JPH1121499A - Acrylic resin for paint, two-pack type acrylic urethane resin composition for paint and acrylic melamine resin composition for paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-pack type acrylic urethane resin composition for paint, an acrylic melamine resin composition for paint having improved weather resistance and having stain resistance, water resistance, chemical resistance and the like, and these Provide acrylic resin for paint used for SOLUTION: The acrylic resin for paint is a polymerizable ultraviolet absorber monomer (a), a vinyl monomer and / or (meth)
It is characterized by comprising an acrylic monomer (b) and a hydroxyl group-containing polymerizable monomer (c), wherein the polymerizable ultraviolet absorber monomer (a) is preferably 2- (2'-hydroxy-5'-methacryloxy). Ethylphenyl) -2H
-Benzotriazole. Further, the two-pack type acrylic urethane resin composition for paint contains the acrylic resin for paint and polyisocyanate, and the acrylic melamine resin composition for paint contains the acrylic resin for paint and amino resin.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION

The present invention relates to an acrylic resin for paint, a two-pack type acrylic urethane resin composition for paint containing the acrylic resin, and an acrylic melamine resin composition for paint, particularly containing a polymerizable ultraviolet absorber monomer. The present invention relates to an acrylic resin for paint, a two-pack type acrylic urethane resin composition for paint containing the acrylic resin, and an acrylic melamine resin composition for paint.

[0002]

2. Description of the Related Art Conventionally, acrylic urethane paints obtained by reacting an acrylic polyol and a polyisocyanate have been used as paints which can be cured at room temperature or low temperature, which require weather resistance. Urethane paints are excellent in drying property, solvent resistance, gloss and the like.
On the other hand, in recent years, from the viewpoint of resource saving and energy saving, there is a strong demand for a paint having higher weather resistance and requiring no maintenance of the coating film.

[0003] In response to such demands, attempts have been made to add an ultraviolet stabilizer or an ultraviolet absorber to an acrylic resin. This improves weather resistance to some extent, but in terms of long-term weather resistance, the problem that added UV stabilizers and UV absorbers fall off the surface of the coating film during outdoor exposure and lose their effects over time. There is.

Japanese Patent Publication No. 61-42751 proposes a method of copolymerizing a glycidyl (meth) acrylate adduct of a benzophenone derivative as a polymerizable ultraviolet absorber monomer. As a result, weather resistance is improved to some extent, but water resistance and chemical resistance are insufficient.

Japanese Patent Publication No. 7-8970 discloses a method of copolymerizing a polymerizable ultraviolet stabilizer monomer, and Japanese Patent Publication No. 7-49453 further discloses a benzophenone derivative glycidyl derivative as a polymerizable ultraviolet absorber monomer. A method of copolymerizing a (meth) acrylate adduct and a polymerizable ultraviolet stabilizer monomer has been proposed. However, in these methods, when the polymerizable ultraviolet stabilizer monomer is used in an amount sufficient to improve weather resistance, the viscosity of the copolymer is significantly increased, and the workability when formed into a coating is poor. There is.

Further, although acrylic silicone resins and solvent-soluble fluorinated resins have come to be used as resins for ultra-weather resistant paints, they have disadvantages such as poor pigment dispersibility and stain resistance.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the weather resistance to the same level as that of a fluororesin or a silicone resin, and at the same time to have a resistance to contamination, water and chemicals at normal or low temperatures. It is an object of the present invention to provide a two-pack type acrylic urethane resin composition for paint, which can be cured by the above, and an acrylic resin for paint used for the composition.

[0008] Another object of the present invention is to provide an acrylic melamine resin composition for paints which has improved weather resistance to the same level as fluororesins and silicone resins, and has stain resistance, water resistance and chemical resistance. To provide an acrylic resin for paint used in the above.

[0009]

The acrylic resin for coating according to claim 1 comprises a polymerizable ultraviolet absorbent monomer (a), a vinyl monomer and / or a (meth) acrylic monomer (b), a hydroxyl group-containing polymerizable monomer ( c).

[0010] In the acrylic resin for coating according to claim 2, the polymerizable ultraviolet absorbent monomer (a) is 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2.
H-benzotriazole.

The acrylic resin for paint according to claim 3 is the acrylic resin for paint according to claim 1 or 2, wherein the polymerizable ultraviolet absorber monomer (a) and the vinyl monomer and / or
Alternatively, in the polymerizable monomer component composed of the (meth) acrylic monomer (b) and the hydroxyl group-containing polymerizable monomer (c), the content of the polymerizable ultraviolet absorber monomer (a) is 0.1 to 1
It is characterized by being 0.0% by weight.

