JP2001122968A - Cold curing coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cold curing coating composition capable of forming a film excellent in weatherability and a luster thereof and excellent in storage properties, initial drying properties and workability in double coating. SOLUTION: An oxidation curing-type silicon-modified vinyl-based resin is formed by bonding an epoxy group-containing vinyl copolymer (a) which is the copolymer of a polymerizable unsaturated monomer containing the epoxy group and another polymerizable unsaturated monomer capable of copolymerizing therewith to a fatty acid ingredient (b) containing unsaturated fatty acid and a silicone resin (c) containing hydroxyl group and/or an alkoxyl group directly bonding to silicon atom and the coating composition comprises the oxidation curing-type silicon-modified vinyl-based resin as a resin component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oxidatively curable silicone-modified vinyl-based resin, and a room-temperature-curable coating composition using the modified vinyl-based resin capable of forming a coating film having excellent weather resistance and initial drying properties. About things.

[0002]

2. Description of the Related Art Conventionally, alkyd resins using unsaturated fatty acids are well known as paint resins which have room temperature curability and are stable for a long time in a solution state. However, this alkyd resin is susceptible to deterioration in weather resistance due to ultraviolet rays, and is insufficient in performance for use in outdoor applications. As a method of solving this problem of weather resistance, for example, British Patent No. 79
Japanese Patent No. 3,776 proposes an acrylic resin modified with a fatty acid. However, the fatty acid-modified acrylic resin, although slightly improved in weather resistance, contains a low-polarity soft component fatty acid, so that the coating performance such as weather resistance, water resistance, and acid / alkali resistance is still low. It was not inadequate.

[0003]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a resin obtained by further modifying a fatty acid-modified acrylic resin with a silicone resin is used as a coating resin. As a result, the weather resistance of the coating film is remarkably improved, and the coating containing the silicone-modified acrylic resin is excellent in storage stability, workability in two-coating, and excellent initial drying property. The invention has been completed.

That is, the present invention relates to an epoxy group-containing vinyl copolymer (a) which is a copolymer of an epoxy group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the monomer. Provided is an oxidation-curable silicone-modified vinyl resin in which a fatty acid component (b) containing an unsaturated fatty acid and a silicone resin (c) containing a hydroxyl group and / or an alkoxyl group directly bonded to a silicon atom are bonded. Things.

Another object of the present invention is to provide a coating composition containing an oxidation-curable silicone-modified vinyl resin as a resin component.

Hereinafter, the present invention will be described in detail.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the oxidation-curable silicone-modified vinyl resin of the present invention will be described. The oxidation-curable silicone-modified vinyl resin of the present invention is a resin obtained by bonding the following fatty acid component (b) and the following silicone resin (c) to the following epoxy group-containing vinyl copolymer (a).

Epoxy group-containing vinyl copolymer (a) The epoxy group-containing vinyl copolymer (a) used in the present invention includes, for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, ) 3,4-epoxycyclohexylmethyl acrylate, (meth)
3,4-epoxycyclohexylpropyl acrylate,
A copolymer of an epoxy group-containing polymerizable unsaturated monomer such as allyl glycidyl ether and another polymerizable unsaturated monomer copolymerizable with the epoxy group-containing polymerizable unsaturated monomer can be exemplified.

The other polymerizable unsaturated monomers include:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Hexyl (meth) acrylate, 2- (meth) acrylate
Ethylhexyl, n-octyl (meth) acrylate,
C1-C24 alkyl esters of acrylic acid or methacrylic acid such as decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) ) Such as acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate α, β-ethylene having an alkylene oxide chain and a hydroxyl group such as hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acid, and polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Hydroxyl group-containing monomers such as sexual unsaturated carboxylic acid ester; (meth) acrylate, isobornyl (meth) acrylic acid 1,2,2,6,6
Pentamethylpiperidyl, 2,2, (meth) acrylic acid
6,6-tetramethylpiperidinyl, 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-
Benzotriazole, styrene and the like can be mentioned.

In the epoxy group-containing vinyl copolymer (a), the copolymerization ratio between the epoxy group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer is usually the same as that of the epoxy group-containing polymerizable unsaturated monomer. Is 3-70% by weight,
It is preferably in the range of 5 to 40% by weight, and the other polymerizable unsaturated monomer is 30 to 97% by weight, preferably 6 to 97% by weight.
It is appropriate that the amount is in the range of 0 to 95% by weight in view of addition reactivity when reacting with the unsaturated fatty acid (b), solubility of the obtained epoxy group-containing vinyl copolymer in a solvent, and the like. .

