 3, (} CH 3 O) 3 Si-S 8 -Si
The molecular weight of the obtained acrylic copolymer (A) may be adjusted by using a chain transfer agent such as (OCH ₃ ) ₃ alone or in combination of two or more kinds. In particular, when a chain transfer agent having an alkoxysilyl group in the molecule such as γ-mercaptopropyltrimethoxysilane is used, it is possible to introduce a reactive silyl group at the terminal of the acrylic copolymer (A). It is preferable because it is possible. The amount of such a chain transfer agent to be used is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, based on the total amount of the polymerization components used.

In the composition of the present invention, a solvent comprising 50% or more of a saturated hydrocarbon and / or an aromatic hydrocarbon having 9 or more carbon atoms in the total solvent and another organic solvent, and / or turpentine oil (B) is contained. Therefore, it is necessary to use the solvent used in the solution polymerization method so that the composition of the present invention satisfies this condition. Examples of the saturated hydrocarbon include, in addition to the hexane and cyclohexane, pentane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and the like. Among these, octane, nonane, decane, undecane, dodecane, and tridecane are preferred from the viewpoint of the appearance of the coating film at the time of coating and the recoatability.
Particularly, nonane, decane, undecane, dodecane, and tridecane are preferred. These saturated hydrocarbon solvents may be used alone or in combination of two or more. 9 carbon atoms
As the above aromatic hydrocarbons, propylbenzene, o
-Ethyltoluene, m-ethyltoluene, p-ethyltoluene, diethylbenzene and the like. Of these, propylbenzene and diethylbenzene are preferred. The other organic solvent is not particularly limited, and may be, for example, toluene, xylene, ethyl acetate, or the like.

In the present invention, as the pigment (C), various pigments usually used for paints can be used depending on a desired color. For example, titanium oxide, ultramarine blue, navy blue,
Inorganic pigments such as zinc white, red iron, lead, white lead, carbon black, transparent iron oxide, and aluminum powder; azo pigments,
Pigments such as organic pigments such as triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments are exemplified.

In the present invention, the hydrolyzable ester compound (D) is not particularly restricted but includes, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate,
Hydrolyzable ester compounds such as ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, trimethyl orthobutyrate, triethyl orthobutyrate, triethyl orthoisobutyrate, triethyl orthoisobutyrate; dimethoxy Methane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-
Dimethoxybutane; ethyl silicate (tetramethoxy silane), methyl silicate (tetramethoxy silane), methyl trimethoxy silane and the like. Of these, methyl orthoacetate is preferred from the viewpoint of the dehydration effect. These may be used alone or in combination of two or more. The hydrolyzable ester compound (D) is used as a dehydrating agent in the present invention.

The curing catalyst (E) is not particularly limited.
For example, a combined use of an organic carboxyl and an organic amine, an organic phosphate, an organic metal compound, and the like can be given. Specific examples of the organic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, octylic acid, 2-ethylhexanoic acid, decanoic acid, dodecanoic acid, benzoic acid, phthalic acid, fumaric acid, and maleic acid. Acids, succinic acid, itaconic acid and anhydrides thereof.
Specific examples of the organic amine include primary amines such as laurylamine, tertiary amines such as triethylamine and dimethyllaurylamine, and cyclic amines such as morpholine. The combination of the organic carboxylic acid and the organic amine may be, for example, acetic acid / dimethyllaurylamine, hexanoic acid / laurylamine, 2-ethylhexanoic acid / dimethyllaurylamine in consideration of the balance between curing activity and pot life. A combination of 2-ethylhexanoic acid / laurylamine is preferred. More preferably, 2
-A combination of ethylhexanoic acid / dimethyllaurylamine and 2-ethylhexanoic acid / laurylamine.

Specific examples of the organic phosphoric acid ester include di (2-ethylhexyl) monophosphate and di (2-ethylhexyl) diphosphate. From the viewpoint of the balance between the curing activity and the pot life, di (2-ethylhexyl) monophosphate is preferred, and this organic phosphate may be used alone or in combination with the organic amine. In this case, preferred combinations are di (2-ethylhexyl) monophosphate / dimethyllaurylamine and di (2-ethylhexyl) monophosphate / laurylamine, and more preferably, di (2
-Ethylhexyl) monophosphate / dimethyllaurylamine. The combination substance may be used alone or in combination of two or more.