[0012] A two-pack type acrylic urethane resin composition for a coating according to a fourth aspect is characterized by containing the acrylic resin for a coating according to any one of the first to third aspects and a polyisocyanate.

[0013] The two-component acrylic urethane resin composition for a coating according to claim 5 is the two-component acrylic urethane resin composition for a coating according to the fourth aspect, wherein the acrylic resin for the coating and the polyisocyanate have a hydroxyl group / isocyanate group. Is contained at a ratio of 0.6 to 1.2 in terms of equivalent ratio.

[0014] The acrylic melamine resin composition for paint according to claim 6 is characterized by containing the acrylic resin for paint according to any one of claims 1 to 3 and an amino resin.

The acrylic melamine resin composition for paint according to claim 7 is the acrylic melamine resin composition for paint according to claim 6, wherein the acrylic resin for paint is 60 to 95% by weight and the amino resin is 5 to 45% by weight. It is characterized by being contained.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic resin for paint of the present invention comprises:
The polymerizable ultraviolet absorber monomer (a), vinyl monomer and / or (meth) acrylic monomer (b) and hydroxyl group-containing polymerizable monomer (c) are essential components.

Polymerizable UV absorber monomer component (a)
Is a compound having a benzotriazole group having an ultraviolet absorbing ability and an ethylenically unsaturated double bond in the same molecule.Therefore, an ultraviolet absorbing functional group is incorporated in an acrylic resin skeleton, and the conventional addition type ultraviolet absorbing The two-part acrylic urethane resin composition for paints and the acrylic melamine resin composition for paints of the present invention have sufficient weather resistance without falling off from the surface of the coating film during outdoor exposure as compared with the case where the agent is used. can do.

Such a polymerizable ultraviolet absorber monomer (a)
Is suitably used as long as its ultraviolet absorption wavelength region is wide. For example, benzotriazole-based 2-
(2'-Hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole can be used. The amount used is 0.1 to 10 in the polymerizable monomer component composed of the polymerizable ultraviolet absorber monomer (a), the vinyl monomer and / or the (meth) acrylic monomer (b), and the hydroxyl group-containing polymerizable monomer (c). 0.0% by weight, preferably 0.2 to 8.0% by weight. If the amount used is less than 0.1% by weight, the weather resistance, which is the object of the present invention, is insufficient. If it exceeds 10.0% by weight, it is economically disadvantageous, and the water resistance and chemical resistance of the coating film are low. Is reduced.

The effective absorption wavelength range differs depending on the type of the ultraviolet absorber, for example, benzotriazole 2- (2 ').
-Hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole have an effective absorption wavelength of 270 to 370 µm, whereas benzophenone-based Of 2,4-hydroxybenzophenone (described in JP-B-61-72751 and JP-B-7-49453) as a raw material of a polymerizable ultraviolet absorber monomer is 280 to 340 μm. Therefore, such an ultraviolet absorption wavelength region is large, for example, 2-
The acrylic resin for coatings of the present invention using (2'hydroxy-5'-methacryloxyethylphenyl) -2H-bendsolicazole exhibits an ultraviolet absorbing ability in a wider ultraviolet wavelength range than conventional ones. can do.

The vinyl monomer and / or (meth) acrylic monomer (b) used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate,
Tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and other alkyl (meth) acrylates; glycidyl (meth) acrylate and the like Epoxy group-containing (meth) acrylate; nitrogen-containing polymerizable monomers such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate; styrene, α-
Aromatic polymerizable monomers such as methylstyrene, vinyltoluene, and paramethylstyrene; vinyl esters such as vinyl acetate; polymerizable cyano compounds such as (meth) acrylonitrile; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, A carboxyl co-containing polymerizable monomer such as monoalkyl maleate and monoalkyl fumarate can be used, and one or more selected from these groups can be used. The amount used is 60.000 in the polymerizable monomer component consisting of the polymerizable ultraviolet absorber monomer (a), the vinyl monomer and / or the (meth) acrylic monomer (b), and the hydroxyl group-containing polymerizable monomer (c).
0 to 95.9% by weight, which is the balance of the polymerizable ultraviolet absorber monomer (a) and the hydroxyl group-containing polymerizable monomer (c).