In the determination of the amount of the hydroxyl group-containing monomer in the epoxy group-containing vinyl copolymer (a),
The amount thereof should be determined so that gelation due to reaction with the glycidyl group in the vinyl copolymer (a) and reaction with the silicone resin do not occur during the reaction with the silicone resin. Usually, the amount of the hydroxyl group-containing monomer to be used is suitably not more than 50 parts by weight in the monomer component constituting the vinyl copolymer (a).

[0012] The copolymerization method for obtaining the epoxy group-containing vinyl copolymer (a) is not particularly limited, but it may be easily reacted with the fatty acid component (b) or the silicone resin (c). In view of the above, a solution polymerization method carried out in an organic solvent in the presence of a radical polymerization initiator is preferred.

The radical polymerization initiator used in the synthesis of the above epoxy group-containing vinyl copolymer by solution polymerization includes, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,2 Azo-based polymerization initiators such as 4-dimethylvaleronitrile); and peroxide-based polymerization initiators such as lauryl peroxide, t-butylperoxy-2-ethylhexanoate, and benzoyl peroxide.

As the organic solvent used in the synthesis by the solution polymerization, for example, n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane,
aliphatic hydrocarbon solvents such as n-nonane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; mineral spirits, "Swazol 1000" (a product of Cosmo Oil), petroleum ether, Petroleum solvents such as petroleum benzine and petroleum naphtha; ketone solvents such as methyl isobutyl ketone; ester solvents such as isobutyl acetate; alcohol solvents such as isopropanol alone or as a mixture of two or more. They can be used as desired.

[0015] The epoxy group-containing vinyl copolymer (a) is
Number average molecular weight of 1,000 to 100,000, especially
It is in the range of 2,000 to 50,000, and the glass transition temperature (Tg) is in the range of 0 ° C to 100 ° C. It is suitable in terms of dryness.

Fatty acid component (b) The fatty acid component (b) constituting the resin of the present invention is a fatty acid component containing an unsaturated fatty acid essentially and, if necessary, a saturated fatty acid, and having an iodine value of about 50. Suitably, it is in the range of ~ 200. When the iodine value is less than about 50, the curability of the coating film is reduced, while the iodine value is about 200
If it exceeds, it is not preferable because gelation may occur during resin production.

Representative examples of unsaturated fatty acids which are essential components of the fatty acid component (b) include fish oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, Eno-oil fatty acids,
Examples include hemp seed oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, and rubber seed oil fatty acids.
The unsaturated fatty acid is an oxidatively curable fatty acid having a polymerizable unsaturated group, and imparts oxidative curability to the silicon-modified vinyl resin of the present invention.

Examples of the saturated fatty acid which the fatty acid component (b) can further contain in addition to the above unsaturated fatty acid, if necessary, include unsaturated fatty acids such as coconut oil fatty acid, hydrogenated coconut oil fatty acid and palm oil fatty acid. Drying oil fatty acids; caproic acid,
Examples thereof include capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. The proportion of the fatty acid component (b) used is in the range of 1 to 60 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the resin solid content of the epoxy group-containing vinyl copolymer (a). Are preferred from the viewpoint of the curability and weather resistance of the obtained coating film.

The silicone resin (c) silicone resin constituting the resin of the present invention (c) is a silicon resin containing a hydroxyl group and / or alkoxyl groups bonded directly to silicon atoms, for example, the following rational formula R ¹ _a (R ² O) _b SiO _{(4-ab) / 2} (wherein, R ¹ is the same or different and represents an alkyl group or an aryl group having 1 to 8 carbon atoms, and R ² is H or 1 to ² carbon atoms)
A represents 0 ≦ a ≦ 3.5, and b represents 0.
0005 ≦ b ≦ 4.0) can be preferably used.

In the above formula, specific examples of the alkyl group having 1 to 8 carbon atoms for R ¹ include, for example, methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, A cyclohexyl group and the like can be mentioned, and specific examples of the aryl group for R ¹ include a phenyl group and a tolyl group. As R ¹ , among these, a methyl group, an ethyl group, and a phenyl group are preferable in terms of availability, reactivity, and the like.

Specific examples of H as R ² and / or an alkyl group having 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl and the like. Of these, you can
Among them, hydrogen, a methyl group and an ethyl group are preferred from the viewpoint of reactivity.

