JP2000129200A - Resin composition for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in low-temperature curability, storage stability and light resistance by including each specific acrylic resin and organoalkoxysilane compound, an antioxidant, and aluminum chelate compound in specified proportions. SOLUTION: This composition is obtained by incorporating (A) 100 pts.wt. of an acrylic resin with epoxy group on the side chain with (B) 0.01-10 pts.wt. of an antioxidant having intramolecular isocyanurate ring such as polymer-type phenolic antioxidant, (C) 0.05-200 pts.wt. of an organoalkoxysilane compound having both glycidyl and hydrolyzable alkoxysilane groups in one molecule, and (D) 0.01-10 pts.wt. of an aluminum chelate compound, and pref. furthermore (E) 1-200 pts.wt. of an epoxy resin 100-2,000 in epoxy equivalent; wherein it is preferable that the acrylic resin has active methylene or hydroxy group on the side chain as a functional group other than the epoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a low temperature (80 ° C. or less)
The present invention relates to a paint resin having excellent curability and excellent weather resistance of the paint, and a paint obtained by using the paint resin.

[0002]

2. Description of the Related Art Conventionally, a one-pack type coating resin excellent in curability at a low temperature (80 ° C. or lower) has been desired, and although the following techniques have been proposed, storage stability and curing have been proposed. No one has a good balance of properties and performance required for many paints.

That is, in the case of a conventionally used curing system of an acrylic polyol having a hydroxyl group in a molecular side chain and a melamine resin or a blocked isocyanate, or an epoxy resin using a latent catalyst (curing agent), 120 ° C.
Curing at the curing temperature lower than this is not enough to obtain a sufficient cross-linking density, and the film performance cannot be expected. For curing at a temperature lower than that, multi-partization is necessary, and many problems remain in workability. In addition, when the polyisocyanate is used, the curability is good, but the toxicity of the isocyanate cannot be ignored.

As a relatively recent technology, there is a technology in which an alkoxysilane group or an epoxy group is disposed on an acrylic resin side chain and an aluminum chelate compound is added thereto (Japanese Patent Publication No. Sho 55-41712, Japanese Patent Publication No. Sho 60-50223). JP, JP-B-60-50225, JP-B-61-2
No. 3816, JP-B-61-23817, JP-A-64-75502, JP-A-4-139281, JP-A-1-259907, JP-A-1-28
No. 7177), this system has difficulty in arranging an alkoxysilane group on the side chain, and has poor storage stability.
This system is 2% for low temperature curing below 80 ° C in the general market.
It is applied as a liquid type.
Curability at low temperature of 0 ° C. or less is insufficient.

[0005] Further, because of having an alkoxysilane group, seeding (aggregation and the like) with a pigment is easily caused.
In addition, only the surface of the coating film is dried and hardened preferentially when applied (therefore, the solvent remains indefinitely inside the coating film, and the expected coating performance cannot be obtained). In some cases, there was a problem that spots were generated on the coating film surface.

When these are used as a one-pack type, it is essential to incorporate a keto-enol tautomer compound such as acetylacetone, diacetone alcohol and t-butylacetylacetonate. Are highly toxic and have safety and health problems as well as environmental problems. Furthermore, the compounding of these compounds significantly impairs the curability of the paint, and may cause poor curing when a thick film is applied.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a coating composition having excellent curability at low temperatures (80 ° C. or lower), storage stability of the coating and weatherability. In particular, the present invention provides a one-pack type coating resin and a coating composition obtained by using the coating resin, and also provides various properties (adhesion, appearance, weather resistance, It is well balanced with chemical resistance, solvent resistance, etc.) and can sufficiently exhibit excellent functions.

