JP2002129097A - Curable resin composition for overcoat and coated product composed of applying the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition which improves adhesion to various base materials, weather resistance, and contamination resistance which are faults, without impairing excellent various characteristics of an acrylic lacquer excellent in coating operability, thick coating, and versatility. SOLUTION: A composite film containing a siloxane bond and a urethane bond is formed by reacting with a multifunctional isocyanate and the resin for coating, wherein the resin is obtained from a vinyl copolymer (B) component containing a silyl group which bonds a hydrolysis group with an acrylic resin (A) component containing a hydroxyl group. Consequently, it is possible to improve weather resistance and contamination resistance compared with only and acrylic resin containing a hydroxyl group. Furthermore, it is possible to improve adhesion to various materials which is hard to improve until now by using only polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable resin composition for a top coat. More specifically, for example, metal,
A curable resin composition for a topcoat paint that can be suitably used for painting of buildings, home appliances, industrial equipment, and the like made of ceramics, glass, cement, ceramic moldings, plastics, wood, paper, fibers, and the like, and the overcoat. The present invention relates to a painted product obtained by applying a curable resin composition for a paint.

[0002]

2. Description of the Related Art Conventionally, surfaces of industrial products such as ceramic compositions, buildings made of concrete and steel, and building materials are coated with paints such as fluororesin paints, acrylic urethane resin paints and acrylic silicone resin paints. By coating, the appearance of a building or the like is improved, and the anticorrosion property, weather resistance, and the like are improved. In particular, acrylic urethane resin paint is a paint excellent in coating workability, thick coatability, and versatility that are the drawbacks of the above-mentioned fluororesin paint and acrylic silicone paint.Especially, from the viewpoint of environmental issues, weak solvent type paint Urethane paint is on the market.

[0003] However, these paints have poor weather resistance,
There is a problem that the stain resistance is insufficient and the period until repainting is shortened. In contrast, Japanese Patent Application Laid-Open
The weak solvent type acrylic silicone paint disclosed in -279480 has high weather resistance and has an advantage of extending the period until recoating, but due to its cross-linking form, compared to a weak solvent type urethane paint. Depending on an object to be coated, there was a problem that the adhesion was insufficient and the adhesion was lacking. In addition, since the solvent resistance tends to be insufficient, there is a case where the epoxy-based paint is coated with a coating and the impact resistance is insufficient when applied to a steel plate.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an acrylic urethane paint excellent in coating workability, thick coatability and versatility, without impairing the excellent performances of the acrylic urethane paint. It is an object of the present invention to provide a coating composition having improved adhesion to a substrate.

[0005]

SUMMARY OF THE INVENTION The present invention provides a novel curable resin composition for a paint having the following constitution, thereby achieving the above object. 1) Hydroxyl-containing acrylic resin (A) component, vinyl copolymer containing silyl group bonded to hydrolyzable group (B)
A curable resin composition for paints, comprising a component, a polyfunctional isocyanate compound (C) component and a weak solvent (D) component. 2) The hydroxyl group-containing acrylic resin (A) component has a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20 to 100.
(KOHmg / g), acid value 0.1-30 (KOHmg
/ G), the curable resin composition for a paint according to claim 1. 3) The curable resin composition for a paint according to claim 1 or 2, wherein the hydroxyl group-containing acrylic resin (A) component comprises a NAD type polyol dispersion (A-1) component. 4) The curable resin composition for paint according to claim 1, wherein the component (B) is blended in an amount of 20 to 250 parts by weight based on 100 parts by weight of the component (A). 5) Component (B) is (a) a vinyl monomer containing a silyl group bonded to a hydrolyzable group, (b) a vinyl monomer containing a hydroxyl group, (c) another copolymerizable monomer. The curable resin composition for a paint according to any one of claims 1 to 4, which is a vinyl copolymer (B-1) obtained by copolymerizing a monomer. 6) The curable resin composition for a paint according to claim 5, comprising (d) an alkyl (meth) acrylate having 5 or more carbon atoms among the (c) other copolymerizable monomers. . 7) A resin obtained by copolymerizing a component (e) of a vinyl group-containing polyester compound (e) in addition to a monomer species constituting the component (B-1) of the vinyl copolymer with the component (B). The curable resin composition for paint according to any one of claims 1 to 6, wherein a component (B-2) is blended. 8) The curable resin composition for a paint according to any one of claims 1 to 7, wherein a (meth) acrylic amide compound (f) is further copolymerized with the component (B-2). . 9) The curable resin composition for a paint according to any one of claims 1 to 8, wherein the weak solvent (D) contains an aliphatic hydrocarbon. 10) Furthermore, the general formula (1)

[0006]

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(Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 10 carbon atoms)
R ² is 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 A represents 0 or 1. The curable resin composition for a paint according to any one of claims 1 to 9, which comprises a silicon compound represented by the formula (1) or a partial hydrolysis condensate (E) thereof. 11) The curable resin composition for a paint according to any one of claims 1 to 10, further comprising an organometallic compound (F) added to the curable resin composition for a paint. 12) The curable resin composition for paints further comprising a monofunctional isocyanate compound (G) component.
The curable resin composition for a paint according to any one of claims 1 to 7. 13) Mixture 100 of component (A-1) and component (B)
The component (F) according to any one of claims 1 to 12, wherein the component (F) is 0.1 to 30 parts by weight and the component (G) is 0.1 to 100 parts by weight with respect to parts by weight. Curable resin composition for paint. (14) The curable resin composition for a paint according to any one of (1) to (13), wherein a pigment (H) is blended into the composition. 15) A coated product obtained by applying the composition for a topcoat coating according to any one of claims 1 to 14.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The hydroxyl group-containing acrylic resin (A) of the present invention means an acrylic polyol generally used in the field of polyurethane, and is mixed and reacted with a polyisocyanate as a curing agent. In the coating film to be formed, it is the main component for forming the coating film.