Examples of the organometallic compound include, for example,
There are organic tin compounds, aluminum chelate compounds and the like. Examples of the organotin compound include dioctyltin bis (2-
Ethylhexylmalate), dioctyltin oxide or condensate of dibutyltin oxide and silicate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethylmalate), dibutyltin bis (butylmalate) , Dibutyltin bis (2-ethylhexylmalate), dibutyltinbis (oleylmalate), stannasoctoate, tin stearate, di-n
-Butyltin laurate oxide and the like. Also, dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-
Examples of organic tin compounds having a sulfur atom in the molecule, such as 3-mercaptopropionate, dibutyltin bisisooctylthioglucolate, dioctyltin bisisooctylthioglucolate, and octylbutyltin bisisooctylthioglucolate. it can.

Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate,
Aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetonate), alkyl acetylacetate aluminum diisopropylate and the like can be mentioned. Among these, when aluminum tris (ethyl acetoacetate) and aluminum tris (acetyl acetonate) are blended with isocyanate, the balance between storage stability and pot life is good, and the contact angle of the coating film is small. Is preferred.

The curing catalyst (E) may be used alone, or two or more of different types or those belonging to the same type may be used in combination.

The present invention is also a composition in which a polyester resin (F) having a polymerizable unsaturated group for dispersing a pigment is further blended with the curable composition for a top coat. As the polyester portion of the resin (F), any resin having a polarity and a molecular structure suitable for pigment dispersion may be used, and an alkyd type resin is generally used. Since the resin (F) has a polymerizable unsaturated group, it is possible to obtain a resin having good compatibility with the acrylic copolymer (A) by copolymerizing with the other polymerizable unsaturated monomer. it can.

The present invention further provides a polyester resin (F) having a polymerizable unsaturated group in the curable composition for topcoat paint of the first aspect or the curable composition for topcoat paint of the first aspect. The compounded curable composition for a top coat according to the second embodiment is further added to the following general formula (2): (R ³ O) _4-b —Si— (R ⁴ ) _b (2) R ³ represents a monovalent hydrocarbon group selected from the group consisting of 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.
R ⁴ is an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms.
And a monovalent hydrocarbon group selected from the group consisting of an aryl group and an aralkyl group having 7 to 10 carbon atoms. When a plurality of R ³ and / or R ⁴ are present, they may be the same or different. b represents 0 or 1. )) And / or a partially hydrolyzed condensate (G) thereof. The above component (G) is a component for improving the stain resistance of a coating film formed from the composition of the present invention and for improving the adhesion between the coating film and an object to be coated. The partially hydrolyzed condensate is obtained by converting a silicon compound represented by the general formula (2) into an alcohol-based solvent,
It is obtained by hydrolysis under acidic conditions. A composition obtained by mixing the silicon compound and / or its partially hydrolyzed condensate (G) with an acrylic copolymer (A) becomes a composition having room temperature curability and heat curability, and is formed using the composition. The resulting coating has excellent stain resistance. Although the reason is not clear, it is probably due to the difference in the relative curing speed between the acrylic copolymer (A) and the above-mentioned component (G) and the compatibility, and the effect of the improvement in surface hardness and hydrophilicity. It is thought that it is doing.

In the above formula (2), R ³ is an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- An alkyl group having 1 to 4 carbon atoms such as a butyl group; an aryl group having 6 to 10 carbon atoms, preferably an aryl group having 6 to 9 carbon atoms such as a phenyl group, and an aralkyl group having 7 to 10 carbon atoms, preferably Is a compound having 7 to 9 carbon atoms such as a benzyl group.
Is a monovalent hydrocarbon group selected from the group consisting of: When the alkyl group has more than 10 carbon atoms, the reactivity of the partially hydrolyzed condensate (G) of the silicon compound decreases. When R ³ is other than the above-mentioned alkyl group, aryl group and aralkyl group, the reactivity of the partially hydrolyzed condensate (G) of the silicon compound similarly decreases.

In the above general formula (2), R ⁴ is a monovalent group selected from the group consisting of 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. Represents a hydrocarbon group. The alkyl group, aryl group, and aralkyl group may be the same as those exemplified for R ³ above.

In the general formula (2), b represents 0 or 1. Therefore, in the general formula (2), (R ³
O) For _4-b, the value of 4-b is 3 or more. From the viewpoint that the curability of the coating film formed from the composition of the present invention is improved, b is preferably 0. When a plurality of R ³ or R ⁴ are present, they may be the same or different.

Specific examples of the silicon compound represented by the general formula (2) include, for example, tetramethyl silicate,
Tetraalkyl silicates such as tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate and tetra i-butyl silicate; methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Silane coupling agents such as silane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrisec-octyloxysilane, methyltriphenoxysilane, methyltriisopropoxysilane, and methyltributoxysilane.