[0008]

That is, according to the present invention, an antioxidant (B) is used in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of an acrylic resin (A) having an epoxy group in a side chain. Organoalkoxysilane compound (C) having a glycidyl group and a hydrolyzable alkoxysilane group
5 to 200 parts by weight and 0.01 to 10 parts by weight of an aluminum chelate compound (D).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic resin (A) having an epoxy group in a side chain according to the present invention can be used for producing an acrylic resin in glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxy. It can be produced by copolymerizing an epoxy group-containing unsaturated monomer such as cyclohexanemethyl methacrylate. Such monomers having an epoxy group may be used alone or as a mixture of two or more.

In order to obtain sufficient curability, storage stability and coating film performance, the monomer is preferably copolymerized as a component constituting the acrylic resin by 2 to 50% by weight. 2
If the amount is less than 50% by weight, sufficient curability may not be obtained. If the amount exceeds 50% by weight, the storage stability of the composition may be deteriorated and the form as a one-pack type composition may not be maintained. . However, when used as a two-pack type, it can exceed 50% by weight, and this is preferred because the curability is improved.

The weight average molecular weight of the acrylic resin measured by GPC as standard polystyrene conversion is 5,000, although it depends on the application and is not limited.
~ 200,000 is preferred. Those with a small molecular weight (50
(50,000 to 50,000) are suitable for use in automotive plastics as a high solid and high appearance type, and those having a high molecular weight (50,000 to 200,000) are suitable for use in high quality building material coatings. However, when the molecular weight is too small, the curability tends to decrease, and when the molecular weight is too large, the storage stability tends to deteriorate.

The acrylic resin is produced as a solvent solution or an aqueous dispersion by ordinary radical copolymerization. In the case of the present invention, toluene, xylene, butyl acetate, ethyl acetate, isopropyl alcohol, n-butyl alcohol,
Using an organic solvent such as ethylene glycol monobutyl ether, α, α′-azobisisobutyronitrile, α, α
An organic azo polymerization initiator such as' -azobis valeronitrile, and an organic peroxide such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate are used as polymerization initiators, and the polymerization temperature is 40 to 150. It is preferably produced by solution polymerization of the monomer having an epoxy group and other copolymerizable monomers at a temperature of ° C.

Here, the other copolymerizable monomers refer to styrene and (meth) acrylates,
For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, lauryl methacrylate, Stearyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate,
T-butyl acrylate, i-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate,
Lauryl acrylate, lauryl acrylate, stearyl acrylate and the like. The monomers may be used alone or as a mixture of two or more. Further, if necessary, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyl Unsaturated monomers having a hydrolyzable alkoxysilane group, such as trimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethyl It is also possible to copolymerize a chain transfer agent (polymerization degree modifier) having a hydrolyzable alkoxysilane group such Shishiran. These monomers and chain transfer agents may be used alone or as a mixture of two or more.

The acrylic resin (A) may have an active methylene group as a functional group other than the epoxy group on the side chain of the polymer. At this time, the UV stability of the composition is improved, and not only the weather resistance of the coating itself obtained from the composition is improved, but also it is extremely effective for protecting the undercoat and the base material from deterioration by ultraviolet rays.

Further, depending on the type of the active methylene group, not only the storage stability as a one-pack type of the composition but also the curability as a contradictory effect is enhanced.

The acrylic resin (A) having an active methylene group as a functional group other than the epoxy group at the side chain or at the terminal of the polymer can be used in the production of the acrylic resin together with the epoxy group-containing unsaturated monomer in diacetone acrylamide, It is produced by copolymerizing unsaturated monomers having an active methylene group such as diacetone methacrylamide, acetoacetoxymethyl acrylate, acetoacetoxyethyl acrylate, acetoacetoxymethyl methacrylate, and acetoacetoxyethyl methacrylate. These monomers may be used alone or as a mixture of two or more.

These monomers are preferably used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the epoxy group-containing unsaturated monomer. If the amount is less than 5 parts by weight, the expected ultraviolet stability of the coating film may not be obtained. If the amount exceeds 100 parts by weight, the viscosity of the composition may increase and the curability may deteriorate.