Such acrylic polyols include:
In the acrylic copolymer, 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 570 manufactured by Toa Gosei Chemical Industry Co., Ltd.
0,4-hydroxystyrene, Nippon Shokubai Chemical Industry Co., Ltd.
HE-10, HE-20, HP-1 and HP-2 manufactured by Toshiba
0 (all of which are acrylic acid ester oligomers having a hydroxyl group at the terminal), Blemmer-P manufactured by NOF Corporation
P series (polypropylene glycol methacrylate)
G) Blemmer-PE series (polyethylene glycol monomethacrylate) Blemmer-PEP series (polyethylene glycol polypropylene glycol methacrylate) Blemmer-AP-400 (polypropylene glycol monoacrylate), Bremma-AE-350
(Polyethylene glycol monoacrylate) and Blemma GLM (glycerol monomethacrylate),
(Meth) such as N-methylol (meth) acrylamide
Hydroxyalkyl esters of acrylic acid, ε-caprolactone-modified hydroxyalkylvinyl-based copolymer compounds Placel FA-1, Placec obtained by reacting a hydroxyl group-containing compound with ε-caprolactone
l FA-4, Placel FM-1, Plac
celFM-4 (manufactured by Daicel Chemical Industries, Ltd.), T
ONE M-201 (manufactured by UCC), a polycarbonate-containing vinyl compound (for example, HEAC-1
(1) Monoethylenically unsaturated monomers having a hydroxyl group such as (manufactured by Daicel Chemical Industries, Ltd.)
An acrylic polyol having two or more hydroxyl groups in the molecule can be used. Among them, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate
2-hydroxybutyl (meth) acrylate, 4-
Hydroxybutyl (meth) acrylate is preferable because it has excellent reactivity with isocyanate and a coating film having good weather resistance, chemical resistance and impact resistance can be obtained. Particularly preferably, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate.

The polyol used in the present invention has a weight average molecular weight of 5,000 to 80,000, preferably 20,000 to 60,000, and a molecular weight of 5,000.
When it is smaller, the curability and durability of the coating film are inferior, and when it is more than 80000, the finish of the coating film is not sufficient. Furthermore, the hydroxyl value is 20-100.
(KOHmg / g), acid value 0.1-30 (KOHmg
/ G) is preferred, and the hydroxyl value is 20 (KOHmg / g)
If it is smaller, the crosslink density is low, and the physical properties of various coatings and stain resistance are inferior. Conversely, if it is more than 100 KOHmg / g, a vinyl copolymer having a silyl group and a hydroxyl group bonded to a hydrolyzable group is used. When mixed with the component (B), the compatibility is lowered and the crosslink density is increased, and the surface orientation of the partially hydrolyzed condensate is undesirably inhibited.
If the acid value is less than 0.1 (KOH mg / g), the dispersibility with the pigment and the curability will decrease, and conversely, 30
(KOH mg / g) is not preferred because it causes a decrease in storage stability as a coating material.

Polyol NAD type resin dispersion (A-1)
The components are those in which the resin is dispersed in a non-aqueous solvent, and a part of the resin contains components that are soluble in the non-aqueous solvent.
Other parts contain components that are insoluble in non-aqueous solvents. The resin portion soluble in the polyol non-aqueous solvent is one having a solubility in the non-aqueous solvent of 99.0% by weight or more. Conversely, the resin portion that does not dissolve in the non-aqueous solvent is one that does not dissolve in the non-aqueous solvent at all or has a very small amount (the solubility is less than 1.0% by weight). Such a NAD-type resin dispersion is of a two-pack type in which NAD-type resin particles are composed of a polyol and isocyanate is used as a curing agent. The NAD type resin dispersion (A-1) component can be used alone or as a mixture of two or more types including the same type. The component (A-1) can be dispersed even in a solvent having a low solubility called a weak solvent, and has a solubility parameter (hereinafter, SP) of 6.5 to 9.5.
Of the degree. The weight average molecular weight of the NAD type resin dispersion (A-1) component is 5000 to 80000, the hydroxyl value is 20 to 100 (KOHmg / g), and the acid value is 0.1 to 3
0 (KOHmg / g) can be used. When the weight average molecular weight is less than 5,000, appropriate viscosity is not obtained as a paint, and the properties of each coating film are inferior. On the other hand, when the weight average molecular weight is more than 80000, vinyl having a silyl group and a hydroxyl group bonded to a hydrolyzable group is used. When mixed with the system copolymer (B) component, the compatibility and the sharpness and gloss of the coating film are deteriorated, which is not preferable. When the hydroxyl value is 20 (K
OH mg / g), the crosslink density is low, and the physical properties of various coatings and stain resistance are poor.
When it is higher than Hmg / g, a vinyl copolymer (B) having a silyl group and a hydroxyl group bonded to a hydrolyzable group
Mixing with the components is not preferable because the compatibility is lowered and the crosslinking density is increased, and the surface orientation of the partially hydrolyzed condensate is inhibited. When the acid value is less than 0.1 (KOH mg / g), the dispersibility with the pigment and the curability decrease, and when the acid value is more than 30 (KOH mg / g), the storage stability as a coating decreases. Is not preferred. In the case of the above-mentioned polyol NAD, (b) to (d)
Can be used. Here, when the NAD-type polyol dispersion (A-1) component is used as the hydroxyl group-containing acrylic resin (A) component, workability such as sagging can be ensured without adding an additive such as an anti-sagging agent. In addition, it is preferable in that the deterioration of the surface state of the coating film due to the additive can be suppressed.

Next, the vinyl copolymer (B) component having a silyl group and a hydroxyl group bonded to a hydrolyzable group has a main chain substantially consisting of a main chain obtained by copolymerization of an acrylic monomer. (Hereinafter also referred to as a main chain substantially consisting of an acrylic copolymer chain), the weather resistance of a coating film formed from the curable resin composition for a paint of the present invention obtained,
Excellent in chemical resistance and the like.

It is noted that the main chain of the acrylic copolymer (B) is substantially composed of an acrylic copolymer chain when 50% of the units constituting the main chain of the acrylic copolymer (B) is used.
The above means that 70% or more is formed from acrylic monomer units.

Further, since the acrylic copolymer (B) contains a silyl group bonded to a hydrolyzable group in a form bonded to a carbon atom, the water resistance and alkali resistance of the coating film are reduced.
Excellent acid resistance and the like.

In the acrylic copolymer (B), the number of silyl groups bonded to the hydrolyzable group is preferably 2 or more, more preferably 3 or more per molecule of the acrylic copolymer (B). The coating film formed from the composition of the present invention is preferable because it has excellent durability such as weather resistance and solvent resistance.

The silyl group bonded to the hydrolyzable group is
It may be bonded to the terminal of the main chain of the acrylic copolymer (B), may be bonded to the side chain, or may be bonded to the terminal and the side chain of the main chain. Examples of a method for introducing a silyl group bonded to a hydrolyzable group include a method of copolymerizing a monomer containing a silyl group bonded to a hydrolyzable group with another monomer, and a method of reacting a silicate compound. Or a method of reacting a silicate compound with a hydroxyl group-containing copolymer. A simple method is to copolymerize a monomer containing a silyl group bonded to a hydrolyzable group with another monomer.