In the above formula, the fact that a is within the range of 0 ≦ a ≦ 3.5 and b is within the range of 0.0005 ≦ b ≦ 4.0 indicates that the epoxy group-containing vinyl copolymer (a ) Or the reactivity of the copolymer (a) with the hydroxyl group in the reaction product of the fatty acid component (b), the physical properties and curability of the obtained coating film,
It is suitable in terms of weather resistance and the like. The silicone resin (c) has a polystyrene equivalent number average molecular weight of 90 to 90.
It is desirable to be within the range of 100,000 from the viewpoint of the physical properties and curability of a coating film formed using the obtained silicon-modified vinyl resin.

Commercially available silicone resins (c) include, for example, SH-6018, DC3074, DC3037,
SR2402 (all, products of Toray Dow Corning Co., Ltd.); KR9218, X-40-9220 (all, products of Shin-Etsu Chemical Co., Ltd.), TSR165, X
R-31B1763 (both are products of Toshiba Silicone Co., Ltd.) and the like.

The silicone resin (c) is selected from the commercially available products described above,
1 of silicone resin containing hydroxyl group or alkoxyl group
A kind or a mixture of two or more kinds, a partial hydrolysis / condensation product of the one kind or two or more kinds of mixtures, a partial hydrolysis / condensation product of a hydroxyl- or alkoxyl-containing silicone resin and an organo or trialkoxysilane, etc. Can be. Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.Examples of the organotrialkoxysilane include methyltrimethoxysilane. Examples thereof include methyltriethoxysilane, methyltriisopropoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

The proportion of the silicone resin (c) used is such that the resin solid content of the epoxy group-containing vinyl copolymer (a) is 100%.
1 to 370 parts by weight, preferably 1 to 20 parts by weight based on parts by weight
0 parts by weight, more preferably in the range of 1 to 100 parts by weight is preferable from the viewpoint of the curability and weather resistance of the obtained coating film.

The epoxy group-containing vinyl copolymer (a), fatty acid component (b) and silicone resin (c) for producing the oxidation-curable silicone-modified vinyl resin of the present invention.
The order of the reaction is not particularly limited, and the above three can be simultaneously reacted. However, the epoxy group-containing vinyl copolymer (a) is reacted with the fatty acid component (b). It is preferable to react the silicone resin (c) with the fatty acid-modified copolymer, which is a reaction product, from the viewpoint of easy control of the reaction.

The above-mentioned epoxy group-containing vinyl copolymer (a)
The reaction between the fatty acid component (b) and the fatty acid component (b) is based on the esterification reaction between the epoxy group in the copolymer (a) and the carboxyl group in the fatty acid component (b). Is generated. In this reaction, if necessary, a solution such as N, N-dimethylaminoethanol
Reaction catalysts such as quaternary ammonium salts such as quaternary amines and tetrabutylammonium bromide can be used. When a reaction catalyst is used, the amount of the catalyst used is determined by the amount of the copolymer (a).
Based on a total of 100 parts by weight of the fatty acid component and the fatty acid component (b).
A range of from 01 to 100 parts by weight is suitable.

The reaction conditions of the copolymer (a) and the fatty acid component (b) are such that the epoxy group and the fatty acid component (b) in the copolymer (a) do not cause a problem such as gelation.
Any condition can be used as long as it can react with the carboxyl group in it,
Generally, heating at about 100 to 170 ° C. for about 2 to 10 hours is suitable.

The reaction between the fatty acid-modified copolymer obtained as described above and the silicone resin (c) may be carried out, if necessary,
In the presence of a reaction catalyst, the reaction can be carried out by heating to cause a dehydration or dealcoholization condensation reaction.
The above-mentioned dehydration or dealcoholization condensation reaction is based on a reaction between a hydroxyl group in the fatty acid-modified copolymer and a hydroxyl group or an alkoxysilyl group in the silicone resin (c). The hydroxyl group in the fatty acid-modified copolymer includes a hydroxyl group originally present in the copolymer (a) and a hydroxyl group generated by a reaction between the copolymer (a) and the fatty acid component (b).