Examples of the hydroxyl-containing polymerizable monomer (c) include, for example, hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate and the like can be used. The amount of the polymerizable ultraviolet absorber monomer (a)
And a vinyl monomer and / or a (meth) acrylic monomer (b) and a hydroxyl group-containing polymerizable monomer (c) in an amount of 4.0 to 30.0% by weight.
This is because in this range, a preferable hydroxyl value is obtained.

In order to improve the dispersibility of the pigment,
The acrylic resin for coating can be modified with an alkyd resin or a polyester resin having a functional group copolymerizable with the components (a) to (c) in the acrylic resin for coating.

The acrylic resin for coating used in the present invention has a hydroxyl value of 20 to 120, preferably 30 to 100. When mixed with polyisocyanate, the hydroxyl value is 2
If it is less than 0, the number of hydroxyl groups is too small, so that even if it is reacted with polyisocyanate, the crosslinking density becomes insufficient and the weather resistance and the solvent resistance deteriorate. If the hydroxyl value exceeds 120, the pot life when mixed with the polyisocyanate becomes short, which is a practical obstacle. In addition, when mixed with an amino resin, if the hydroxyl value is less than 20, the crosslinking density between the amino resin and the acrylic resin is low, and sufficient coating film performance cannot be obtained. Is reduced.

Further, the acrylic resin for paint preferably has an acid value of 1.0 to 15. When it is in this range, it can suitably act as an internal catalyst for accelerating the curing reaction with the polyisocyanate. If the acid value is too large, the pot life becomes short, which is not preferable. Further, it can suitably act as an internal catalyst for the curing reaction with the amino resin, and if the acid value is too large, the storage stability of the acrylic melamine resin composition for paints is reduced.

The acrylic resin for paint of the present invention is obtained by blending the polymerizable ultraviolet absorber monomer (a), vinyl monomer and / or (meth) acrylic monomer (b), and hydroxyl group-containing polymerizable monomer (c). The polymerizable monomer component can be obtained by polymerizing the polymerizable monomer component by a known method, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or the like.

The most suitable method is a solution polymerization method. Specifically, a solvent is charged into a reaction vessel, and a liquid obtained by previously mixing the polymerizable monomer component and the polymerization initiator is dropped at a constant rate while stirring. Or, or with the polymerizable monomer component,
The polymerization is carried out by simultaneously dropping the polymerization initiator and the polymerization initiator at a constant rate.

Solvents usable in this case include aromatic hydrocarbons such as toluene and xylene; acetates such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethylene glycol monomethyl ether acetate; Acetates of alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate can be used, and these organic solvents are used alone or as a mixed solvent.

In preparing the acrylic resin for coating used in the acrylic melamine resin composition for coating, in addition to the above-mentioned solvent, alcohols such as isopropanol, normal butanol, isobutanol; ethylene glycol monomethyl ether, ethylene glycol monoethylene; Alkylene glycol monoalkyl ethers such as ethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and diethylene glycol monoethyl ether can be used, and these organic solvents are used alone or as a mixed solvent.

As the polymerization initiator, a conventional radical polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tertiary butyl peroxybenzoate, etc. can be used. Is used in the range of 0.1 to 5% by weight based on the total weight of the polymerizable monomer component. Further, if necessary, a chain transfer agent such as lauryl mercaptan or 2-mercaptoethanol can be used.

The polymerization reaction temperature ranges from room temperature to 180 ° C., preferably 60 to 150 ° C., and the reaction is carried out by heating for 1 to 10 hours. This reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or in a gas stream. By such a solution polymerization method, usually 3,000 to 300,000, preferably 8,000 to 120,00
An acrylic copolymer resin having a weight average molecular weight of 0 is obtained.

The two-pack type acrylic urethane resin composition for paints of the present invention contains the acrylic resin for paints and polyisocyanate.

Examples of the polyisocyanate used in the two-pack acrylic urethane resin composition for paints of the present invention include hexamethylene diisocyanate, non-yellowing type isocyanate, isophorone diisocyanate, and 1,3-
Known ones such as bis (isocyanatomethyl) cyclohexane and dicyclohexylmethane-4,4'-diisocyanate can be used alone or in a mixture of two or more. Adducts, burettes and the like thereof can also be used.

The acrylic resin for coating and the polyisocyanate have a hydroxyl / isocyanate equivalent ratio of 0.1.
It is preferable to mix them so as to be 6 to 1.2. 0.
If it is less than 6, the unreacted polyisocyanate deteriorates the performance of the cured coating film, and the water resistance and mechanical properties decrease. If it exceeds 1.2, the crosslinking density decreases, and the water resistance and mechanical properties decrease. .