The acrylic resin (A) may have a hydroxyl group as a functional group other than an epoxy group on the side chain or at the terminal of the polymer. Thereby, the solvent resistance of the cured coating film (solvent rubbing property (resistance of the coating film to the solvent when the coating film is rubbed with a solvent), gasohol property (gasoline / methyl alcohol = 1/1 (capacity) The resistance of the coating film to the solvent when immersed in the solution of the ratio) is dramatically improved. Therefore, if a paint using the composition of the present invention is used, lifting (coating is eroded by solvent and swells and shrinks) at the time of touch-up (repainting to correct the defect of the paint defect portion). It does not wake up and improves workability. Also, for the same reason, lifting does not occur during recoating (repainting of defective parts or painting on old coatings), and the coating properties such as adhesion, coating appearance, weather resistance, etc. are excellent. . The amount of the monomer used is preferably 50% by weight or less of the acrylic resin (A) from the viewpoint of alcohol solvent resistance, water resistance and weather resistance.

The acrylic resin (A) having a hydroxyl group as a functional group other than an epoxy group on the side chain or at the terminal of the polymer is:
When producing an acrylic resin, 2-hydroxyethyl methacrylate together with the epoxy group-containing unsaturated monomer,
2-hydroxypropyl methacrylate, methacrylic acid 4
-Hydroxybutyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid 4
-Copolymerizing hydroxyl-containing unsaturated monomers such as hydroxybutyl, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monoacrylate, and polytetramethylene glycol monomethacrylate. It can be manufactured by the following. These monomers may be used alone or as a mixture of two or more.

These monomers are preferably used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the epoxy group-containing unsaturated monomer. If the amount is less than 5 parts by weight, the expected solvent resistance may not be obtained. If the amount exceeds 100 parts by weight, the viscosity of the composition may increase and the storage stability may decrease.

The antioxidant (B) includes 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, stearyl-β- (3,5-di-tert-butyl-4-).
(Hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol)
(Chemical Products of Reference 13398, Kagaku Kogyo Nippo (1998), p1038-p1047) and the like, and these may be used alone or as a mixture of two or more.

The antioxidant (B) not only dramatically improves the storage stability of the composition without the addition of a highly toxic compound such as acetylacetone, but also cures the same as when acetylacetone is blended. Does not cause inhibition. In addition, it exhibits its original function as an antioxidant,
Improves the weather resistance of paints.

The antioxidant (B) is an acrylic resin (A) 1
0.01 to 10 parts by weight is added to 00 parts by weight.
If the amount is less than 0.01 part by weight, no sufficient effect on the storage stability can be obtained, and if the amount exceeds 10 parts by weight, the curability deteriorates.

The antioxidant (B) is a polymer type phenol having an isocyanurate ring, for example, tris- (3,3)
5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, the effect is more remarkable, and the storage stability, curability, and weather resistance are further improved.

The organoalkoxysilane compounds (C) having a glycidyl group and a hydrolyzable alkoxysilane group in one molecule include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxy. Silane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethoxysilane, and the like. These compounds can be used alone or It may be a mixture of two or more. Further, partial condensates of these compounds may be used.

Organoalkoxysilane compound (C)
Is 0.05 with respect to 100 parts by weight of the acrylic resin (A).
In this case, a paint having excellent properties such as curability, storage stability and weather resistance can be obtained. 0.05
If the amount is less than 200 parts by weight, resilience tends to occur and the appearance of the coating film deteriorates.

The aluminum chelate compound (D) of the present invention includes aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetate), aluminum bisethyl acetoacetate monoacetylacetonate and the like. These may be used alone or as a mixture of two or more. The compound is
The curable resin composition of the present application functions as a starter for curing.