Examples of the silicon hydrolyzable group bonded to the hydrolyzable group include a halogen group and an alkoxy group. Among them, an alkoxy group is preferable from the viewpoint of easy control of the reaction, and is represented by the following general formula.

General formula (2)

[0019]

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R ³ in the general formula (2) is a hydrogen atom or a carbon atom having 1 to 10, preferably, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-propyl group.
It is a C1-C4 alkyl group, such as a butyl group and an i-butyl group. If the alkyl group has more than 10 carbon atoms, the reactivity of the silyl group bonded to the hydrolyzable group will decrease. Also, when the group bonded to oxygen of the alkoxy group is a group other than an alkyl group such as a phenyl group or a benzyl group, the reactivity of the silyl group bonded to the hydrolyzable group is reduced.

R ⁴ in the general formula (2) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, an alkyl group having 1 to 4 carbon atoms as exemplified in the aforementioned R ³ ;
For example, it is a monovalent hydrocarbon group selected from an aryl group preferably having 6 to 25 carbon atoms such as a phenyl group and an aralkyl group preferably having 7 to 12 carbon atoms such as a benzyl 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.

In the general formula (2), (R ³ O) _3-b
Is such that 3-b is 1 or more and 3 or less, that is, b is 0
B is preferably 0 or 1, from the viewpoint that the curability of the acrylic copolymer (B) is improved. Therefore, the number of bonds of R ⁴ is preferably 0 to 1.

[0023] Formula (2) present in the (R _³ O) _^3-b or if the number is two or more R ⁴ _b, R contained 2 or more
3 or R4 may be the same or different.

Specific examples of the silyl group bonded to a hydrolyzable group bonded to a carbon atom represented by the general formula (2) include, for example, a monomer containing a silyl group bonded to a hydrolyzable group described below. Examples include groups contained in the body. The component (B) includes, for example, (a) a vinyl monomer containing a silyl group bonded to a hydrolyzable group, (b) a vinyl monomer containing a hydroxyl group, and (c) other copolymerizable monomers. Can be obtained by copolymerizing various monomer parts by weight.

The content ratio of the monomer unit in the acrylic copolymer (B) is such that the coating film formed using the composition of the present invention has excellent durability and strength. Therefore, it is preferably from 1 to 90% by weight, more preferably from 2 to 70% by weight, particularly preferably from 3 to 50% by weight.

Specific examples of the silyl group-containing vinyl copolymer (a) component bonded to a hydrolyzable group include, for example,

[0027]

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General formula (3) such as

[0029]

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[0030]

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General formula (4) such as

[0032]

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[0033]

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General formula (5) such as

[0035]

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[0036]

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General formula (6) such as

[0038]

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[0039]

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General formula (7) such as

[0041]

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(Wherein R ³ , R ⁴ , R ⁵ and b are the same as defined above in formulas (2) and (3), and m and n are 1 to 14)
And p represents an integer of 0 to 20), or (meth) acrylic acid having a silyl group bonded to a hydrolyzable group bonded to a carbon atom at a terminal via a urethane bond or a siloxane bond. -And the like. Among them, the compound represented by the 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 silyl group-containing vinyl monomers (a) bonded to the hydrolyzable groups may be used alone or in combination of two or more.

Specific examples of the hydroxyl group-containing vinyl monomer and / or its derivative (b) component include the above-mentioned (A)
It is the same as that obtained by copolymerizing an ethylenically unsaturated monomer containing a hydroxyl group used in copolymerizing the acrylic polyol in the component. The amount used is preferably 20 (KOHmg / g) or more in terms of hydroxyl value.

These alcoholic hydroxyl group-containing vinyl monomers (b) may be used alone or in combination of two or more. The amount used is 2 to 40% by weight.
It is preferably 3 to 30% by weight from the viewpoint of sufficiently exhibiting curability, adhesion and solvent resistance, and particularly preferably 5 to 30% by weight.
-20% by weight is even more preferred.

Specific examples of the copolymerizable monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 3,3,5, -trimethylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) Acrylate, benzyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, isobornyl (meth) acrylate, hydroxy (meth) acrylic acid Phosphate ester group-containing (meth) such as condensation products of alkyl esters and phosphoric acid or phosphoric esters
An acrylic compound and a (meth) acrylate derivative such as a (meth) acrylate containing a urethane bond or a siloxane bond are exemplified. Other copolymerizable monomers include aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; 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 An amide group-containing vinyl compound 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; Other vinyl compounds such as propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, and vinyl sulfonic acid are included.

These copolymerizable monomer (c) components may be used alone or in combination of two or more. In the component (B) of the present invention, among the other copolymerizable vinyl monomers (c) constituting the component (B),
It is preferable to copolymerize (meth) acrylic acid having 5 or more carbon atoms and / or a derivative (d) component thereof. Specific examples of the component (d) include, for example, pentyl (meth) acrylate, hexyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, laurylmethyl (meth) acrylate, palmitoyl ( meth) acrylate - DOO, stearyl (meth) acrylate - DOO, Burenma -SLMA ((meth) mixture of C ₁₂ -C ₁₈ alkyl esters of acrylic acid; manufactured by NOF Corporation
Manufactured). From the viewpoint of improving the solubility when the weak solvent is a solvent containing an aliphatic compound, 2
-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, lauryl methyl (meth) acrylate, Palmitoyl (meth) acrylate, stearyl (meth) acrylate, and Bremma-SLMA are preferred. In particular, laurylmethyl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (meth) acrylate,
Bremma-SLMA is more preferred.

The amount used is preferably from 2 to 70% by weight, and more preferably from 5 to 60% by weight, particularly from 10 to 50% by weight, from the viewpoints of solubility in a solvent during polymerization and dilution and polymerization stability. % By weight is more preferred.

The total amount of the components (b), (c) and (d) used depends on the type and amount of the silyl group-containing vinyl monomer (a) bonded to the hydrolyzable group. The amount may be appropriately adjusted according to the requirements.
It is preferably from 0 to 99% by weight, more preferably from 30 to 98% by weight, particularly preferably from 50 to 97% by weight. The amount of the component (a) used is preferably 1 to 90% by weight, more preferably 2 to 70% by weight, and particularly preferably 3 to 50% by weight of the polymerization component.

The acrylic copolymer (B) may use two or more different resin components in combination. The resin (B) component may contain a group such as a carboxyl group or an amino group, and in that case, curability and adhesion are improved. In particular,
In the case where a carboxyl group is bonded to the polymer chain, curability can be obtained without blending the organometallic compound (F).
Coating properties such as weather resistance can be ensured.

