JP2008063528A - Coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition excellent in both coating material storing stability and coating film surface drying properties, and useful as a putty for repairing, in particular. <P>SOLUTION: The coating composition contains (A) an unsaturated polyester resin, (B) a compound having a prescribed constitutional unit and (C) a polymerizable unsaturated compound other than the components (A) and (B). (A), (B) and (C) are contained in the ranges of 20-90 mass%, 1-70 mass% and 5-75 mass%, respectively, based on the total mass of the components (A), (B) and (C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coating composition. The present invention particularly relates to a coating composition which is excellent in storage stability of a coating material and surface drying property of a coating film, and particularly useful as a putty for repair.

  Unsaturated polyester resins are generally relatively inexpensive compared to other resins, and are excellent in workability because they are cured in a short time even at room temperature. Furthermore, various physical and chemical properties are excellent depending on the choice of main raw materials. Therefore, it is widely used in various applications such as repair putty paints for vehicles such as automobiles, woodwork paints, molded products, and sealing materials.

  The unsaturated polyester resin composition used in these applications has (1) that it is rapidly cured at room temperature, has excellent surface drying properties, and (2) has excellent adhesion to the substrate. Etc. are required. In particular, the surface drying property at normal temperature (1) is an important factor for workability.

  Conventionally, styrene monomers have been used as reactive diluents for such unsaturated polyester resins from the viewpoints of curability and physical properties. However, in recent years, the use of styrene monomers is being regulated in terms of odor. Therefore, Patent Document 1 discloses an unsaturated polyester resin composition using hydroxyalkyl methacrylate as a reactive diluent instead of styrene monomer without reducing curability and physical properties. According to this composition, although the odor is low, the curing stability is excellent, and the surface drying property is excellent, the adhesion to the substrate may be insufficient.

  Regarding such problems, for example, Patent Document 2 describes a putty or coating composition containing a specific amount of a specific aromatic amine compound in an unsaturated polyester resin and a polymerizable unsaturated compound. According to such a composition, the surface drying property is good, the finished surface after top coating has a good appearance without yellowing, and the internal drying property when thickly coated is excellent. Although it is possible to form a coating film with excellent adhesion to the top coat, there is a possibility that the surface of the composition may be skinned during storage. Since the film surface drying property is lowered, it is extremely difficult to achieve both the storage stability of the paint and the surface drying property of the coating film.

JP 2002-332316 A JP 2005-206781 A

  An object of the present invention is to provide a coating composition which is excellent in both coating storage stability and coating film surface drying property and is particularly useful as a repair putty.

  As a result of intensive studies on the above problems, the present inventors have found that a compound having a specific structural unit in the molecule has oxygen scavenging ability and radical polymerizability, and a coating composition containing the compound has internal curability. The inventors have found that the surface drying property is good, and further that the coating material storage stability and the coating film surface drying property can be compatible, and the present invention has been achieved.

  Therefore, the present invention provides means having the following configuration.

  1. A coating composition containing an unsaturated polyester resin (A), a compound (B) having a structural unit represented by formula (1), and a polymerizable unsaturated compound (C) other than component (A) and component (B) Then, based on the total mass of component (A), component (B) and component (C), (A) is 20 to 90% by mass, (B) is 1 to 70% by mass, and (C) is 5 to 5%. A coating composition characterized by containing in a range of 75% by mass.

(In formula (1), R ¹ and R ² may be the same or different and each represents a hydrogen atom or an organic group having 1 to 10 carbon atoms)
2. 2. The coating composition according to 1 above, wherein the compound (B) is a compound derived from a carboxylic acid compound having a conjugated double bond conjugated to a carbonyl moiety of a carboxyl group.

  3. 3. The paint according to 1 or 2 above, wherein the compound (B) is a reaction product obtained by reacting a carboxylic acid compound having a conjugated double bond conjugated to a carbonyl moiety of a carboxyl group and an epoxy group-containing compound. Composition.

  4). The coating composition according to any one of the above 1 to 3, wherein the compound (B) has two or more structural units represented by the formula (1) in the molecule.

  5. The coating composition according to any one of the above 1 to 4, wherein the polymerizable unsaturated compound (C) comprises a hydroxyalkyl (meth) acrylate and / or a dicyclopentenyl group-containing polymerizable unsaturated compound as a part of the component. object.