As a specific example of the partially hydrolyzed condensate of the silicon compound represented by the above general formula (2), for example, water is added to the above tetraalkylsilicate or trialkoxysilane by a usual method, Examples thereof include those obtained by condensation, for example, MSI51, MSI53,
ESI28, ESI40, ESI48, HAS-1, H
AS-10 (above, trade name) (manufactured by Colcoat); MS
51, MS56, MS56S, MS51B15, MS5
6SB5 (above, trade name) (manufactured by Mitsubishi Chemical Corporation); M silicate 51, methyl silicate 56, silicate 40, silicate 45, silicate 48, ES48, FR-3
Partially hydrolyzed and condensed condensates of tetraalkoxysilane such as (trade name) (manufactured by Tama Chemical Co., Ltd.); Objects and the like.

Among the above-mentioned partially hydrolyzed decomposed condensates of the silicon compound, the compatibility with the acrylic copolymer (A) is excellent, and the curability of the obtained composition of the present invention is good. MSI51 and MI51 are excellent in hardness of the coating film formed by using the material and controlling the adhesion of contaminants.
S51, MS56, MS56S (partially hydrolyzed condensate of tetramethoxysilane), ESI40, silicate 45, silicate 48, ESI48, ES-48 (partially hydrolyzed condensate of tetraethoxysilane), FR-3
It is preferable to use a partially hydrolyzed decomposed condensate of tetraalkoxysilane such as (partially methoxy-substituted condensate of partially hydrolyzed condensate of tetraethoxysilane), particularly MS56S, silicate 4 having a weight average molecular weight of more than 1,000.
Compounds such as 8, ES-48, ESI48, and FR-3 are more preferable in that the compounding amount can be reduced. It is preferable to add methyl orthoacetate as a dehydrating agent in advance to these partially hydrolyzed decomposed condensates of the silicon compound from the viewpoint of storage stability after blending with the component (A).

The partially hydrolyzed condensate of the silicon compound is obtained by hydrolyzing the silicon compound represented by the above general formula (2) in an alcoholic solvent under acidic conditions.
Examples of the alcohol-based solvent include methanol,
Examples include ethanol, isopropanol, n-butanol, and isobutyl alcohol. These may be used alone or in combination of two or more. Among them, methanol, ethanol and isopropanol are preferred from the viewpoint of improving stability.

The above-mentioned acidic conditions refer to conditions such as (1) addition of an acidic substance and (2) treatment with a cation exchange resin. (1) As acidic substances, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid,
Inorganic acids such as sulfurous acid; phosphate esters such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, dioctyl phosphate, didecyl phosphate; formic acid, acetic acid, maleic acid, adipic acid, oxalic acid, succinic acid And sulfonic acid compounds such as dodecylbenzenesulfonic acid, paratoluenesulfonic acid, 1-naphthalenesulfonic acid, and 2-naphthalenesulfonic acid. Among these, hydrochloric acid, nitric acid, sulfurous acid, and formic acid, which have relatively low boiling points, are preferred because they can easily remove the acid after the acid treatment. (2) Examples of the treatment with a cation exchange resin include:
After treatment with a cation exchange resin such as Amberlyst 15 (trade name) (manufactured by Rohm and Haas) and Duolite C-433 (trade name) (manufactured by Sumitomo Chemical Co., Ltd.) and water, filtration and decane For example, a method of removing the cation exchange resin by a treatment or the like may be used. The above component (G) may be used alone or in combination of two or more.

The present invention further relates to a curable composition for a topcoat paint according to the first aspect, a curable composition for a topcoat paint according to the second aspect, or a curable composition for a topcoat paint according to the first aspect. The composition or the curable composition for a top coat according to the second embodiment, which further comprises the above component (G), is further mixed with an aminosilane and an epoxysilane. And a curable composition for a topcoat containing a silane coupling agent (H) comprising at least one compound selected from the group consisting of these reaction products. The above silane coupling agent (H)
Is blended in order to impart adhesion to the base with an epoxy-based intermediate coating agent or the like. The above silane coupling agent (H)
For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 2-aminoethylaminopropyltrimethoxysilane, 2-aminoethylaminopropyltriethoxysilane, N-phenylpropyltrimethoxysilane, N- Phenylpropyltriethoxysilane, 2.2: 1 (molar ratio) reaction product of γ-glycidylpropyloxytrimethoxysilane and 2-aminoethylaminopropyltrimethoxysilane, Epikote 828 (trade name) (Yuka Shell Epoxy Co., Ltd.) And a γ-aminopropyltriethoxysilane in a ratio of 1: 2 (molar ratio).