The aluminum chelate compound (D) is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic resin (A).
Use parts by weight. If the amount is less than 0.01 part by weight, the curability of the coating material deteriorates, the crosslinking is delayed, and the solvent resistance and weather resistance of the coating film are reduced. If it exceeds 10 parts by weight, it will not be able to be sufficiently dissolved in the acrylic resin, and conversely, the curability will be deteriorated, and there will be bumps on the coating film (there is a foreign material in the coating film and the surface will be rough). Occurs and the appearance of the coating film deteriorates.

The coating resin composition of the present invention may further contain an epoxy resin, preferably an alicyclic epoxy resin having an oxirane bond directly bonded to a cycloalkyl group. The main purpose of this is to greatly improve the curability of the paint, and to obtain a paint composition having improved weather resistance, chemical resistance, and excellent metal corrosion protection.

The epoxy resin (E) can be arbitrarily selected from many commercially available resins and used.
That is, these include a polyphenol type, a polyglycidylamine type, an alcohol type, an ester type, an alicyclic type, and others (reference: 13197, a chemical product, Kagaku Kogyo Nippo, published in 1997, P923-P931). These epoxy resins may be used alone or as a mixture of two or more. In order to obtain sufficient curability, storage stability and coating film performance, the epoxy resin has an epoxy equivalent of 100.
~ 2000. If the epoxy equivalent is less than 100, the coating film becomes hard and brittle, and if it exceeds 2,000, sufficient curability cannot be obtained.

The epoxy resin (E) is an acrylic resin (A)
1 to 200 parts by weight is blended with respect to 100 parts by weight. 1
If the amount is less than parts by weight, the desired curability cannot be obtained, and
When the amount exceeds the weight part, the storage stability tends to deteriorate.

The composition of the present invention is obtained by uniformly mixing an acrylic resin (A) having an epoxy group in a side chain, an antioxidant (B), an organoalkoxysilane compound (C), and an aluminum chelate compound (D). If it is manufactured by any means, the object can be achieved.

Briefly, while stirring the acrylic resin (A), the antioxidant (B) and the aluminum chelate compound (D) are charged little by little and dissolved. Next, the organoalkoxysilane compound (C) is added, and stirring is continued until the mixture becomes uniform. Heating may be used if necessary during this manufacturing process, but sufficient manufacturing is possible at room temperature, and stability of the manufacturing (because the curing reaction proceeds during the manufacturing and no gel is formed), storage From the viewpoint of stability, 2
It is preferably produced at 0 to 50 ° C.

Further, a hydrophilic organic solvent, preferably having a vapor pressure at 20 ° C. of 15 hPa or less and a molecular weight of 80
By adding the diluent containing the above (poly) propylene glycol ether and stirring and mixing until the mixture becomes uniform, the curability at low temperatures can be further improved.

The resin composition of the present invention can be used as a resin composition or as a paint, that is, if necessary, a pigment such as titanium dioxide, carbon black or aluminum paste, or a well-known paint. Agents (leveling agents, pigment dispersants, anti-settling agents, ultraviolet absorbers, light stabilizers (HA
(LS), an antifoaming agent, etc.) and a solvent for dilution, and then used as a base coat (undercoat) or a topcoat (overcoat). In addition, other paints such as acrylic urethane resin paint, urethane resin paint, alkyd resin paint, epoxy resin paint, fluororesin paint,
It can also be used in combination with silicone resin paints, acrylic silicone resin paints, etc. (reference: 13197, a chemical product, published by Chemical Industry Daily (1997)). That is, to give an example, it is also possible to apply a paint prepared using the composition of the present application as a base coat and then use an acrylic urethane resin paint as a top coat.

Base materials that can be coated include ABS (acrylonitrile-styrene-butadiene resin), polystyrene,
Plastics such as polycarbonate and nylon, metals such as iron, aluminum, galvanized iron, tinplate, etc., and those subjected to chemical conversion treatment and those subjected to cationic or anion electrodeposition coating, mortar, cement, asbestos cement, asbestos cement perlite Building materials such as bricks, tiles, slate, etc.