  6). 6. The coating composition according to any one of 1 to 5, further comprising a rust inhibitor.

  7). The coating composition according to any one of the above 1 to 6, further comprising an aromatic amine.

  8). The coating method which coats the base material surface with the coating composition in any one of said 1-7.

  9. The coating method which coats the base material surface after coating the coating composition in any one of said 1-7.

  According to the coating composition of the present invention, a compound having a conjugated double bond conjugated to a carbonyl group in a molecule is blended with a coating composition containing an unsaturated polyester resin and a polymerizable unsaturated compound. By optimizing the blending ratio, it is possible to achieve both paint storage stability and coating surface drying. This coating composition has a moderate pot life, good coating workability, and excellent performance such as water resistance adhesion.

  Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to these embodiments, and it is understood that various modifications can be made within the spirit and scope of the present invention. I want to be.

  Hereinafter, each component contained in the coating composition of this invention is demonstrated in order.

Unsaturated polyester resin (A)
As the unsaturated polyester resin (A) used in the present invention, those conventionally used in paints and putty can be applied without limitation, and the surface of the coating film formed using the paint composition of the present invention is dried. From the viewpoint of good properties, it is desirable to have an allyl ether unit of a polyhydric alcohol.

  As a polyhydric alcohol as a manufacturing raw material of the unsaturated polyester resin which has the allyl ether unit of the said polyhydric alcohol, the allyl compound which has a hydroxyl group can be mentioned, for example.

  Examples of the allyl compound having a hydroxyl group include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl. Ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl And ether, pentaerythritol triallyl ether, etc. .

  In the present invention, the unsaturated polyester resin (A) is a total number of moles of all structural units of the unsaturated polyester resin (A) from the viewpoint of coating film internal curability and coating film surface drying. Based on the above, it is desirable to contain 5 to 50 mol%, preferably 10 to 35 mol%.

  Other polyhydric alcohols other than allyl compounds having a hydroxyl group can be used for the unsaturated polyester resin (A). Examples of other polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol 1,9-nonanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2- Chrohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7 -Decalin glycol, bishydroxyethyl terephthalate, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

  Unsaturated polyester resin (A) can be manufactured by the condensation reaction of the said polyhydric alcohol and a polybasic acid.

  Examples of polybasic acids include unsaturated polybasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and tetrabromophthalic anhydride. Examples thereof include acid, tetrachlorophthalic anhydride, het acid anhydride, and hymic anhydride, and these can be used alone or in combination of two or more.

  The unsaturated polybasic acid may be used in combination with a saturated polybasic acid. Examples of the saturated polybasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, hexahydro Phthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, dialkyl esters thereof, and the like. Can be used alone or in combination of two or more.

  The unsaturated polyester resin (A) may be modified with a fatty acid as necessary. Such fatty acids are preferably dry oil fatty acids and / or semi-dry oil fatty acids, such as 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 acid, hemp seed fatty acid, grape kernel oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, Heidiene fatty acid, etc. Can be used alone or in combination of two or more.

  Unsaturated polyester resin (A) can be manufactured by a conventional method, for example, is obtained by carrying out the condensation reaction of the component containing the said polyhydric alcohol and a polybasic acid in nitrogen atmosphere. The heating temperature during the condensation reaction is desirably in the range of 140 to 250 ° C, preferably 160 to 200 ° C, from the viewpoint of preventing gelation.

  The acid value of the unsaturated polyester resin (A) is desirably in the range of 10 to 50 mgKOH / g, preferably 20 to 40 mgKOH / g, from the viewpoint of adhesion to the substrate.

  The weight average molecular weight of the unsaturated polyester resin (A) is 1,000 to 100,000, preferably 2,000 to 50,000.

  In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted to polystyrene. “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) can be used as a gel permeation chromatograph, and “TSKgel G-4000H × L” and “TSKgel G-3000H × L” are used as columns for this. , “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade name) can be used. Here, tetrahydrofuran was used as the mobile phase, the measurement temperature was 40 ° C., the flow rate was 1 cc / min, and the RI refractometer was used as the detector.

Compound (B)
In the present invention, the compound (B) is an essential component blended in order to achieve both the storage stability of the coating composition of the present invention and the surface drying property of the coating film formed using the coating composition, A compound having at least one constitutional unit represented by the formula (1) in the molecule. Here, R ₁ and R ₂ in Formula (1) are preferably hydrogen, and when R ₁ and R ₂ are organic groups, they are preferably alkyl groups, particularly methyl groups.