In the present invention, when a combination of an organic carboxylic acid or an organic phosphoric acid and an organic amine and / or an organometallic compound is used as the curing catalyst (E), the overcoating of each of the above-mentioned embodiments is carried out. The curable composition for paints may further contain a mercapto group-containing hydrocarbon and / or mercaptosilane (I). Examples of the mercapto group-containing hydrocarbon and / or mercaptosilane (I) include n-dodecylmercaptan, t-dodecylmercaptan, n-butylmercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, α- Mercaptomethylpentamethyldisiloxane, γ-mercaptopropylpentamethyldisiloxane, γ-mercaptopropyltris (trimethylsiloxy) silane, (CH ₃ O) ₃ Si-S-S-Si
(OCH ₃ ) ₃ , (CH ₃ O) ₃ Si—S ₈ —Si (O
CH ₃ ) _3, etc., from the viewpoints of availability, storage stability when blended with the organometallic compound in the curing catalyst (E), and the like, γ-mercaptopropyltrimethoxysilane, γ- Mercaptopropyltriethoxysilane is preferred. These can be used alone or in combination of two or more. When the mixture is blended with the acrylic copolymer (A), the pot life can be extended.

In order to obtain the curable resin composition for a top coating composition of the present invention, the acrylic copolymer (A), saturated hydrocarbon and / or aromatic hydrocarbon having 9 or more carbon atoms is required.
A solvent composed of at least% by weight and another organic solvent, and / or
Or a turpentine oil (B), a pigment (C), a hydrolyzable ester compound (D), and a curing catalyst (E);
If desired, a polyester resin (F) having a polymerizable unsaturated group for pigment dispersion may be mixed with a stirrer or the like. Further, in addition to the above composition, the above-mentioned general formula (2)
By mixing the silicon compound represented by the formula (I) and / or its partial hydrolysis condensate (G), the silane coupling agent (H), the mercapto group-containing hydrocarbon and / or the mercaptosilane (I). The curable resin composition for a top coating material according to the above aspect can be obtained.

The mixing ratio of these components is as follows. The following compounding ratio is the acrylic copolymer (A)
The value is based on 100 parts by weight. The above component (B) is composed of 5
１５０150 parts by weight. If it is outside the above range, the coating viscosity cannot be satisfied. The pigment (C) is 5-1.
50 parts by weight. If the amount is less than 5 parts by weight, a sufficient coloring effect cannot be obtained, and if the amount exceeds 150 parts by weight, the appearance of the coating film deteriorates. Within the above range, an amount capable of obtaining a desired coloring effect can be appropriately compounded.

The hydrolyzable ester compound (D) blended as a dehydrating agent is 0.1 to 150 parts by weight. 0.
If the amount is less than 1 part by weight, the dewatering effect is insufficient, and
When the amount exceeds the weight part, the finished appearance of the coating film is deteriorated. Depending on the pigment to be blended within the above range, the amount necessary for exhibiting the dehydration effect is appropriately blended, and usually 200 parts by weight based on 100 parts by weight of the total of the components (A) and (G). It is used in an amount of at most 100 parts by weight, more preferably at most 50 parts by weight, even more preferably at most 50 parts by weight. The acrylic copolymer (A) may be added to the component before the polymerization, may be added during the polymerization of the acrylic copolymer (A), or the obtained acrylic copolymer ( It may be added at the time of mixing A) with other components.

The dehydrating agent is preferably added after hydrolyzing a silicon compound or a partially hydrolyzed condensate of the silicon compound in an alcoholic solvent under acidic conditions. In this case, the amount of the dehydrating agent is not particularly limited, but usually, the total amount of the dehydrating agent and the alkyl alcohol is 0.5 part with respect to 100 parts by weight of the resin solid content of the partial hydrolysis condensate of the silicon compound. ~ 20 parts, especially 2-1
It is preferably about 0 part.

The curing catalyst (E) is used in an amount of 0.1 to 20 parts by weight. When the amount of the curing catalyst (E) is less than 0.1 part by weight, the obtained coating film has insufficient curability and does not exhibit weather resistance. If the amount is more than 20 parts by weight, a coating film formed using the composition tends to decrease in appearance such as surface gloss, which is not preferable. Preferably it is 0.2 to 13 parts by weight, more preferably 0.5 to 10 parts by weight.

The above component (F) is blended in an amount of 5 to 150 parts by weight. When the amount of the component (F) is less than 5 parts, the pigment dispersibility is insufficient, and when the amount exceeds 150 parts by weight, the weather resistance of the coating film decreases. Preferably it is 5 to 100 parts by weight, more preferably 10 to 50 parts by weight.

The above component (G) is blended in an amount of 2 to 70 parts by weight. If the amount of the component (G) is less than 2 parts by weight, the effect of improving the curability and stain resistance of a coating film formed using the obtained composition will be insufficient, and 70 parts by weight. If it exceeds 300, appearance properties such as surface gloss of the coating film will be reduced, and cracks will be generated. Preferably 2-5
0 parts by weight, more preferably 2 to 30 parts by weight. The component (G) can be added during the polymerization of the component (A) in order to improve the compatibility with the component (A), and can be hot-blended with the component (A).