The acrylic resin for paint may be used, if necessary, with materials commonly used by those skilled in the art, for example, pigments such as organic solvents, organic pigments, inorganic coloring pigments and inorganic pigments, defoamers, dispersants, and leveling. Agents and additives such as antioxidants,
In addition, a curing catalyst such as an organic tin compound or a tertiary amine can be dispersed and mixed by a known method.

The acrylic melamine resin composition for a paint of the present invention contains the acrylic resin for a paint and an amino resin.

The amino resin used in the acrylic melamine resin composition for paints of the present invention includes methyletherified melamine resin, butyletherified melamine resin, methylbutyletherified melamine resin, butyletherified benzoguanamine resin, butyletherified cyclohexylbenzoguanamine resin, and the like. Species or a mixture of two or more can be used.

The acrylic resin for paint and the amino resin are preferably blended so that the acrylic resin for paint is 60 to 95% by weight and the amino resin is 5 to 40% by weight. If the amount is less than 5% by weight, the crosslinked density of the cured film is low, so that the weather resistance, solvent resistance and water resistance of the film become insufficient. Physical properties such as feel and impact resistance are reduced.

The acrylic resin for paint may contain, if necessary, materials commonly used by those skilled in the art, for example, pigments such as organic solvents, organic pigments, inorganic coloring pigments and inorganic extenders, defoamers,
Additives such as a dispersant, a leveling agent and an antioxidant, and a curing catalyst can be dispersed and mixed by a known method.
As the curing catalyst, an external acid catalyst such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, or an amine neutralized product thereof can be used.

The two-pack type urethane resin composition for paints and the acrylic melamine resin composition for paints of the present invention can be prepared by a known method. For example, a small amount of acrylic resin for paint and pigment are added in a sand mill. According to the above, an organic solvent is added, and a dispersion operation is performed by stirring until a desired particle size is obtained, and after preparing a seed enamel, the remaining acrylic resin for a coating material, an organic solvent, various additives as necessary, a curing catalyst, etc. Is added and mixed to prepare an enamel. Next, a polyisocyanate is added to the above enamel immediately before use, and the viscosity is adjusted with an organic solvent to obtain a two-pack type acrylic urethane resin composition for a paint of the present invention. In addition, an amino resin is mixed with the above enamel, and the viscosity is adjusted with an organic solvent to obtain the acrylic melamine resin composition for a paint of the present invention.

The two-pack type urethane resin composition for paints of the present invention can be prepared by various coating methods such as on-site coating such as spray coating, roll coating and brush coating, and factory coating such as roll coater coating and flow coater coating. After coating on metal, slate, roof tile, etc., a coating film excellent in gloss, weather resistance and water resistance can be formed through a room temperature curing process or a heating forced drying process.

The acrylic melamine resin composition for paints of the present invention is applied to wood, metal, slate, tile, etc. by factory coating such as spray coating, roll coater coating, flow coater coating and the like, and then subjected to a thermosetting process to obtain a luster. And a coating film having excellent weather resistance can be formed.

[0042]

The present invention will be described with reference to the following examples and comparative examples. Parts and% mean parts by weight and% by weight, respectively, unless otherwise specified.

Examples 1 to 5, 14 to 16, 18, 19,
21 A four-necked flask equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube was charged with toluene and butyl acetate solvent in the proportions shown in Table 1 at 110 to 120 ° C under a nitrogen gas stream.
Wherein methyl methacrylate, n-butyl methacrylate, ethyl acrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2- (2′-hydroxy-
A mixture of 5 'methacryloxyethylphenyl) -2H-benzotriazole, t-butylperoxyisopropyl carbonate and azobisisobutyronitrile was added dropwise to the solvent over 3 hours to carry out a polymerization reaction. Acrylic resin solutions for paints (1) to (5), (1)
4) to (16), (18), (19) and (21) were obtained. Table 1 shows the characteristic values of the obtained resin.

Next, titanium oxide and xylene as pigments were blended in the obtained acrylic resin solution for paint in the ratio shown in Table 2, 200 g of alumina beads were added, and the mixture was shaken with a paint conditioner for 1.5 hours. After confirming that the average particle size of the titanium oxide was 10 μm or less by using a tub gauge, the alumina beads were taken out, an acrylic resin for coating and xylene were added, and the mixture was further shaken for 20 minutes to prepare an enamel.