  The compound (B) used in the present invention may be, for example, a carboxylic acid compound having a conjugated double bond conjugated to the carbonyl moiety of the carboxyl group.

  Specific examples of such carboxylic acid compounds include, for example, sorbic acid, 2,4-pentadienoic acid, trienic acid, 6-phenyl-2,4,6-heptatrienoic acid, retinoic acid (vitamin A), 5-phenyl-2 , 4-pentadienoic acid, muconic acid, hexaene dicarboxylic acid and the like can be exemplified, and sorbic acid is particularly preferred.

  In the present invention, the carboxylic acid compound can be blended as it is, but from the viewpoints of compatibility with the polymerizable unsaturated compound (C) described later and the coating surface drying property, an epoxy group-containing compound, a vinyl ether group. It is desirable to blend as a reaction product obtained by reacting a compound selected from the group consisting of a containing compound and an oxetane compound with the carboxylic acid compound.

  The above compound for reacting with the carboxylic acid compound is an epoxy group-containing compound from the viewpoint of ease of production, compatibility with the polymerizable unsaturated compound (C) described later, adhesion of the formed coating film, and the like. Is preferred.

  Such an epoxy group-containing compound is a compound having at least one alicyclic epoxy group or glycidyl group having a cyclohexene oxide or cyclopentene oxide structure in one molecule, and having an epoxy equivalent of 70 to 5,000, Preferably 80-3,000 can be used suitably. In this epoxy group-containing compound, both an alicyclic epoxy group and a glycidyl group may be mixed in one molecule.

  In the present invention, when the compound (B) has two or more structural units represented by the formula (1) in the molecule, the internal curability of the coating film formed from the coating composition of the present invention and the coating film Since there is an effect of improving both surface drying properties, when the carboxylic acid compound is a monocarboxylic acid, the epoxy group-containing compound may be a compound having two or more epoxy groups in one molecule. desirable.

  Examples of the epoxy group-containing compound containing an alicyclic epoxy group include dicyclopentadiene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl). ) Ether, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy -6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) acetal, bis (3,4-epoxycyclohexyl) ether of ethylene glycol, 3,4-epoxycyclohexanecarboxylic acid diester of ethylene glycol "Epolide GT300" (Daicel Chemical Industries, trade name, trifunctional alicyclic epoxy resin), "Epolide GT400" (Daicel Chemical Industries, trade name, tetrafunctional alicyclic epoxy resin) , “EHPE-3150” (Daicel Chemical Industries, Ltd., trade name, polyfunctional alicyclic epoxy resin), 3,4-epoxycyclohexylmethyl (meth) acrylate and other alicyclic epoxy group-containing ethylenic unsaturation Examples thereof include an alicyclic epoxy group-containing (co) polymer obtained by (co) polymerizing a monomer and, if necessary, another polymerizable unsaturated monomer.

  On the other hand, as an epoxy group-containing compound containing a glycidyl group, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, spiroglycol diglycidyl ether, 2,6-diglycidyl phenyl ether, Sorbitol polyglycidyl ether, triglycidyl isocyanurate, bisphenol A diglycidyl ether , Butadiene dioxide, diglycidyl phthalate, bisphenol type epoxy resin, ε-caprolactone modified bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl group-containing ethylenic polymer Examples thereof include a glycidyl group-containing (co) polymer obtained by (co) polymerizing a saturated monomer and, if necessary, another polymerizable unsaturated monomer.

  Examples of the epoxy group-containing compound include alicyclic epoxy group-containing ethylenically unsaturated monomers such as vinylcyclohexene dioxide, limonene dioxide, and 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl (meta ) Containing an alicyclic epoxy group and a glycidyl group obtained by (co) polymerizing a glycidyl group-containing ethylenically unsaturated monomer such as an acrylate and, if necessary, another polymerizable unsaturated monomer. It may be a polymer or the like.

  The esterification reaction between the carboxylic acid compound and the epoxy group-containing compound usually allows the carboxyl group and the epoxy group to react smoothly in the presence of a polymerization inhibitor without causing a reaction problem such as gelation. It can be carried out under conditions, and is usually suitable by heating at a temperature of about 80 to about 180 ° C. for about 0.5 to about 24 hours.