The coating method used is a coating prepared using the composition of the present invention, such as spray coating, brush coating, roller coating, coating with a roll coater, curtain coating, anionic electrodeposition coating, and cationic electrodeposition coating. The methods commonly used in the industry can be applied.

[0038] The painted articles can be used in a wide variety of industries. That is, for example, plastic parts and metal materials of automobiles and motorcycles (from small to large), plastic parts and metal members of household appliances,
There are outer wall materials (sizing boards, curtain walls, aluminum sashes), roof tiles, and the like.

Hereinafter, an embodiment will be described in detail. Unless otherwise specified, the number of parts indicates parts by weight and the composition ratio indicates% by weight.

[0040]

Example 1 Methacryl solution-polymerized using α, α'-azobisisobutyronitrile as a polymerization initiator and a toluene / propylene glycol methyl ether (= 80/20) solvent at a polymerization temperature of 93 ° C. Methyl acrylate (MMA) / n-butyl methacrylate (BMA) / n-butyl acrylate (B
A) / Glycidyl methacrylate (GMA) (= 40/2)
0/20/20) of an acrylic copolymer (= solid content 50%, weight average molecular weight 35,000) was charged in a stainless beaker equipped with a stirrer (1000 g), and "TTAD" (an antioxidant; N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide; a product of Toray Industries, Inc.) 10 g, "Aluminum chelate A (W)" (aluminum chelate compound; (aluminum tris) (Acetyl acetate)); 10 g of Kawaken Fine Chemical Co., Ltd.) is charged and stirred until it is uniformly dissolved.

100 g of "S-510" (an organoalkoxysilane compound having a glycidyl group and a hydrolyzable alkoxysilane group in one molecule; 3-glycidoxypropyltrimethoxysilane; a product of Chisso Corporation)
Was added, and the mixture was stirred and mixed until the mixture became uniform, to produce the resin composition for coating of Example 1.

Example 2 "TTIC"(antioxidant; tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate; Toray Industries, Inc.) in Example 1 instead of "TTAD" A resin composition for a coating material of Example 2 was produced in the same manner as in Example 1 except that the product was used.

Example 3 A coating resin composition of Example 3 was produced in the same manner as in Example 1 except that the amount of “TTIC” was changed to 0.05 g.

Example 4 A coating resin composition of Example 4 was produced in the same manner as in Example 1 except that the amount of “TTIC” was changed to 50 g.

Example 5 MMA prepared by solution polymerization using α, α′-azobisisobutyronitrile as a polymerization initiator at a polymerization temperature of 93 ° C. and toluene / propylene glycol methyl ether (= 80/20) as a solvent. BMA / BA / 3,4-epoxycyclohexylmethyl methacrylate (EMA) (= 4
0/20/20/20) acrylic copolymer (=
1000 g of a solid content of 50% and a weight-average molecular weight of 420,000 were charged into a stainless steel beaker equipped with a stirrer, and "TTAD"(antioxidant; N, N'-hexamethylenebis (3,5-di- 10 g of "-t-butyl-4-hydroxy-hydrocinnamide; product of Toray Industries, Inc." and 10 g of "Aluminum chelate A (W)" are stirred and stirred until they are uniformly dissolved, and 100 g of "S-510" is added thereto. The mixture was added, stirred and mixed until the mixture became uniform, to produce a resin composition for coating of Example 5.

Example 6 MMA prepared by solution polymerization using α, α′-azobisisobutyronitrile as a polymerization initiator at a polymerization temperature of 93 ° C. and toluene / propylene glycol methyl ether (= 80/20) as a solvent. BMA / BA / EMA (= 40 /
20/20/20) of an acrylic copolymer (= solid content 50%, weight average molecular weight 42,000) was charged in a stainless beaker equipped with a stirrer (1000 g), and “TTIC” 10 g, “ERL- 4221 "(alicyclic epoxy resin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate;
100 g of Union Carbide Nippon Co., Ltd.) are charged and stirred and mixed until uniform. Next, 10 g of “aluminum chelate A (W)” is charged and stirred until it is uniformly dissolved. To this, 100 g of "S-510" was added,
The resin composition for coating of Example 5 was manufactured by stirring and mixing until the mixture became uniform.