The component (H) is used in an amount of 0.1 to 300 parts by weight. If the amount of the component (H) is less than 0.1 part by weight, the adhesion to the undercoat, the intermediate coat, and the undercoat is insufficient. On the other hand, when the amount exceeds 300 parts by weight, defects such as poor coating film appearance and cracks are caused. Preferably 0.2 to
100 parts by weight, more preferably 0.5 to 50 parts by weight.

The above component (I) is usually preferably added in an amount of 0.1 to 20 parts by weight. More preferably, 0.
It is 1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

The composition of the present invention further comprises a diluent,
Additives such as ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents; fibrous materials such as nitrocellulose, cellulose acetate butyrate; epoxy resins, melamine resins, vinyl chloride resins, fluororesins, chlorinated polypropylene, chlorinated rubber And resins such as polyvinyl butyral and polysiloxane may be added as appropriate.

The curable resin composition for a topcoat paint of the present invention is applied to an object to be coated by an ordinary method such as dipping, spraying, application using a brush, etc. Bake at about ℃ or more to cure.

The curable composition for a top coating composition of the present invention is generally used in a multilayer film. At this time, a permeable epoxy sealer, an acrylic rubber-based waterproof coating, an acrylic emulsion, a reactive epoxy emulsion containing an inorganic filler, or the like is used as an undercoat. Further, it is usually used as an overcoat for the purpose of ensuring the durability (prevention of cracking, etc.) by improving the adhesion to the undercoat or the base material, improving the impact resistance, and improving the followability to the undercoat. Acrylic paint, urethane paint, fluororesin paint, etc.
It can be used as an intermediate coat and / or undercoat.
Further, as these paints, low-contamination type paints containing the silicate components described above can also be used.

The curable composition for a top coating composition of the present invention can be used, for example, in a building made of metal, ceramics, glass, cement, ceramic molding, plastic, wood, paper, fiber, etc., home electric appliance, industrial equipment and the like. It is suitably used as a top coating.

[0095]

EXAMPLES The curable composition for a top coating composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Hereinafter, unless otherwise specified, parts mean parts by weight.

Comparative Production Example 1 Acrylic copolymer (A)-
20 parts of xylene was charged into a reactor equipped with the production stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel of No. 1, and heated to 110 ° C. while introducing nitrogen gas. Then, γ-
Methacryloxypropyltrimethoxysilane 12 parts, methyl methacrylate 57 parts, n-butyl acrylate 3
0 parts, n-methylol acrylamide 1 part, xylene 1
A mixture consisting of 0 parts and 0.9 parts of AIBN (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped at a constant speed over 5 hours by a dropping funnel. After completion of the dropwise addition, 0.1 parts of AIBN, 4 parts of xylene and 12 parts of toluene were added dropwise at a constant speed over 1 hour.
After aging for a period of time, the mixture was cooled, and xylene was added to the resin solution to obtain an acrylic copolymer (A) -1 having a resin solid content of 50%.
I got The average molecular weight of the obtained acrylic copolymer (A) -1 was 15,000.

Production Example 1 Preparation of acrylic copolymer (A) -2
A reactor equipped with a production stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was charged with 25 parts of Solvesso-100 (manufactured by Exxon Chemical Co., Ltd.), and heated to 110 ° C. while introducing nitrogen gas. . Thereafter, 10 parts of γ-methacryloxypropyltrimethoxysilane, 10 parts of stearyl methacrylate, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and 5 parts of n-butyl acrylate
, 15 parts of styrene, 10 parts of Solvesso-100 and 0.56 part of V-59 (manufactured by Wako Pure Chemical Industries, Ltd.) were dropped at a constant rate over 4 hours by a dropping funnel. After dropping, 0.1 part of V-59 and 4 parts of Solvesso-100 were added.
Parts, 12 parts of Shellsol S (manufactured by Shell Japan),
After dropping at a constant speed over 30 minutes, the mixture was aged at 110 ° C. for 1.5 hours and then cooled, and Solvesso-100 was added to the resin solution to obtain an acrylic copolymer (A) having a resin solid content of 50%.
-2 was obtained. The average molecular weight of the obtained acrylic copolymer (A) -2 was 20,000.

Production Example 2 Preparation of acrylic copolymer (A) -3
Production In Production Example 1, 10 parts of γ-methacryloxypropyltrimethoxysilane was used as 15 parts, stearyl methacrylate was kept at 10 parts, and 30 parts of methyl methacrylate was used as 3 parts.
5 parts, 30 parts of n-butyl acrylate was changed to 25 parts, 5 parts of n-butyl methacrylate was changed to 10 parts, 15 parts of styrene was changed to 5 parts, and V-59 was changed to 0.9 part. In the same manner as in Example 1, an acrylic copolymer (A) -3 having a resin solid content of 50% was obtained. The number average molecular weight of the obtained acrylic copolymer (A) -3 was 10,000.