  The equivalent ratio of carboxyl group to epoxy group is preferably 0.75: 1 to 1.25: 1, more preferably 0.8: 1 to 1.2: 1. Can do.

  In this reaction, an esterification reaction catalyst such as a tertiary amine such as N, N-dimethylaminoethanol, a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used. By using an inert organic solvent or a polymerizable unsaturated compound (C) described later, the viscosity in the system can be adjusted so that the reaction proceeds smoothly.

  Examples of the polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, and trihydroquinone; nitrobenzene, nitro Nitro compounds such as benzoic acid, o-, m- or p-dinitrobenzene, 2,4-dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, picric acid; p-benzoquinone, 1,4-naphthonone, dichlorobenzoquinone Quinone compounds such as chloroanil, anthraquinone and phenanthroquinone; nitroso compounds such as nitrosobenzene and nitroso-β-naphthol, and the like, and radical polymerization inhibitors known per se can be mentioned. It can be used in combination on.

Polymerizable unsaturated compound (C)
In the present invention, the polymerizable unsaturated compound (C) acts as a reactive diluent that can lower the viscosity of the composition during coating to improve coating workability and can also be a film-forming component. A compound having a polymerizable unsaturated group, which may be a compound other than the resin (A) and the compound (B). Specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene and divinylbenzene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meta ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonane Di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,2-bis (4- (3-methacryloxy-2-hydroxypropoxy) -phenyl) propane, di (Meth) acrylic acid esters of mono- or polyhydric alcohols such as (methacryloxyethyl) trimethylhexamethylenediurethane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane; 2-hydroxyethyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as: dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxypropyl acrylate, dicyclopentenyloxypropyl methacrylate, dicyclopentenyl acrylate Dicyclopentenyl group-containing polymerizable unsaturated compounds such as dicyclopentenyl methacrylate; ethylene glycol dimaleate, propylene glycol diitaconate, etc .; 4- (meth) acryloyloxymethoxycarbonylphthalic acid, 4- (meth) acryloyloxy 4- (meth) acryloyloxy group-containing aromatic polycarboxylic acid such as ethoxycarbonylphthalic acid and its anhydride; allyl compounds such as diallyl phthalate, diallyl isophthalate, triallyl phthalate; epoxy (meth) acrylate, polyester Examples include oligomers such as (meth) acrylate, polydimethylsilicon di (meth) acrylate, and urethane (meth) acrylate, and these can be used alone or in combination of two or more.

  Among these, from the viewpoints of coating film surface dryness and adhesion to a substrate, the polymerizable unsaturated compound (C) includes, as at least a part of its components, hydroxyalkyl (meth) acrylate and / or dicyclohexane. Those containing a pentenyl group-containing polymerizable unsaturated compound are desirable.

  In the present invention, when a hydroxyalkyl (meth) acrylate and a compound having a dicyclopentenyl group are used in combination, the use ratio is a mass ratio of the hydroxyalkyl (meth) acrylate / dicyclopentenyl group-containing polymerizable unsaturated compound. If it is within the range of 95/5 to 5/95, preferably 90/10 to 10/90, it is possible to achieve both surface drying and adhesion to the substrate, which is desirable.

Coating composition The coating composition of the present invention contains the resin (A), the compound (B) and the compound (C) as essential components, and is composed of the resin (A), the compound (B) and the compound (C). Based on the total mass of the resin (A), the compound (B) and the compound (C), the use ratio is 20 to 90% by mass, preferably 25 to 85% by mass, and 1 to 70 (B). It is contained in a range of 5% by mass, preferably 3 to 63% by mass, and 5 to 75% by mass, preferably 10 to 70% by mass.

  When (A) is less than 20% by mass, the internal curability of the coating film and the coating film surface drying property are insufficient. On the other hand, when it exceeds 90% by mass, the viscosity becomes high and the coating workability decreases.

  When (B) is less than 1% by mass, the coating film drying property and the storage stability are insufficient. On the other hand, when it exceeds 70% by mass, the coating workability is lowered.

  Further, when (C) is less than 5% by mass, the coating film surface drying property and the coating workability are insufficient, while when it exceeds 75% by mass, the adhesion to the substrate is lowered.