Example 7 MMA prepared by solution polymerization using α, α'-azobisisobutyronitrile as a polymerization initiator at a polymerization temperature of 93 ° C. and toluene / propylene glycol methyl ether (= 80/20) as a solvent. BMA / BA / GMA / 2-hydroxyethyl methacrylate (HEMA) (= 40/15
/ 15/10/20) of an acrylic copolymer (= 50% solids, weight average molecular weight 36,000) in a stainless beaker equipped with a stirrer, 10 g of “TTAD” while stirring, 10 g of “Aluminum Chelate A (W) "
Charge 10 g and stir until homogeneously dissolved.

In addition, "SH-6040" (an organoalkoxysilane compound having a glycidyl group and a hydrolyzable alkoxysilane group in one molecule; 3-glycidoxypropyltrimethoxysilane; Dow Corning Toray Silicone Co., Ltd.) Was added, and the mixture was stirred and mixed until it became uniform, to produce a coating resin composition of Example 7.

Example 8 MMA obtained by solution polymerization using α, α′-azobisisobutyronitrile as a polymerization initiator and a toluene / propylene glycol methyl ether (= 80/20) solvent at a polymerization temperature of 93 ° C.) / BMA / BA / GMA / trimethylsiloxyethyl methacrylate (SMA) (= 30
/ 20/20/20/10) was charged into a stainless beaker equipped with a stirrer with 1000 g of an acrylic copolymer (= solid content: 50%, weight average molecular weight: 420,000), and 10 g of “TTIC” was stirred. "Aluminum chelate A
(W) ", and stirred until homogeneously dissolved. To this, 100 g of "S-510" was added, and the mixture was stirred and mixed until the mixture became uniform, whereby the resin composition for coating of Example 1 was produced.

Example 9 In Example 1, "Aluminum chelate A (W)" was used.
Was prepared in the same manner as in Example 1 except that the compounding amount of was adjusted to 0.05 g.

Example 10 In Example 1, "Aluminum chelate A (W)" was used.
Was prepared in the same manner as in Example 1 except that the compounding amount of was changed to 50 g.

Example 11 Using α, α'-azobisisobutyronitrile as a polymerization initiator, MMA prepared by solution polymerization at a polymerization temperature of 93 ° C. and toluene / propylene glycol methyl ether (= 80/20) as a solvent. BMA / BA / GMA / 3-methacryloyloxypropyltrimethoxysilane (MP
S) (= 35/20/20/20/5) acrylic copolymer (= solid content 50%, weight average molecular weight 3.5)
1000) in a stainless beaker with a stirrer.
g, 10 g of “TTIC” and 10 g of “aluminum chelate A (W)” are charged with stirring and stirred until they are uniformly dissolved. To this, 100 g of “S-510” was added, and the mixture was stirred and mixed until the mixture became uniform, whereby a resin composition for coating of Example 11 was produced.

Example 12 A coating resin composition of Example 12 was produced in the same manner as in Example 7 except that the amount of “SH-6040” was changed to 0.3 g.

Example 13 A coating resin composition of Example 13 was produced in the same manner as in Example 7, except that the amount of “SH-6040” was changed to 1000 g.