The resin (B) component is described in, for example,
It can be produced by a hydrosilylation method described in JP-A-4-36395, JP-A-57-55954, or the like, or a solution polymerization method using a monomer containing a silyl group bonded to a hydrolyzable group. Azo series such as azobisisobutyronitrile and V-59 (manufactured by Wako Pure Chemical Industries, Ltd.) using a monomer containing a silyl group bonded to a hydrolyzable group in view of ease of synthesis and the like. It is particularly preferable to produce by a solution polymerization method using a radical polymerization initiator.

The resin (B) component obtained in this manner has a high number of acrylic copolymer parts in view of excellent properties such as durability of a coating film formed using the composition of the present invention. The average molecular weight is from 1,000 to 30,000, especially 3
It is preferably from 000 to 25000. Furthermore, it is preferable to mix 20 to 250 parts by weight with respect to the component (A-1) from the viewpoint that physical properties such as durability of the coating film are excellent. When the amount is 20 parts by weight or less, the durability of the coating film deteriorates, and when the amount is 250 parts by weight or more, A and (A-1)
It is not preferable because the compatibility with the components is reduced.

In the composition of the present invention, in addition to the monomer species constituting the component (B-1), a polyester compound (e) containing a vinyl group is copolymerized for the purpose of improving pigment dispersibility. The resin (B-2) component obtained can be blended. Among monomers other than the monomer species constituting the component (B-1), the polyester compound (e) having a vinyl group is generally an alkyd type resin. By having a polymerizable unsaturated group, a resin having good compatibility with the vinyl copolymer (B) can be obtained by copolymerizing with another polymerizable unsaturated monomer. Further, from the viewpoint that the dispersion stability can be improved, it is preferable that the component (B-2) is copolymerized with the component (f) of the (meth) acrylamide-based compound. As the component (f), N, N-dimethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxy Methyl (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acryloylmorpholine, Aronix M-5700, AS-6 which is a macromonomer, AN-
6, AA-6, AB-6, AK-6 and the like (all manufactured by Toa Gosei Chemical Industry Co., Ltd.). Among them, N, N-dimethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, ( (Meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide and N-methyl (meth) acrylamide are preferred. Particularly, N, N-dimethyl (meth) acrylamide is more preferred.

The component (B-2) is preferably produced by the same method as the component (B-1).

The resin (B-2) component obtained in this manner is excellent in physical properties such as durability of a coating film formed by using the composition of the present invention. Has an average molecular weight of 1,000 to 30,000, particularly 3
It is preferably from 000 to 25000.

The resin (B-2) component as described above may be used alone or in combination of two or more.

Further, the composition of the present invention contains (A-
The polyfunctional isocyanate compound (C) component having two or more isocyanate groups as a crosslinking agent for the components (1), (B) and (E) is contained. Examples of the polyfunctional isocyanate compound (C) include aliphatic and aromatic compounds.

Specific examples of the aliphatic polyfunctional isocyanate compound include hexamethylene diisocyanate, dicyclohexylmethane 4,4'-isocyanate and 2,2,4-trimethyl-1 for curing at room temperature. , 6-hexamethylene diisocyanate and isophorone diisocyanate, and its structure includes a monomer, a buret type, a urezio type and an isocyanurate type.

As the aromatic polyfunctional isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4
'-Diisocyanate, xylene diisocyanate, polymethylene-polyphenylene-polyisocyanate, and the like. Also, there are a burette type, a urezio type and an isocyanurate type.

There is a block type for heat curing. Examples of the blocking agent include methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, methyl cellosolve, ethyl cellosolve,
Butyl cellosolve, benzyl alcohol, furfuryl alcohol, cyclohexyl alcohol, phenol, o
-Cresol, m-cresol, p-cresol, p-
tert-Butylphenol, thymol, p-nitrophenol, β-naphthol and the like. These isocyanate compounds can be used as they are, but if they are reacted with an alcohol component to form an allophanate type, the solubility for the component (C) can be further improved. This is preferable because there is an advantage that the appearance is improved during film formation.

These compounds can be used as a mixture of two or more kinds. The amount of the polyfunctional isocyanate compound (C) used is 0.7 to 0.7% in NCO / OH ratio.
2.0, preferably at a ratio of 0.8 to 1.5. When the component (C) is smaller than 0.7, the curability of the obtained composition is lowered. When the component exceeds 2.0, unreacted isocyanate is added to the coating film obtained using the composition. In addition to the fact that the compound or isocyanate group remains, which causes the occurrence of blemishes at the time of recoating, the contact angle of the coating film surface with water is hardly reduced, which adversely affects the improvement of stain resistance.

As the solvent used in the solution polymerization method, the component (D) is essential. Here, the weak solvent is a third type organic solvent of the Industrial Safety and Health Act and a solvent corresponding to the third type organic solvent. For example, Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.) containing 100% of aromatic hydrocarbons may be mentioned. In addition, those containing an aliphatic hydrocarbon as the component (C) are preferable. Specifically, a non-aqueous solvent having an aromatic content of 50% or less can be mentioned. A Solvent (manufactured by Nippon Oil Co., Ltd.), Exxon Naphtha No. 6 (manufactured by Exxon Chemical Co., Ltd.), Laws (Shell Chemical Co., Ltd.)
Exxon Naphtha No. Exxonnaphtha No. 5
3 (manufactured by Exxon Chemical Co., Ltd.), Isopar-E, Isopar-G (manufactured by Nippon Oil Co., Ltd.), IP Solvent 1620,
IP Solvent 2028 (made by Idemitsu Oil Co., Ltd.), Exol D40, Exol D80 (Exxon Chemical Co., Ltd.)
Manufactured).

In the solution polymerization, if necessary, for example, N-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, (CH ₃ O) ₃ Si-S-S-S-S
i (OCH ₃ ) ₃ , (CH ₃ O) ₃ Si—S ₈ —Si (OC
The molecular weight of the obtained resin (B) component may be adjusted by using a chain transfer agent such as H ₃ ) ₃ alone or in combination of two or more kinds. In particular, when a chain transfer agent having an alkoxysilyl group such as γ-mercaptopropyltrimethoxysilane in the molecule is used, a silyl group bonded to a hydrolyzable group is introduced into the terminal of the resin (B) component. This is preferable because The amount of the chain transfer agent to be used is from 0.05 to 10%, especially from 0.1 to 10% of the total amount of the polymerization components used.
Preferably, it is 8%.