Pigment In the present invention, the pigment is blended in consideration of the coating workability and finish of the coating composition of the present invention, and conventionally known pigments can be used. , Talc, Mica, Barium sulfate, Kaolin, Calcium carbonate, Clay, Silica, Quartz, Glass and other extender pigments; Titanium white, Bengala, Carbon black, Iron black, etc. Can also be used. These can be used alone or in combination of two or more.

  In addition, the amount of the pigment used is 70 to 500 mass with respect to 100 mass parts of the resin solid content contained in the coating composition from the viewpoint of polishing workability, finish, and water adhesion when used for putty. Part, preferably in the range of 80 to 200 parts by weight.

Rust preventive agent The paint composition of the present invention may contain a rust preventive agent from the viewpoint of improving the water-resistant adhesion of the formed coating film. Examples of the rust preventive include phosphates such as zinc phosphate, calcium phosphate, zinc phosphite, potassium phosphite, and calcium phosphite; polyphosphates such as aluminum dihydrogen tripolyphosphate; zinc molybdate, molybdic acid Molybdate system such as calcium, phosphomolybdate system such as aluminum phosphomolybdate; borate system; metaborate system such as barium metaborate; cyanamide zinc calcium system; calcium, zinc, cobalt, lead, strontium, Modified silica in which cations such as barium are bonded to porous silica particles, ion exchange silica by binding cations by ion exchange; aluminum pyrophosphate type; rust preventive pigments such as zinc oxide, and 1- (benzothiazole- 2-ylthio) succinic acid, (2-benzothiazol) 2-ylthio) succinic acid di _{- (C 12 to 14} alkyl) benzothiazole compounds such as ammonium salts; 4-methyl -γ-oxo - addition reaction product of benzene butanoic acid and N- ethylmorpholine, 4-methyl - Examples thereof include organic rust preventives such as ketocarboxylic acids such as an addition reaction product of γ-oxo-benzenebutanoic acid and zirconium, and these can be used alone or in combination of two or more. Among these, phosphate-based rust preventive pigments are particularly suitable from the viewpoint of improving the water-resistant adhesion on the steel plate surface.

  The compounding amount of the rust preventive is selected from the viewpoints of polishing workability and finishability when used for putty, curability and drying properties, spatability, heat-resistant yellowing, etc., unsaturated polyester resin (A), compound ( B) and the polymerizable unsaturated compound (C) may be in the range of 3 to 50 parts by mass, preferably 5 to 45 parts by mass with respect to 100 parts by mass of the total.

Aromatic amine A curing accelerator can be blended in the coating composition of the present invention as necessary for the purpose of further improving the curability. As the curing accelerator, conventionally known ones can be used without any particular limitation, but aromatic amines are particularly preferable from the viewpoints of curability and drying properties, and the top coating film coated on the putty composition should have little yellowing. Therefore, among such aromatic amines, compounds having a dimethylamino group are preferred. Specifically, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate 3-dimethylaminobenzoic acid, ethyl 3-dimethylaminobenzoate, ethyl 3-dimethylaminobenzoate (n-butoxy), isoamyl 3-dimethylaminobenzoate, 2-dimethylhexyl 3-dimethylaminobenzoate, 2-dimethyl Examples include aminobenzoic acid, ethyl 2-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate (n-butoxy), isoamyl 2-dimethylaminobenzoate, 2-ethylhexyl 2-dimethylaminobenzoate, and the like. Species can be used alone or in combination of two or more Of these, 4-dimethylaminobenzoic acid and 3-dimethylaminobenzoic acid are particularly suitable.

  The amount of the aromatic amine used is 0.01 to 2.0 parts by mass, preferably 100 parts by mass of the total mass of the unsaturated polyester resin (A), compound (B) and polymerizable unsaturated compound (C). Is preferably in the range of 0.05 to 1.5 parts by mass from the viewpoints of pot life (gelation time), air drying property and polishing property of the formed coating film, and heat yellowing of the top coating film.

  Examples of curing accelerators other than the aromatic amine include, for example, metal dryers such as cobalt naphthenate, copper naphthenate, barium naphthenate, cobalt octenoate, manganese octenoate, zinc octenoate, and vanadium octenoate; Examples include tertiary amines and quaternary ammonium salts other than the aromatic amines exemplified, and these can be used alone or in combination of two or more. When using the said metal dryer, the quantity is the range of 0.01-5 mass parts with respect to 100 mass parts of total mass of unsaturated polyester resin (A), a compound (B), and a polymerizable unsaturated compound (B). Is suitable.