As the reaction catalyst in the above dehydration and dealcoholization condensation reaction, metal alkoxide compounds, metal chelate compounds, metal ester compounds and the like are used. Examples of the metal alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, and aluminum tri-sec-.
Aluminum alkoxides such as butoxide and aluminum tri-tert-butoxide; tetramethyl titanate;
Tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-
Titanium alkoxides such as lauryl titanate; tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-
Butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-
Zirconium alkoxides such as pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate and tetra-n-stearyl zirconate; Butoxide and the like, as the metal chelate compound, for example,
Tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum,
Tris (n-butyl acetoacetate) aluminum,
Isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum,
Tris (proponylacetonato) aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonatobis (propionylacetonato) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, acetylacetonatoaluminum disec- Butyrate, methyl acetoacetate aluminum di-tert-butylate, bis (acetylacetonato) aluminum mono-sec-butylate, di (methylacetoacetate) aluminum mono-tert-butylate
Aluminum chelate compounds such as butyrate; titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate, di-n-butoxybis (acetylacetonato) titanate; tetrakis Zirconium chelate compounds such as (acetylacetonato) zirconium, tetrakis (n-propylacetoacetate) zirconium, and tetrakis (ethylacetoacetate) zirconium; dibutyltin bis (acetylacetonate); and metal ester compounds include, for example, , Dibutyltin diacetate, dibutyltin di (2-ethylhexylate), dibenzyltin di (2-ethylhexylate), dibutyltin dilaurate, dibutyltin diisooctylma Tin ester compounds such as benzoate and the like. These reaction catalysts can be used alone or in combination of two or more.

The above reaction catalyst is used in an amount of 0.1 parts by weight based on 100 parts by weight of the total of the fatty acid-modified copolymer and the silicone resin (c).
It is appropriate to use 001 to 5 parts by weight, preferably 0.005 to 1 part by weight, from the viewpoint of promoting the reaction.

Fatty acid-modified copolymer and silicone resin (c)
The reaction conditions for the reaction with are not particularly limited as long as the dehydration and dealcoholization condensation reaction proceeds, and the reaction temperature is usually 60 to 250 ° C, preferably 80 to 200 ° C, and more preferably Is 100-180 ° C
And the reaction time is suitably in the range of 0.5 to 24 hours, preferably 1 to 12 hours. Further, in the above reaction, the water and alcohol generated by the reaction are removed from the system, so that the reaction can proceed smoothly.

In the above reaction, the dehydration or dealcoholization condensation reaction may be carried out until the obtained resin can exhibit the performance as a resin for coating. All of the hydroxyl groups may have reacted. The degree of progress of the reaction is measured by infrared absorption spectrum (IR).
It can be known by a method for determining the absorption intensity due to the hydroxyl group by measurement, a method for measuring the amounts of water and alcohol generated by the reaction, and an increase in the viscosity of the system.

Coating Composition The oxidation-curable silicone-modified vinyl polymer of the present invention obtained as described above can be suitably used as a coating resin. The oxidation-curable silicone-modified vinyl polymer of the present invention can be used alone as a coating composition, but if necessary, an oxidation-curing reaction catalyst, pigments, an organic solvent, an ultraviolet absorber, a light Stabilizers, surface conditioners,
A coating composition can be prepared by adding a coating additive such as a pigment dispersant, a rheology control agent, a coating liquid anti-skinning agent, a fungicide, an anti-algal agent, a plasticizer, and an antifoaming agent.

The above-mentioned oxidation-curing reaction catalyst has an action of accelerating a cross-linking reaction by oxidation of reactive double bonds based on unsaturated fatty acids in an oxidation-curable silicone-modified vinyl polymer. Examples thereof include organic metal compounds such as cobalt octylate, cobalt naphthenate, manganese octylate, manganese naphthenate, zirconium octylate, zirconium naphthenate, and lead octylate.

The coating film obtained from the composition of the present invention has very good appearance such as surface gloss, excellent weather resistance and chemical resistance, and has a slight It can be cured in a few hours and shows excellent room temperature curability.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” mean “parts by weight” and “% by weight”, respectively. Example 1 A flask was charged with 100 parts of mineral spirits and heated to 115 ° C. with stirring while flowing nitrogen gas. Next, a mixture of the following monomers and the like was added dropwise over 4 hours while maintaining the temperature at 115 ° C.