As described above, the weak solvent (D) component in the composition of the present invention can be used at the time of polymerization of the component (B), and can also be used for diluting the resin composition for a top coating composition. Can be. There is no particular limitation on the amount used,
At the time of dilution, it can be adjusted appropriately.

In the present invention, general formula (1):

[0065]

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(Where R¹Is an alkyl having 1 to 10 carbons
Group, an aryl group having 6 to 10 carbon atoms and 7 to 10 carbon atoms
A monovalent hydrocarbon group selected from aralkyl groups of^TwoIs
C1-C10 alkyl group, C6-C10 aryl
And aralkyl groups having 7 to 10 carbon atoms
A monovalent hydrocarbon group, a represents 0 or 1)
Silicon compound and / or silicon compound
Compound hydrolyzed under acidic conditions in coal solvent
(E) Component 0 to 200 parts by weight (hereinafter referred to as silicon compound)
Partially hydrolyzed condensate (referred to as component (E)) is used.
(E) Ingredient further improves contamination resistance
Can be done. In the general formula (1), R¹
Has 1 to 10 carbon atoms, preferably, for example, a methyl group,
Group, n-propyl group, i-propyl group, n-butyl
Group, an alkyl group having 1 to 4 carbon atoms such as i-butyl group,
Aryl group having 6 to 10 primes, aralkyl having 7 to 10 carbons
Group, preferably having 6 to 6 carbon atoms such as a phenyl group.
9 to 9 carbon atoms such as an aryl group and a benzyl group;
It is a monovalent hydrocarbon group selected from aralkyl groups. Previous
When the alkyl group has more than 10 carbon atoms,
Low reactivity of the component (E)
It comes down. Also, R ¹Is the alkyl group, ant
Reactivity also decreases in cases other than phenolic and aralkyl groups
Become like

In the general formula (1), R ² is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an araryl group having 7 to 10 carbon atoms, preferably R ¹
Is a monovalent hydrocarbon selected from the same aralkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 9 carbon atoms, and aralkyl groups having 7 to 9 carbon atoms. In the general formula (1),
(R ¹ O) _4-a is selected such that 4-a becomes 3 or more, that is, a becomes 0 to 1, but the curability of a coating film formed from the composition of the present invention is improved. In terms of doing
a is preferably 0. When the number of (R ¹ O) _4-a present in the general formula (1) is plural, they may be the same or different.

Specific examples of the silicon compound (E) include, for example, tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate, tetra i-butyl silicate and the like. Tetraalkyl silicate; methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, E
SI28, methyltrisec-octyloxysilane,
Examples thereof include silane coupling agents such as methyltriphenoxysilane, methyltriisopropoxysilane, and methyltributoxysilane.

Specific examples of the partially hydrolyzed condensate (E) of the silicon compound (E) include, for example, water added to the above tetraalkylsilicate or trialkoxysilane by a conventional method to condense. Such as MSI51, ESI40, ES
I48, EMCi48 (30/70), ESi48 (5
0/50) ESi48 (75/25) (all manufactured by Colcoat Co., Ltd.), MS51, MS56, MS56S (all manufactured by Mitsubishi Chemical Corporation), M silicate 51, FR-
3, silicate 40, silicate 45, silicate 4
8. Partial hydrolysis and condensate of tetraalkoxysilane such as ES-48 (manufactured by Tama Chemical Co., Ltd.) and partial hydrolysis of trialkoxysilane such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) And condensates. Among the partially hydrolyzed condensates of the silicon compound of the component (E), the present invention is characterized in that it exhibits appropriate compatibility with the resin (A-1) and the component (B) to exhibit stain resistance. MSI51, MS51, MS5 from the viewpoint that the curability of the composition is good and that the hardness of the coating film formed using the composition is increased to control the adhesion of contaminants.
6. Part of tetraalkoxysilane such as MS56S (partially hydrolyzed condensate of tetramethoxysilane), ESI48, HAS-1 (partially hydrolyzed condensate of tetraethoxysilane) FR-3 (methoxy-ethoxy composite type silicate) It is preferable to use a hydrolyzed condensate, especially MS56S having a weight average molecular weight of more than 1000,
Compounds such as FR-3 and ESI48 are more preferred because they can reduce the compounding amount. The component (E) such as the silicon compound may be used alone or in combination of two or more. The partially hydrolyzed condensate of the silicon compound as the component (E) is also obtained by subjecting the silicon compound and / or the partially hydrolyzed condensate of the silicon compound to an alcohol-based solvent.
It can also be obtained by hydrolysis under acidic conditions. Specific examples include HAS-1 and HAS-10 (all manufactured by Colcoat Co., Ltd.). In addition, as said alcoholic solvent, methanol, ethanol, isopropanol, n-butanol, isobutyl alcohol, etc. are mentioned, for example.

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 acidic condition means (1) adding an acidic substance,
(2) Refers to conditions for treating with a cation exchange resin. (1) The acidic substance is an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and sulfurous acid; a phosphate ester such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, dioctyl phosphate, and didecyl phosphate; Carboxylic acid compounds such as formic acid, acetic acid, maleic acid, adipic acid, oxalic acid, and succinic acid; sulfonic acid compounds such as dodecylbenzenesulfonic acid, paratoluenesulfonic acid, 1-naphthalenesulfonic acid, and 2-naphthalenesulfonic acid; No. Among these, hydrochloric acid, nitric acid, sulfurous acid, and formic acid, which have relatively low boiling points, are preferable in that the acid is easily removed after the acid treatment. (2) Cation exchange resins include, for example, Amberlyst 15 (manufactured by Rohm and Haas), Duolite C
-433 (manufactured by Sumitomo Chemical Co., Ltd.). After the treatment with the cation exchange resin and water, it is preferable to remove the cation exchange resin by filtration, decantation, or the like.

The component (E) is used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the mixed component of (A-1) and (B).
0 parts by weight, preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight. When the use amount of the component (E) exceeds 200 parts by weight, the appearance such as the surface gloss of the coating film is reduced, and cracks and the like occur.

The component (E) is added to the component (B) at the time of polymerization of the component (B) in order to improve the compatibility between the component (B) and the component (E). (E)
The components can be hot blended.