Next, as shown in Table 3, the obtained enamel was mixed with an isocyanate so that the equivalent ratio of OH / NCO became a predetermined value, and the viscosity was adjusted to Ford cup # 4.
Add xylene so that it becomes about 13.5 to 15 seconds,
In each case, a two-pack type acrylic urethane resin composition for a paint of the present invention was obtained.

Examples 17 and 20 The present invention was carried out in accordance with Tables 2 and 3, except that acrylic resin solutions (17) and (20) for paints of the present invention were obtained by further using styrene at the compounding ratios shown in Table 1. To obtain a two-component acrylic urethane resin composition for paint.

Examples 6 to 13, 19 to 21 Acrylic resins for coatings (6) to (1) at the compounding ratios shown in Table 1.
3), (19) to (21) were synthesized, and then enamels were prepared according to Example 1 at the mixing ratios shown in Table 2. Next, as shown in Table 4, the obtained enamel was mixed with a melamine resin and an acid catalyst, and xylene was added to adjust the viscosity so that bar coater coating was possible. A melamine resin composition was obtained.

COMPARATIVE EXAMPLE 1 A polymerizable ultraviolet absorber monomer, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-
A two-pack type acrylic urethane resin composition for a paint was obtained in the same manner as in Example 1 except that benzotriazole was not contained and according to the compounding ratios shown in Tables 1 to 3.

Comparative Example 2 Polymerizable ultraviolet absorber monomer 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-
A polymerizable UV stabilizer monomer of 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate was used in place of benzotriazole, and the paint was applied in accordance with the mixing ratio shown in Tables 1 to 3 according to Example 1. An acrylic urethane resin composition for use was obtained.

Comparative Examples 3 and 4 The polymerizable UV absorber monomer 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-
TINUVIN 1130 instead of benzotriazole
An acrylic urethane resin composition for a paint was obtained according to Example 1 using (additional ultraviolet absorber manufactured by Ciba-Geigy) in accordance with the ratios shown in Tables 1 to 3.

Comparative Example 5 Polymerizable UV absorber monomer 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-
Benzotriazole was contained at 0.05% by weight.
An acrylic urethane resin composition for a paint was obtained according to the mixing ratio shown in Example 3 and according to Example 1.

Comparative Example 11 A polymerizable ultraviolet absorber monomer, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-
A two-pack acrylic urethane resin composition for a paint was obtained in the same manner as in Example 17, except that benzotriazole was not contained, and according to the compounding ratios shown in Tables 1 to 3.

Comparative Examples 6 to 10, 12 According to Tables 1, 2 and 4, an acrylic melamine resin composition for paint was obtained according to Example 6.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

Test Example Bond type 144-treated mild steel plate and gypsum board were used as a base material of a two-pack type acrylic urethane resin composition for a paint, and a primer was previously applied with a commercially available epoxy primer. Next, after spraying each base material with the two-pack type acrylic urethane resin composition for paints obtained in Examples 1 to 5, 14 to 21 and Comparative Examples 1 to 5, 11 at 80 ° C.
After drying for 20 minutes and aging for 7 days, each test plate was subjected to the following test.

The base material of the acrylic melamine resin composition for paints was a mild steel sheet treated with Bonde # 144, which was previously primed with a commercially available epoxy primer. Then, Examples 6-13, 19-21 and Comparative Examples 6-10, 1
The acrylic melamine resin composition for coating obtained in 2 was coated with a bar coater so that the film thickness became 20 to 25 μm, and after setting for 5 minutes, baking was performed at 140 ° C. for 20 minutes, and each test plate was Was subjected to the following test.

Pencil hardness: Tested with Mitsubishi Pencil Uni, and shows maximum hardness without damage. Acid resistance: A test plate for a two-pack acrylic urethane resin composition for paint was dipped in a 5% hydrochloric acid aqueous solution for 14 days, and a test plate for an acrylic melamine resin composition for paint was dipped for 7 days, and the state of the coating film was visually observed. I do. Alkali resistance: One test plate for a two-pack type acrylic urethane resin composition for paint was placed in a 5% aqueous sodium hydroxide solution.
On the 4th, the test plate relating to the acrylic melamine resin composition for a paint was immersed for 7 days, and the state of the coating film was visually observed. Water resistance: Each test plate is immersed in water at 20 ° C. for 14 days, and the state of the coating film is visually observed. Accelerated weathering test: Each test plate was irradiated with ultraviolet light 6 using a QUV accelerated weathering tester (ATLAS-UVCON).
After exposure for a predetermined time under a cycle condition of 0 ° C. × 4 hours + condensation at 40 ° C. × 4 hours, 60 ° gloss was measured. The results are shown in Table 5 for the two-component acrylic urethane resin composition for paints, and Table 6 for the acrylic melamine resin composition for paints.