Styrene 25 parts N-butyl methacrylate 15 parts i-butyl methacrylate 20 parts 2-ethylhexyl acrylate 20 parts Glycidyl methacrylate 20 parts 2,2'-azobisisobutyronitrile 1 part Then 2 at 115 ° C After aging for 30 hours, the temperature was raised to 140 ° C., and 30 parts of linseed oil fatty acid and N, N
160 parts of dimethylaminoethanol
For 5 hours to carry out an addition reaction of the fatty acid. The resin acid value was traced by a KOH titration method, and the time when the resin acid value became 1.0 or less was defined as the end point. After completion of the reaction, 45 parts of xylene was added to dilute to obtain a brown transparent and viscous fatty acid-modified copolymer (A-1) solution having a nonvolatile content of 50%. Next, the mixture was cooled to 100 ° C., and the flask was equipped with a water separator.
20 parts of H-6018 (manufactured by Dow Corning Toray Silicone Co., Ltd.), 14 parts of mineral spirit, 6 parts of xylene and 0.20 part of tetra-n-butyl titanate as a reaction catalyst were added, and the temperature was raised to 165 ° C. The mixture was reacted for 5 hours while separating water with a water separator in a reflux system to obtain a brown transparent and viscous silicon-modified vinyl resin solution having a nonvolatile content of about 50%.

Example 2 289.4 parts of a 50% non-volatile content fatty acid-modified copolymer (A-1) solution obtained in the preceding step of Example 1, 10 parts of silicone resin SH-6018, and 7 parts of mineral spirit , 3 parts of xylene and 0.10 part of tetra-n-butyl titanate as a reaction catalyst were charged into a flask equipped with a water separator, the temperature was raised to 165 ° C, and water was separated by a water separator in a reflux system. While reacting for 5 hours, a brown transparent and viscous silicon-modified vinyl resin solution having a nonvolatile content of 50% was obtained.

Example 3 A flask was charged with 100 parts of mineral spirits, and heated to 115 ° C. with stirring while flowing nitrogen gas. Next, a mixture of the following monomers and the like was added dropwise over 4 hours while maintaining the temperature at 115 ° C.

Styrene 20 parts n-butyl methacrylate 15 parts i-butyl methacrylate 20 parts 2-ethylhexyl acrylate 20 parts glycidyl methacrylate 20 parts RUVA-093 (Note 1) 5 parts 2,2′-azobisisobutyi Lonitrile 1 part After aging at 115 ° C for 2 hours, the temperature was raised to 140 ° C, and then linseed oil fatty acid 30 parts and N, N
160 parts of dimethylaminoethanol
For 5 hours to carry out an addition reaction of the fatty acid. The resin acid value was traced by a KOH titration method, and the time when the resin acid value became 1.0 or less was defined as the end point. After completion of the reaction, the mixture was diluted with 45 parts of xylene to obtain a brown transparent viscous fatty acid-modified copolymer solution having a nonvolatile content of 50%.

Then, the mixture was cooled to 100 ° C., the flask was equipped with a water separator, 5 parts of silicone resin SH-6018, 3.5 parts of mineral spirit, 1.5 parts of xylene, and tetra-n- as a reaction catalyst. Add 0.05 parts of butyl titanate, raise the temperature to 165 ° C, and react for 8 hours in a reflux system while separating water with a water separator. A brown transparent, viscous silicone-modified vinyl resin with a nonvolatile content of 50% A solution was obtained.

(Note 1) RUVA-093: 2- (2'-
Hydroxy-5'-methacryloxyphenyl) -2H
-Benzotriazole, manufactured by Otsuka Chemical Co., Ltd.

Examples 4 to 6 0.3 part by weight of cobalt naphthenate and 1.0 part by weight of lead naphthenate were added to 200 parts of the silicon-modified vinyl resin solution having a nonvolatile content of 50% obtained in each example as a curing catalyst. After the addition of parts, the mixture was stirred until it became uniform to obtain each room temperature-curable coating composition. Example 4 used Example 1, Example 5 used Example 2, and Example 6 used the silicon-modified vinyl-based resin solution of Example 3 having a nonvolatile content of 50%.

Comparative Example 1 To 200 parts of the fatty acid-modified copolymer (A-1) solution having a nonvolatile content of 50% obtained in the preceding step of Example 1, 0.3 part by weight of cobalt naphthenate as a curing catalyst and naphthenic acid Lead 1.
After adding 0 parts by weight, the mixture was stirred until it became uniform to obtain a room temperature curable coating composition.

Performance Test The storage stability of each of the cold-curable coating compositions obtained in Examples 4 to 6 and Comparative Example 1 when stored at 20 ° C. for 1 week was evaluated based on the presence or absence of sediment (物). : No sediment, good storage stability). Further, various tests were conducted on the coated plate coated with each of the room temperature curable coating compositions based on the following test methods. The test results are shown in Table 1 below.