Example 14 MMA prepared by solution polymerization using α, α′-azobisisobutyronitrile as a polymerization initiator and toluene / propylene glycol methyl ether (= 80/20) as a solvent at a polymerization temperature of 93 ° C. BMA / BA / GMA / HEMA
(= 40/15/15/10/20) acrylic copolymer (= solid content 50%, weight average molecular weight 36,000)
Into a stainless beaker equipped with a stirrer, 10 g of “TTIC” and “ERL-4” while stirring.
221 "is stirred and mixed until uniform.
Further, 10 g of "aluminum chelate A (W)" is charged and stirred until it is uniformly dissolved. To this, 100 g of "S-510" was added, and the mixture was stirred and mixed until it became uniform, whereby a resin composition for coating materials of Example 14 was produced.

Example 15 In Example 14, the amount of “ERL-4221” was changed to 1000.
A coating resin composition of Example 15 was produced in the same manner as in Example 15 except that the amount was changed to g.

Example 16 In Example 14, the amount of “ERL-4221” was changed to 150 g.
A resin composition for a coating material of Example 16 was produced in the same manner as in Example 14 except for the above.

Example 17 A coating resin composition of Example 17 was produced in the same manner as in Example 16, except that the amount of “Aluminum chelate A (W)” was changed to 0.05 g.

Example 18 A coating resin composition of Example 18 was produced in the same manner as in Example 16, except that the amount of “Aluminum chelate A (W)” was changed to 50 g.

Example 19 In Example 16, the compounding amount of "S-510" was changed to 500 g.
A coating resin composition of Example 19 was produced in the same manner as in Example 16, except that

Example 20 MMA prepared by solution polymerization using α, α′-azobisisobutyronitrile as a polymerization initiator at a polymerization temperature of 93 ° C. and toluene / propylene glycol methyl ether (= 80/20) as a solvent. BMA / BA / GMA / HEMA
(= 40/15/15/10/20) acrylic copolymer (= solid content 50%, weight average molecular weight 36,000)
Into a stainless beaker equipped with a stirrer, 10 g of “TTIC” and “ERL-4” while stirring.
221 ", 50 g of" Eporide GT302 "(alicyclic epoxy resin; product of Daisail Chemical Industries, Ltd.) 10
0 g is stirred and mixed until uniform. Further, 20 g of aluminum chelate A (W) is charged and stirred until it is uniformly dissolved. To this, 200 g of "S-510" was added, and the mixture was stirred and mixed until the mixture became uniform to produce the resin composition for coating of Example 20.

Example 21 MMA prepared by solution polymerization using α, α′-azobisisobutyronitrile as a polymerization initiator at a polymerization temperature of 93 ° C. and toluene / propylene glycol methyl ether (= 80/20) as a solvent. BMA / BA / GMA / HEMA
/ Diacetone acrylamide (polymerizable unsaturated monomer having active methylene group) (= 35/15/15/10 //
20/5) acrylic copolymer (= 50 solids)
%, Weight average molecular weight 42,000) was charged to a stainless steel beaker equipped with a stirrer, and stirred.
10 g of “TIC” and 150 g of “ERL-4221” are mixed and stirred until uniform. Further, 20 g of "Aluminum chelate A (W)" is charged and stirred until it is uniformly dissolved. To this, 150 g of “S-510” was added, and the mixture was stirred and mixed until the mixture became uniform, to produce a resin composition for coating of Example 21.

Comparative Example 1 A coating resin composition of Comparative Example 1 was produced in the same manner as in Example 1 except that the amount of “TTAD” was changed to 0.04 g.

Comparative Example 2 A coating resin composition of Comparative Example 2 was produced in the same manner as in Example 1 except that the amount of “TTAD” was changed to 55 g.

Comparative Example 3 A coating resin composition for Comparative Example 3 was produced in the same manner as in Example 16 except that the amount of “S-510” was changed to 0.2 g.

Comparative Example 4 A coating resin composition of Comparative Example 4 was produced in the same manner as in Example 16 except that the amount of “Aluminum chelate A (W)” was changed to 0.04 g.

Comparative Example 5 In Example 16, the compounding amount of “Aluminum chelate A (W)” was changed to 5
A coating resin composition of Comparative Example 5 was produced in the same manner as in Example 16 except that the amount was changed to 5 g.