An organometallic compound (F) is used as a curing catalyst to be blended with the components (A-1) and (B). Among them, tin compounds are preferred from the viewpoint of curability of the coating film. Further, a compound having an S atom in the molecule and an aluminum chelate compound are more preferable in consideration of storage stability and curing activity. Specific examples of the tin compound include dioctyltin bis (2-ethylhexyl maleate).
G), dioctyltin oxide or a condensate of dibutyltin oxide and silicate, dibutyltin dioctoate
, Dibutyltin dilaurate, dibutyltin distearate
Dibutyltin diacetylacetonate, dibutyltin bis (ethyl maleate), dibutyl tin bis (butyl maleate)
G), dibutyltin bis (2-ethylhexyl maleate)
G), dibutyltin bis (oleyl maleate), stanna octoate, tin stearate, and di-n-butyltin rallate oxide. Examples of the tin compound having an S atom in the molecule include dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, Examples thereof include dibutyltin bisisooctylthioglucolate, dioctyltin bisisooctylthioglucolate, and octylbutyltin bisisooctylthioglucolate.
Among the tin compounds, compounds having an S atom in the molecule are preferred because of good storage stability and pot life when isocyanate is blended, and particularly preferred is dibutyltin bisisononyl-3-mercaptopropionate. Onet
And dibutyltin bisisooctylthioglucolate are preferred from the viewpoint of the balance between curability, storage stability and pot life.

The above-mentioned aluminum chelate compounds are also preferable, and examples thereof include ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetonate), and alkyl acetyl acetate aluminum diisopropylate.

As the aluminum chelate compound, when aluminum tris (ethyl acetoacetate) and aluminum tris (acetyl acetonate) are blended with isocyanate, the balance between storage stability and pot life is good, This is preferable because the angle becomes smaller.

The organometallic compound (F) component may be used alone or in combination of two or more.

The amount of component (F) used is 0.1 to 3 parts by weight per 100 parts by weight of the mixed component of (A-1) and (B).
0 parts by weight, preferably 1.2 to 13 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 0.5 to 5 parts by weight.
Parts by weight. Further, when the amount of the organometallic compound (F) exceeds 30 parts by weight, a coating film formed using the composition tends to decrease in appearance such as surface gloss, which is not preferable.

The compounded monofunctional isocyanate compound (G) is mixed to remove water from the curing agent. Specific examples thereof include isocyanic acid and methyl isocyanate.
G, ethyl isocyanate, isopropyl isocyanate
G, hexyl isocyanate, vinyl isocyanate,
Isopropenyl isocyanate, phenyl isocyanate
G, tolyl isocyanate, nitrophenyl isocyanate, naphthyl isocyanate, tosyl isocyanate
Hexyl isocyanate, tolyl isocyanate and tosyl isocyanate are preferred from the viewpoint of dehydration ability and stability of the compound itself. Among them, tosyl isocyanate is particularly preferred from the viewpoint of the durability of the dehydration effect. These can be used alone or in combination of two or more. Thereby, the curing agent is dehydrated, and the storage stability when the polyisocyanate, the organometallic compound, and the monofunctional isocyanate compound are mixed is remarkably improved. The amount of the monofunctional isocyanate compound (G) is 0.1 to 100 parts by weight. From the viewpoint of the dehydration effect and the maintenance of curability, 0.1 to 50 parts by weight is preferable, and 0.5 to
20 parts by weight are more preferred.

The curable resin composition for paints of the present invention comprises a polyol NAD (A-1) component, a vinyl copolymer (B) component containing a silyl group bonded to a hydrolyzable group, an isocyanate compound The (C) component, the weak solvent (D) component, the partially hydrolyzed condensate (E) component of the silicon compound, the organometallic compound (F) component, and the monofunctional isocyanate (G) component are mixed using, for example, a stirrer. The resin (A-1) and the component (B) and the component (E) such as a silicon compound may be further mixed with a dehydrating agent. Thereby, the storage stability of the composition can be improved over a long period of time.

Specific examples of the dehydrating agent include, 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, trimethyl orthoisobutyrate, triethyl orthoisobutyrate; or , Dimethoxymethane,
1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane; or ethyl silicate (tetramethoxysilane), methyl silicate (tetramethoxysilane), methyltrimethoxysilane, 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 dehydrating agent is used in an amount of not more than 200 parts by weight, preferably not more than 100 parts by weight, more preferably not more than 50 parts by weight, based on 100 parts by weight of the total of the components (A-1) and (B) and the component (E). Used in:

The resin (B) component may be added to the component before the polymerization, may be added during the polymerization of the resin (B) component, or the obtained resin (B) component and (A- 1) It may be added at the time of mixing with the component, and there is no particular limitation. However, after the component (E), a silicon compound or a partially hydrolyzed condensate of the silicon compound, is hydrolyzed in an alcoholic solvent under acidic conditions. It is preferable to keep it.

The curable resin composition for paints of the present invention contains a pigment (H) component usually used in paints, for example, titanium oxide, ultramarine, navy blue, zinc white, red bengal, graphite, lead white, and carbon black. Pigments such as inorganic pigments such as transparent iron oxide and aluminum powder, organic pigments such as azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments; diluents, ultraviolet absorbers, and light stabilizers Additives such as agents, anti-sagging agents, leveling agents; fibrous materials such as nitrocellulose and cellulose acetate butyrate; epoxy resins, melamine resins, vinyl chloride resins, fluororesins, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, and polysiloxane And the like may be appropriately added.

The curable resin composition for a coating material of the present invention is applied to an object to be coated by a usual method such as immersion, spraying, application using a brush or the like, and usually at room temperature or at 30 ° C. or more. Bake and cure. The curable resin composition for paints of the present invention is, for example, metal, ceramics, glass, cement, mortar, ceramic moldings,
It is suitably used as a top coating for buildings such as plastics, woods, papers, fibers, and iron parts, home appliances, and industrial equipment. Further, the inorganic base material is used as a top coat after applying a microelastic reactive undercoat.

[0085]

Next, the curable resin composition for paints of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Synthesis Example of Vinyl Copolymer Resin (B) Component Solvent (1) was charged into a reactor equipped with a stirrer, a thermometer, a cooling reflux unit, a nitrogen gas inlet tube and a dropping funnel. After the temperature was raised to 110 ° C. while introducing gas, the vinyl monomer composition was dropped at a constant speed from the dropping funnel over 5 hours. Next, the solvent (2) was dropped into the reaction vessel at a constant speed over 1 hour. Thereafter, the mixture was continuously stirred at 110 ° C. for 2 hours, and then cooled to room temperature. Finally, the solvent (3) was added thereto and stirred to obtain a silyl group-containing acrylic copolymer (B) component bonded to a hydroxyl group and a hydrolyzable group. The solvents (1), (2), (3) and the vinyl monomer composition are described in Table 1.