Test method (* 1) Initial drying property: Each cold-curable coating composition was coated on a glass plate with a 300 μm applicator, and then applied at 20 ° C. and 7 ° C.
After being left in a room at 5% RH for 6 hours, the dryness to the touch of the coating film was examined.

◎: No fingerprint is attached at all ○: Fingerprint is slightly attached Δ: Fingerprint is attached ×: The coating film adheres to the finger.

(* 2) Double coating workability: After coating each room-temperature-curable coating composition on a glass plate with a 300 μm applicator, the coating was left for 6 hours in a room at 20 ° C. and 75% RH. Each dry-curable coating composition is dried with a brush to a dry film thickness of 80 to
The coating workability and the state of the coating film when the coating was performed to 100 μm were observed.

：: No abnormality Δ: Smear is observed in the coating film X: The coating film is redissolved at the first coating, and the brushing becomes heavier.

(* 3) Gloss of the coating film: 30 ordinary cold-curable coating compositions were coated on a slate plate coated with “Ales Cera Mild” (a white matte paint manufactured by Kansai Paint Co., Ltd.).
After coating with a 0 μm applicator and drying for one week, the 60 ° specular reflectance was measured.

◎: 90% or more ○: 80% or more, less than 90% Δ: 70% or more, less than 80% ×: Less than 70%.

(* 4) Weather resistance: "Aressera Mild"
Each of the room-temperature-curable coating compositions was placed on a slate plate coated with a white matte paint (manufactured by Kansai Paint Co., Ltd.) in a thickness of 300 μm.
After being coated with an applicator of m and dried for one week, it was evaluated by the gloss retention when exposed for 1500 hours with a sunshine weatherometer.

◎: 90% or more ：: 80% or more and less than 90% Δ: 70% or more and less than 80% ×: less than 70%.

(* 5) Water resistance: Each room temperature curable coating composition was applied on a slate plate with a 300 μm applicator.
The coated plate that had been dried in a room at 20 ° C. and 75% RH for 3 days was immersed in tap water (20 ° C.) for 3 days, and the state of the coating film was visually observed.

：: No abnormality Δ: Slight blistering observed X: Extremely blistering observed

(* 6) Acid resistance: (* 1) 0.5N aqueous 0.1N sulfuric acid solution was applied to the coated plate obtained in the same manner as in the initial drying test.
After cc was dropped, the mixture was left at 20 ° C. for 24 hours, washed with water, and the state of the coating film was observed.

：: No abnormality Δ: Slight whitening observed X: Remarkably whitened and etching of the coating film surface was observed.

[0059]

[Table 1] Table 1

[0060]

The oxidation-curable silicone-modified vinyl resin of the present invention has a main chain of a vinyl polymer, and has an unsaturated fatty acid added to the polymer to impart dryness at room temperature.
Further, a silicone resin is added to improve the weather resistance of the obtained coating film. The coating composition of the present invention contains the oxidation-curable silicone-modified vinyl-based resin of the present invention as a resin component, and has excellent weather resistance and coating film gloss, as well as storability, initial drying property, and two coating operations. It is a room temperature curable coating composition capable of forming a coating film having excellent properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08F 8/14 C08F 8/14 F term (Reference) 4J002 CP171 GH01 4J031 AA05 AA08 AA20 AA47 AA59 AB01 AB06 AC05 AC13 AD03 AE02 AF12 4J035 CA051 CA061 GA02 GB02 GB10 LB01 4J038 DB211 DB351 DB421 NA03 PA18 4J100 AE18Q AL03P AL04P AL05P AL08P AL08Q AL09P AL10Q BA03P BA08P BC08P BC54Q BC74P CA04 CA23 CA31 HC53 HA55 HC01

Claims (3)

[Claims] 1. An epoxy group-containing vinyl copolymer (a) which is a copolymer of an epoxy group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the monomer.
And a fatty acid component (b) containing an unsaturated fatty acid, and a silicon resin (c) containing a hydroxyl group and / or an alkoxyl group directly bonded to a silicon atom. 2. An epoxy group-containing vinyl copolymer (a)
2. The oxidation-curable silicone-modified vinyl resin according to claim 1, which is obtained by adding a fatty acid component (b) to the mixture and then adding a silicone resin (c). 3. A coating composition containing the oxidation-curable silicone-modified vinyl resin according to claim 1 or 2 as a resin component.