Production Example 3 Acrylic copolymer (A) -4
In Production Example 1, 10 parts of γ-methacryloxypropyltrimethoxysilane was added to 13 parts, 2-hydroxyethyl methacrylate to 2 parts, and stearyl methacrylate 10 to 10 parts.
7 parts, 30 parts of methyl methacrylate to 25 parts, n
-30 parts of butyl methacrylate was changed to 43 parts, 5 parts of n-butyl acrylate was changed to 10 parts, and 0.56 part of azobisisobutyronitrile was changed to 1 part. 50% acrylic copolymer (A)-
4 was obtained. The number average molecular weight of the obtained acrylic copolymer (A) -4 was 10,000.

Production Example 4 Acrylic copolymer (A) -5
In Production Example 2, FR-3 (manufactured by Tama Chemical Co., Ltd.) (G) -1 which is a silicate compound in addition to the solvent initially charged
, And polymerized in the same manner as the others, and the solid content concentration was 50%.
Acrylic copolymer (A) -5 was obtained. The number average molecular weight of the obtained acrylic copolymer (A) -5 is 1200
It was 0.

Production Example 5 Preparation of polyester resin (F) -1
They were charged 20 parts of xylene initially prepared, 8 parts of γ- methacrolein trimethoxysilane, 10 parts of styrene,
A mixture of 40 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 12 parts of a polymerizable unsaturated group-containing polyester resin, 1.3 parts of AIBN, and 5 parts of toluene was added dropwise over 5 hours. After dropping, AI
A mixture consisting of 0.14 parts of BN and 10 parts of xylene was dropped at a constant speed over 1 hour. Then, it aged at the same temperature for 2 hours. The obtained reaction product was diluted with xylene to a resin solid content of 50%. The number average molecular weight of the obtained polyester resin (F) -1 was 10,000.

Production Example 6 Preparation of polyester resin (F) -2
Were charged 20 parts of Solvesso -100 initially prepared, 8 parts of γ- methacrolein trimethoxysilane, styrene 1
0 parts, methyl methacrylate 25 parts, n-butyl acrylate 10 parts, n-butyl methacrylate 30 parts, stearyl methacrylate 5 parts, polymerizable unsaturated group-containing polyester resin 12 parts, V-59 1.3 parts, Solvesso-
A mixture of 5 parts of 100 was dropped over 4 hours. After dropping, 0.14 parts of V-59, Solvesso-
A mixture of 10 parts of 100 and 10 parts of shell sol was dropped at a constant speed over 30 minutes. Then, it aged for 1.5 hours at the same temperature. The obtained reaction product was dissolved in Solvesso-1
It was diluted to a resin solid content of 50% with 00 / Shellsol S = 1/1. The number average molecular weight of the obtained polyester resin (F) -2 was 10,000.

Example 1 95 parts of titanium oxide CR-95 (manufactured by Ishihara Sangyo Co., Ltd.) as pigment (C) -1 and hydrolyzed ester compound (D) -1 so as to be 5% by weight with respect to the total resin solid content. Was added, and 30 parts of the polyester resin (F) -2 obtained in Production Example 6 was used. The acrylic resin obtained in Production Example 1 was dispersed in a paste dispersed using glass beads for 2 hours with a paint conditioner. 20 parts of FR-3 (a partially hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane manufactured by Tama Chemical Co., Ltd.) was added as silicon compound (G) -1 to 100 parts of resin solid content of polymer (A) -2. The mixed solution was added and diluted with the solvent (B) -2 to obtain a white enamel having a solid content of 60%. The obtained white enamel was mixed with dibutyltin bisbutylmalate (E) -2 as a curing catalyst (E) and γ-aminopropyltriethoxysilane as a silane coupling agent (H) in a ratio of 2: 1 (molar ratio). ) Of the reactant (H) -1 and γ-aminopropyltriethoxysilane (H) -3 with respect to 100 parts of the acrylic copolymer (A) -1 and the polyester resin (F) in total, 2 parts each.
1 part, (E) -1, (H) -1 and (H) -3 were previously mixed and added. Further, the solvent (B) -2
Was added and stirred for 5 minutes using a stirrer to obtain a composition having a solid content of 45%.