[0087]

[Table 1]

The solid content concentration and the number average molecular weight of the obtained thermosetting resin composition at room temperature were measured by gel permeation chromatography (GPC) and are shown in Table 1.

A) Production of Top Coating Paint Hydroxyl group-containing acrylic resin (A-1-1-3), vinyl copolymer containing a silyl group bonded to a hydrolyzable group (B-1-1-4, B-1-1) -2-1-2), polyfunctional isocyanate compound (C), solvent (D), silicate compound (E), organometallic compound (F), and monofunctional isocyanate compound (G) are shown in Table 2. It was compounded by such a method. Examples AR1 to 7 A leveling agent (Kusumoto Kasei Co., Ltd., Dispalon L-1) was added to 100 parts by weight of the resin solids compounded in accordance with the composition shown in Table 2.
984-50), 0.4 parts by weight of an ultraviolet absorber (Tinuvin 384 manufactured by Ciba-Geigy) and 1 part by weight of light stabilizer (Tinuvin 123 manufactured by Ciba-Geigy) were added to obtain a top coat. Examples AR8-13 According to the formulations shown in Table 2, coating compositions were obtained in the following manner.

Resin (A-1) component in Table 2, (B)
Add titanium oxide to the component, silicate compound (E),
The mixture was dispersed in a paint conditioner for 2 hours using a glass bead to obtain a white enamel having a solid content of 60%.
Further, a mixed component 1 of the resin (A-1) component and the component (B)
The polyfunctional isocyanate compound (C), the organometallic compound (F), and the monofunctional isocyanate compound (G) were mixed in advance in amounts of 00 parts by weight and added in advance. . Further, the solvent (D) was added and the mixture was stirred for 5 minutes using a stirrer to obtain a composition having a solid concentration of 45%. (For detailed paint composition and dilution amount, see Table 2
Shown in ) The composition was applied to a glass plate by air spray and cured at 23 ° C for 7 days to obtain a coating film. As a comparative example, as shown in Table 2, a resin obtained from a composite coating film having a urethane bond was used to obtain an overcoat according to the composition shown in Table 2. The details of the paint are shown below.

Details of Ingredients in Paints Polyfunctional Isocyanate Compound (C) ● Duranate TSA-100 (Allophanate-modified type, manufactured by Asahi Kasei Co.) ● Duranate TSS-100 (Allophanate-modified, Asahi Kasei Co., Ltd.) Type) ☆ Organic solvent (D) ● Solvesso 100 (manufactured by Exxon Chemical) ● Naphtha No. 6 (Exxon Chemical Co., Ltd.) ☆ Silicate compound (E) ● FR-3; Methoxy-ethoxy composite type silicate compound (Tama Chemical Co., Ltd.) ● ESi48; Ethoxy type silicate compound (Corcot, Inc.) ) ● EMSi48 (75/25); Methoxy-ethoxy composite type silicate compound (manufactured by Corcot) ☆ Organometallic compound-based compound (F) ● F-1: Dibutyltin bisbutylmaleate ● F-2: Dibutyltin Bisisononyl-3-mercaptopropionate ● F-3; dibutyltin bisisooctylthioglycolate

[0092]

[Table 2]

In Table 2, (* 1) A-1-1 is U-3501A (manufactured by Nippon Carbide Industry Co., Ltd.) as a polyol NAD component. (* 2) A-1-2 represents U as a polyol NAD component.
-3508A (manufactured by Nippon Carbide Industry Co., Ltd.). (* 3) A-1-3 is a pigment dispersing resin for polyol NAD KP-1788A (manufactured by Nippon Carbide Industry Co., Ltd.)
It is. (* 4) CR-95 is manufactured by Ishihara Sangyo Co., Ltd.

[0094]

[Table 3]

The physical properties of the coating film formed using the obtained coating composition were evaluated according to the following methods.

The obtained composition was directly applied to various substrates such as steel plate, untreated aluminum plate (A5052P), SUS304, steel plate, mortar, and glass plate. In addition, a fine elastic filler undercoat (soft surf; manufactured by SK Kaken Co., Ltd.) was applied on the slate plate with 1 day 1 coat as an overcoat.

The overcoat was applied to a dry film thickness of 20 to 30 μm to obtain a sample. The adhesiveness of each substrate and the overcoating were self-recovered on the first day, the second day, the third day, the sixth day, the tenth day, and the 14th day, and it was confirmed that the coating film was free of any dirt.

Further, a weak solvent type epoxy primer (Epol Mild; manufactured by Dainippon Paint) and then a weak solvent epoxy intermediate coating (V Top H middle coated Mild; manufactured by Dainippon Paint) were applied to the steel sheet at a dry film thickness. Dry film thickness of 1 day 1 coat on the one coated to 40 to 60 μm
A sample was prepared by painting to a thickness of 0 to 30 μm. The sample was scratched to reach the substrate with a cutter, and after 1 day, 2 days, 3 days, 6 days, 10 days, and 14 days after the top coating, the weak solvent epoxy primer and weak solvent epoxy The coating was applied, and the state of the coating film in each period was observed, and it was confirmed that there was no spot or the like. Surface condition of the obtained coating film, gloss, stain resistance, weather resistance, contact angle, adhesion, intermediate coating
The deterioration at low temperatures and the low-temperature curability of the coating film were evaluated according to the following methods. A) Surface condition The coating film surface was visually observed and evaluated based on the following evaluation criteria. (Evaluation criteria) ：: No cracks were observed at all, and the surface condition was good. B) Gloss The gloss of the coating film surface should be GM according to JIS K 5400.
It measured using the 268 gloss meter (made by Minolta). (20
/ 60 ° gloss) c) Stain resistance (ΔL value) CR-300 color difference meter (Minolta) The difference (ΔL value) from the L value before exposure was determined from the obtained L value (brightness). D) Weather resistance (gloss retention) Using a sunshine weatherometer, the gloss of the coating surface immediately after formation and the gloss of the coating surface after 2,000 hours were measured, and the gloss retention (%) after 2,000 hours had elapsed. ). E) Contact angle The static contact angle of the coating film surface with water immediately after formation was measured with a contact angle measuring device (CA-S150, manufactured by Kyowa Interface Science Co., Ltd.). F) Adhesion The coated sample prepared above was subjected to room temperature (23 ° C, humidity 55).
%), The adhesiveness after curing for 14 days was evaluated by measuring the cross-cut adhesiveness at 2-point intervals by a 10-point method in accordance with JIS K 5400.