Table 1 shows the results. The evaluation method is as follows.

(1) Storage Stability The degree of viscosity increase after storing the composition at 40 ° C. for 2 months was evaluated. ○ The viscosity increase is within 2 times the initial viscosity, which is good. The curing reactivity is the same as the initial one. Pass. × The viscosity increase is twice or more the initial initial viscosity or gelation. failure.

(2) Gel fraction The composition was applied to a polypropylene plate and dried by heating at 80 ° C for 30 minutes. The coating film was peeled off from the polypropylene plate, and the solvent insoluble matter (gel fraction) was measured using a Soxhlet extractor using acetone / methanol (50/50 vol%) as a solvent. The higher the gel fraction (the larger the numerical value), the better the crosslinkability. Pass if 70% or more.
The gel fraction is calculated by the following equation. Gel fraction (%) = (weight of dried coating film after solvent extraction / weight of initial coating film) × 100

(3) Weather Resistance The composition was coated on an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) plate degreased with isopropyl alcohol so that the coating thickness became 30 μm,
After drying for 30 minutes, it was dried by heating at 80 ° C. for 30 minutes. Using this coated plate, a metal weather-accelerated weathering tester (a tester manufactured by Daipler Wintes Co., Ltd.)
The test was performed for 68 hours. Gloss retention of coating film (GR
(%)) And the color to be changed (color difference) (ΔE) (that is, to see how much the coating film can suppress the deterioration of the ABS due to ultraviolet rays (color to be changed)). Gloss retention rate is 9
Pass 0% or more. ΔE is 5 or less.

[0072]

[Table 1]

Table 1 shows that Examples 1 to 21 of the present invention are excellent in storage stability, curability and weather resistance. When the amount of the antioxidant (B) was insufficient (Comparative Example 1), the storage stability was poor, and there was also a problem in weather resistance. On the other hand, when the compounding amount of the antioxidant (B) is too large (Comparative Example 2), since a complex formation reaction occurs between the antioxidant and the aluminum chelate compound, the curability is not affected, but the storage stability is not affected. Gets worse. When the amount of the organoalkoxysilane compound (C) was small (Comparative Example 3), not only storage stability but also curability and weather resistance were deteriorated. When the amount of the aluminum chelate compound (D) was small (Comparative Example 4), the storage stability was good, but the curability deteriorated. When the amount was too large (Comparative Example 5), the curability was deteriorated, the aluminum chelate compound was not completely dissolved in the composition, and the aluminum chelate compound was deposited on the surface of the coating film, and the coating film was full.

[0074]

The coating resin composition of the present invention can be used as a one-pack type resin composition as it is or as a coating composition for various substrates.
(0 ° C. or lower), excellent in curability, storage stability, and weather resistance.

Claims (5)

[Claims] An antioxidant (B) is added to 100 parts by weight of an acrylic resin (A) having an epoxy group in a side chain.
1 to 10 parts by weight, 0.05 to 200 parts by weight of an organoalkoxysilane compound (C) having a glycidyl group and a hydrolyzable alkoxysilane group in one molecule, and 0.01 to 10 parts by weight of an aluminum chelate compound (D) A resin composition for paints blended. 2. The resin composition according to claim 1, wherein the antioxidant (B) is a high molecular weight phenolic antioxidant having an isocyanurate ring in the molecule. 3. The resin composition according to claim 1, wherein the acrylic resin (A) has an active methylene group in a side chain as a functional group other than an epoxy group. 4. The coating resin composition according to claim 1, wherein the acrylic resin (A) has a hydroxyl group in a side chain as a functional group other than an epoxy group. 5. A resin composition for paints, further comprising 1 to 200 parts by weight of an epoxy resin having an epoxy equivalent of 100 to 2,000 per 100 parts by weight of the acrylic resin (A).