The obtained composition was coated on a slate plate with an E-spec primer (Isamu tile A; manufactured by Isamu Paint Co., Ltd.) in an amount of 1.4 to
1.6 kg / m ² painted on top
A sample was prepared by coating with a dry film thickness of 20 to 30 μm using day 1 coat. The sample was scratched to reach the substrate with a cutter, and 1 day, 2 days, 3 days, 6 days
On the 10th, 14th and 14th days, the top coat was applied with a brush, and the state of the coating film in each period was observed, and the presence or absence of spots and the like was observed.

The surface state, gloss, stain resistance, weather resistance, contact angle, adhesiveness, and recoating recoating of the obtained coating film were evaluated according to the following methods. Table 2 summarizes the results. (A) Surface condition The coating film surface was visually observed and evaluated based on the following evaluation criteria. (Evaluation Criteria) A: No cracks were observed and the surface condition was good. B: Fine cracks are partially observed. C: Cracks are observed throughout. (B) Gloss The gloss of the coating film surface is determined by GM according to JIS K5400.
It was measured using a 268 gloss meter (Minolta) (60
° gloss). (C) Stain resistance (ΔL value) The color of the coating surface immediately after formation and the color of the coating surface after being left outdoors for 3 months (outdoor exposure) in Settsu-shi, Osaka are CR-300 color difference meter (Minolta) And the obtained L was measured.
The difference (ΔL value) was determined from the value (brightness). (D) Weather resistance (gloss retention) The gloss of the coating surface immediately after formation and the gloss of the coating surface after 2,000 hours were measured using a sunshine weatherometer, and the gloss retention after 2,000 hours (%) I asked. (E) Contact angle The static contact angle of the coating film surface with water immediately after formation was measured with a contact angle measuring instrument (model CA-S150, manufactured by Kyowa Interface Science Co., Ltd.).

(F) Adhesion A slate plate was coated with a commercially available undercoat of E specification (manufactured by Isamu Co., Ltd.), and the next day was coated with a topcoat. Room temperature (23 ° C,
(55% humidity) by JIS K540
Evaluation was made by measuring the grid adhesion according to 0. (Evaluation Results) 10: 100/100 8: 80/100 6: 60/100 4: 40/100 2: 20/100 0: 0/100 (g) Degree The debris at the time of overcoat recoating is based on the following criteria. evaluated. (Evaluation criteria) ：: No abnormality is observed in the coating film. ぢ: Spotting occurs only in the cut portion. ×: Spotting occurs in the entire recoat part. (H) Odor When the composition is applied by splat or roller coating Was evaluated according to the following criteria. (Evaluation criteria) ：: No nose-like odor is felt, and it can withstand painting for a long time. ×: Strong odor, cannot withstand long-time coating.

Examples 2 to 12 and Comparative Examples 1 to 3 A white enamel having a solid content of 60% was prepared in the same manner as in Example 1 except that the composition was shown in Table 1. % Of the composition was obtained.

The compositions obtained in Examples 2 to 12 and Comparative Examples 1 to 3 were coated on a slate plate with an undercoating of specification E (Isam Tile A; manufactured by Isamu Paint Co., Ltd.).
It was applied by air spray so as to have a thickness of 30 μm, and cured under the curing conditions shown in Table 1 to form a coating film. Further, in Comparative Examples 1 and 2, for the purpose of comparing the taste, a bisphenol A type bifunctional epoxy compound (Epicoat 828; manufactured by Yuka Shell Epoxy) and γ-aminopropyltriethoxysilane were 1: 2 (molar ratio). Reactant (H) -1 and aminoethylaminopropyltrimethoxysilane (H) -4
Was mixed in an amount of 2 parts and 0.8 part with respect to 100 parts of the resin solid content of the acrylic copolymer (A).

The coating film was evaluated in the same manner as in Example 1. The results are summarized in Table 2.

[0110]

[Table 1 (Part 1)]

[0111]

[Table 1 (Part 2)]

[0112]

[Table 2]

The compositions blended in Examples 1 to 12 and Comparative Examples 1 to 3 are as follows. Solvent (B) (B) -1; Xylene (B) -2; Solvesso-100 / Shellsol-S =
1/1 (weight ratio) (B) -3; turpentine pigment (C) (C) -1; CR-95 (white; titanium oxide) (C) -2; iron oxide (red) (C) -3 Phthalocyanine blue hydrolysable ester (D) (D) -1; methyl orthoacetate (D) -2; methyl orthoformate curing catalyst (E) (E) -1; dioctyltin bis (2-ethylhexylmalate) (E) -2; dibutyltin bisbutylmalate (E) -3; dibutyltinbisoleylmalate (E) -4; 2-ethylhexanoic acid / dimethyldodecylamine having an acid / base equivalent of 1 / 1.03. A mixture formulated to be