0 means that the area of the peeling is 6
5% or more.

In No. 6, both sides of the cut and the intersection are peeled off, and the area of the defect is 5 to 15% of the area of the entire square.

In No. 8, there is a slight peeling off from the intersection of the cuts, no peeling off at a glance, and the area of the defect is within 5% of the area of the entire square. 10 is cut 1
Each book is thin and smooth on both sides, indicating that there is no separation at the intersection of the cut and the square at a glance. G) Dust during self-recoating Dust during topcoat, weak solvent epoxy primer, and weak solvent epoxy intermediate coating was evaluated according to the following criteria. (Evaluation criteria) ；: No abnormality is observed in the coating film. Δ: Bleeding occurs only in the cut portion. ×: Spots occurred on the entire surface of the recoat portion. H) Low-temperature curability (gel fraction) The obtained coating composition was applied on a tin pad, and a free film having a thickness of about 40 μm obtained at 5 ° C. × 1 day and a thickness of about 50 × was obtained.
It was cut into a size of 50 mm, wrapped in 200 mesh stainless steel metal (W0) that had been precisely weighed in advance, and weighed precisely (W
1) Thereafter, the sample was immersed in acetone for 24 hours to perform extraction, then dried and precisely weighed (W2), and the following formula: gel fraction (%) = [(W2-W0) / (W1-W0)] ×
The gel fraction (%) was determined based on 100.

Tables 2 and 3 show the evaluation results of the coating film properties. As shown in Table 2, the coating resin obtained from the vinyl copolymer (B) containing a silyl group bonded to a hydrolyzable group in the hydroxyl group-containing acrylic resin (A) component was mixed with a silicate compound. The compatibility was good, the measured contact angle also showed good hydrophilicity, and it was found that the stain resistance was excellent. Furthermore, by blending the component (B), the weather resistance and the low-temperature curability (gel fraction) could be improved.

As shown in Table 3, the coating resin obtained from the vinyl copolymer (B) containing a silyl group bonded to a hydrolyzable group in the hydroxyl group-containing acrylic resin (A) component has a hydroxyl group Compared to the acrylic resin (A) component alone, it shows good adhesion to untreated aluminum plate, SUS304, steel plate, mortar, and glass plate, for which it is usually difficult to secure adhesion. In addition, good results were obtained with no blemishes at the time of self-recoating on the microelastic filler, and at the time of repairing with a weak solvent type epoxy primer or intermediate coating.

EFFECTS OF THE INVENTION The curable resin composition for a topcoat paint of the present invention has the disadvantages of weather resistance, stain resistance, adhesion to various substrates and self-recoat without impairing the excellent properties of acrylic urethane paint. The repairability with other paints was greatly improved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J027 AB01 BA02 BA05 BA07 BA08 BA10 BA11 BA12 BA14 CD08 4J034 DA01 DP02 DP03 DP06 DP18 HA04 HA07 HA13 MA22 RA07 4J038 DG181 DG191 DG251 DG271 DG281 DG291 DG301 GA03 GA06 GA09 GA03 JA01 JC38 JC41 KA04 KA06 KA08 MA14 NA03 NA05 NA12 NA23 NA24 4J100 AB02R AB07Q AE10Q AG08P AL03R AL08P AL08R AL09Q AM21Q AP16P BA02P BA03P BA03Q BA11P BA15P BA28P BA38P BA75P BA77P BA81P BC04R BC43 BC01

Claims (15)

[Claims] 1. A hydroxyl group-containing acrylic resin (A) component, a vinyl copolymer (B) component containing a silyl group bonded to a hydrolyzable group, a polyfunctional isocyanate compound (C) component, a weak solvent ( D) A curable resin composition for paints, which contains the component. 2. The hydroxyl-containing acrylic resin (A) component has a weight average molecular weight of 5,000 to 80,000 and a hydroxyl value of 20.
-100 (KOHmg / g), acid value 0.1-30 (K
OH mg / g). 3. The method according to claim 1, wherein the hydroxyl group-containing acrylic resin (A) is
The curable resin composition for a paint according to claim 1 or 2, comprising an AD type polyol dispersion (A-1) component. 4. The composition according to claim 1, wherein the component (B) is blended in an amount of 20 to 250 parts by weight based on 100 parts by weight of the component (A).
3. The curable resin composition for coating according to item 3. 5. Component (B) is (a) a vinyl monomer containing a silyl group bonded to a hydrolyzable group, (b) a vinyl monomer containing a hydroxyl group, (c) other copolymers. The curable resin composition for paint according to any one of claims 1 to 4, which is a vinyl copolymer (B-1) obtained by copolymerizing a possible monomer. 6. The curable composition according to claim 5, wherein said (c) other copolymerizable monomer contains (d) an alkyl (meth) acrylate having 5 or more carbon atoms. Resin composition. 7. A polyester compound (e) containing a vinyl group in addition to the monomer constituting the vinyl copolymer (B-1) is copolymerized with the composition (B). The curable resin composition for a paint according to any one of claims 1 to 6, further comprising a resin (B-2) component. 8. The curable resin for paints according to claim 1, wherein the component (B-2) is further copolymerized with a (meth) acrylic amide compound (f). Composition. 9. The curable resin composition for a paint according to claim 1, wherein the weak solvent (D) component contains an aliphatic hydrocarbon. 10. The compound of the general formula (1) (Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms)
Monovalent hydrocarbon group selected from aryl and aralkyl group having 7 to 10 carbon atoms to 10, R ² is a carbon number 1 to 1
A represents 0 or 1; a monovalent hydrocarbon group selected from an alkyl group having 0, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; The curable resin composition for a paint according to any one of claims 1 to 9, which comprises a silicon compound represented by the formula (1) or a partial hydrolysis condensate (E) thereof. 11. A curable resin composition for coatings, further comprising an organometallic compound (F) component.
The curable resin composition for a paint according to any one of the above. 12. The curable resin composition for paints according to claim 1, further comprising a monofunctional isocyanate compound (G) added to the curable resin composition for paints. 13. The component (F) is used in an amount of 0.1 to 3 based on 100 parts by weight of the mixture of the component (A-1) and the component (B).
The curable resin composition for a paint according to any one of claims 1 to 12, wherein 0 parts by weight and 0.1 to 100 parts by weight of the component (G) are blended. 14. The curable resin composition for a paint according to claim 1, wherein a pigment (H) is blended with the composition. 15. A coated article obtained by applying the composition for a top coating composition according to claim 1.