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

The two-component acrylic urethane resin composition for paints of the present invention obtained by using the acrylic resin for paints of the present invention has excellent weather resistance, balance of stain resistance, water resistance and chemical resistance. A cured coating film that can be cured at room temperature or can be forcedly dried by heating can be provided.

The acrylic melamine resin composition for paints of the present invention obtained by using the acrylic resin for paints of the present invention has excellent weather resistance, and has a good balance between stain resistance, water resistance and chemical resistance. A membrane can be applied.

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[Procedure amendment]

[Submission date] July 18, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to improve the weather resistance to the same level as that of a fluororesin or a silicone resin, and to provide a room temperature curing or stain resistant film having water resistance and chemical resistance. An object of the present invention is to provide a two-pack type acrylic urethane resin composition for paint that can be forcibly dried by heating and an acrylic resin for paint used in the composition.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

The vinyl monomer and / or (meth) acrylic monomer (b) used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate,
Tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and other alkyl (meth) acrylates; glycidyl (meth) acrylate and the like Epoxy group-containing (meth) acrylate; nitrogen-containing polymerizable monomers such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate; styrene, α-
Aromatic polymerizable monomers such as methylstyrene, vinyltoluene, and paramethylstyrene; vinyl esters such as vinyl acetate; polymerizable cyano compounds such as (meth) acrylonitrile; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, Carboxyl group-containing polymerizable monomers such as monoalkyl maleate and monoalkyl fumarate can be used, and one or more selected from these groups can be used. The amount used is 60.000 in the polymerizable monomer component consisting of the polymerizable ultraviolet absorber monomer (a), the vinyl monomer and / or the (meth) acrylic monomer (b), and the hydroxyl group-containing polymerizable monomer (c).
0 to 95.9% by weight, which is the balance of the polymerizable ultraviolet absorber monomer (a) and the hydroxyl group-containing polymerizable monomer (c).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

Examples 1 to 5, 14 to 16, 18, 19,
21 A four-necked flask equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube was charged with toluene and butyl acetate solvent in the proportions shown in Table 1 at 110 to 120 ° C under a nitrogen gas stream.
Wherein methyl methacrylate, n-butyl methacrylate, ethyl acrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2- (2′-hydroxy-
5'-methacryloxyethylphenyl) -2H-benzotriazole, t-butylperoxyisopropyl carbonate and azobisisobutyronitrile
The polymerization reaction was carried out by dropping into the solvent over time, and the acrylic resin solutions (1) to (5), (1)
4) to (16), (18), (19) and (21) were obtained. Table 1 shows the characteristic values of the obtained resin.

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Claims (7)

[Claims] 1. An acrylic resin for a paint, comprising a polymerizable ultraviolet absorber monomer (a), a vinyl monomer and / or a (meth) acrylic monomer (b), and a hydroxyl group-containing polymerizable monomer (c). . 2. A polymerizable ultraviolet absorber monomer (a) comprising 2
The acrylic resin for paints according to claim 1, wherein the acrylic resin is-(2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. 3. A polymerizable ultraviolet absorber in a polymerizable monomer component comprising a polymerizable ultraviolet absorber monomer (a), a vinyl monomer and / or a (meth) acrylic monomer (b), and a hydroxyl group-containing polymerizable monomer (c). The acrylic resin for paint according to claim 1 or 2, wherein the content of the agent monomer (a) is 0.1 to 10.0% by weight. 4. A two-pack acrylic urethane resin composition for paints, comprising the acrylic resin for paints according to claim 1 and a polyisocyanate. 5. An acrylic resin for coatings and a polyisocyanate having an equivalent ratio of hydroxyl group / isocyanate group of 0.6 to 0.6.
The two-component acrylic urethane resin composition for a paint according to claim 4, wherein the composition is contained at a ratio of 1.2. 6. An acrylic melamine resin composition for paints, comprising the acrylic resin for paints according to claim 1 and an amino resin. 7. The acrylic melamine resin composition for a paint according to claim 6, wherein the acrylic resin for a paint contains 60 to 95% by weight and the amino resin contains 5 to 40% by weight.