Silicate Compound (G) (G) -1; FR-3 (manufactured by Tama Chemical) (G) -2; Silicate 48 (manufactured by Tama Chemical) (G) -3; ES-48 (Tama Chemical) (G) -4; ethyl silicate 48 (manufactured by Colcoat) silane coupling agent (H) (H) -1; bisphenol A type bifunctional epoxy compound (epicoat 828; manufactured by Yuka Shell Epoxy) and γ-
1: 2 (molar ratio) of aminopropyltriethoxysilane
(H) -2: 1: 2.2 (molar ratio) of aminoethylaminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane Reactant (H) -3; γ-aminopropyltriethoxy Silane (H) -4; aminoethylaminopropyltrimethoxysilane Mercapto group-containing hydrocarbon and / or mercaptosilane (I) (I) -1; γ-mercaptopropyltrimethoxysilane (I) -2; γ-dodecyl mercaptan

As shown in Table 2, the cured coating films obtained in Examples 1 to 12 had excellent recoatability, and had a small surface contact angle when a silicon compound (G) was blended. It turns out that it shows excellent stain resistance.

[0116]

As described above, the curable composition for paints of the present invention exhibits excellent recoating properties on various substrates and undercoats, and provides paints with low odor. Further, when the silicon compound (G) is blended, the contact angle of the coating film is small and the coating film is excellent in stain resistance. Further, the coated product obtained by applying the curable composition for coating of the present invention is excellent in the adhesion of the coating film,
It has excellent stain resistance.

Claims (8)

[Claims] 1. The following general formula (1): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 carbon atoms. ~ 1
Represents a monovalent group selected from the group consisting of 0 aralkyl groups. When a plurality of R ¹ or R ² are present, they may be the same or different. a represents an integer of 0 to 2. A) an acrylic copolymer having at least two hydrolyzable silyl groups bonded to carbon atoms represented by the formula (1), wherein the number of carbon atoms of the alkyl group is 8 or more and less than 20; 100 parts by weight of an acrylic copolymer (A), which is an acrylic copolymer obtained by copolymerizing a monomer mixture containing 50 to 50% by weight, a saturated hydrocarbon and / or an aromatic hydrocarbon having 9 or more carbon atoms. Hydrogen 5
A solvent comprising 0% by weight or more and another organic solvent, and / or 5 to 150 parts by weight of turpentine oil (B), 5 to 150 parts by weight of pigment (C), 0.1 of hydrolyzable ester compound (D) To 150 parts by weight, and a curing catalyst (E)
A curable composition for a top coat, comprising 0.1 to 20 parts by weight. 2. A curable composition for a top coat according to claim 1, further comprising a polyester resin (F) having a polymerizable unsaturated group for dispersing a pigment, and an acrylic copolymer (A).
A curable composition for a topcoat paint, comprising 5 to 150 parts by weight per 100 parts by weight. 3. The curable composition for a top coat according to claim 1 or the curable composition for a top coat according to claim 2, further comprising the following general formula (2): (R ³ O) _4-b − Si- (R ⁴ ) _b (2) (wherein, R ³ is selected from the group consisting of 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. Represents a monovalent hydrocarbon group.
R ⁴ is an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms.
And a monovalent hydrocarbon group selected from the group consisting of an aryl group and an aralkyl group having 7 to 10 carbon atoms. When a plurality of R ³ and / or R ⁴ are present, they may be the same or different. b represents 0 or 1. ), Wherein the silicon compound and / or the partially hydrolyzed condensate (G) thereof is contained in an amount of 2 to 70 parts by weight based on 100 parts by weight of the acrylic copolymer (A). Composition. 4. An acrylic copolymer (A) is obtained by copolymerizing a monomer mixture containing 3 to 90% by weight of a monomer containing a hydrolyzable silyl group represented by the general formula (1). 4. The curable composition for a topcoat paint according to claim 1, wherein the curable composition is obtained by: 5. The curable composition for a top coat according to claim 1, the curable composition for a top coat according to claim 2, or
A silane coupling agent (H) comprising at least one compound selected from the group consisting of aminosilanes, epoxysilanes, and reaction products thereof, is further added to the curable composition for topcoat paints according to claim 3 by acryl. A curable composition for a topcoat paint, comprising 0.1 to 300 parts by weight based on 100 parts by weight of the system copolymer (A). 6. The curing catalyst (E) is a combination of an organic carboxylic acid or an organic phosphoric acid and an organic amine, and / or
The curable composition for a topcoat paint according to any one of claims 1 to 5, which is an organometallic compound. 7. The curable composition for a topcoat paint according to claim 6, further comprising a mercapto group-containing hydrocarbon and / or mercaptosilane (I). 8. A coated article obtained by applying the curable composition for a top coating composition according to any one of claims 1 to 7.