  If necessary, the composition of the present invention may further contain a curing aid accelerator known in the art, a polymerization inhibitor as listed in the description of the compound (B), and the like.

  Examples of the curing accelerator include aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl). ) -P-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) ) N, N-substituted anilines such as aniline and diethanolaniline, N, N-substituted p -Amines such as toluidine and 4- (N, N-substituted amino) benzaldehyde. These curing aid accelerators may be used alone or in combination of two or more.

  If necessary, the coating composition of the present invention further includes, for example, an ultraviolet stabilizer, an ultraviolet absorber, a low shrinkage agent, an antioxidant, an anti-skinning agent, a plasticizer, an aggregate, a flame retardant, a stabilizer, Viscosity modifiers such as reinforcing materials, thinning agents, pigment dispersants, modifying resins, solvents, thixotropic agents, thixotropic agents, antifoaming agents, leveling agents, silane coupling agents, paraffin and other air barrier agents, aldehydes A scavenger or the like can be blended.

  The coating composition of the present invention can provide a coating film having good coating workability and excellent physical properties even when an organic solvent is not substantially blended. For example, it can be suitably used as a putty application. However, if necessary, an organic solvent such as toluene, xylene, methanol, ethanol, propanol, butanol, ethyl acetate, butyl acetate, acetone, or methyl ethyl ketone can be added as a viscosity modifier.

  The coating composition of the present invention can contain a radical curing agent for curing the coating film. Examples of such radical curing agents include organic peroxides, specifically diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyls. Conventionally known ones such as peresters and percarbonates can be used, and these may be used alone or in combination of two or more.

  The blending amount of the radical curing agent is not particularly limited and can be appropriately adjusted according to the coating environment and the physical properties of the coating film. However, the unsaturated polyester resin (A), the compound (B), and the polymerizable unsaturated It is preferable to be within a range of 0.1 to 6 parts by mass with respect to 100 parts by mass of the total mass of the compound (C).

  The radical curing agent is preferably mixed and blended immediately before use, for example, by making the coating composition of the present invention into a two-pack type.

  The composition of the present invention can be applied by a conventionally known method, and the coated film can be cured to the inside of the film by drying at normal temperature or by forced drying. Examples of the substrate surface include metal surfaces such as iron, zinc, and aluminum, chemically treated surfaces thereof, plastics, wood, etc., and old paint surfaces painted on them. It is appropriate to perform sanding around the damaged part as necessary.

  In the present invention, a top coat may be applied to the coating film of the above composition. As the top coat, acrylic lacquer, acrylic melamine resin-based paint, urethane curable paint, acrylic urethane resin-based paint, acid-epoxy curable type Commonly used organic solvent-based, water-based, powder, and other paints such as paints, fluororesin paints, alkyd resin paints, alkyd resin melamine resin paints, and polyester melamine resin paints can be used without particular limitation.

  Hereinafter, the present invention will be further described with reference to examples. Here, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Production and production example 1 of unsaturated polyester resin
Diethylene glycol 397.5 g, dipropylene glycol 134 g, fumaric acid 580 g, pentaerythritol triallyl ether were added to a 2 liter four-necked flask equipped with a stirrer, gas introduction tube, rectifying column, thermometer, decompression device and reflux condenser. 256 g and hydroquinone 0.5 g were added, heated to 150 ° C. while blowing nitrogen gas, and then heated to 180 ° C. Subsequently, the rectification column is changed to a water separator at the same temperature, and the condensation reaction is performed by refluxing toluene. After the reaction, toluene is removed under reduced pressure, and the acid value is 35 mg KOH / g, the weight average molecular weight is 3,000. Unsaturated polyester resin (A) was obtained.

Production and production example 2 of sorbic acid ester
A 500 ml round bottom flask equipped with a stirrer, a thermometer, an air introduction tube and a cooling tube is equipped with 100 g of “Epicoat 828” (trade name, manufactured by Japan Epoxy Resin, bisphenol A type epoxy resin having an epoxy equivalent of 186) and 62.3 g of sorbic acid. Then, 3.5 g of tetrabutylammonium bromide and 0.33 g of 2,6-di-tert-butyl-4-methylphenol were charged and stirred at 105 ° C. for 7 hours to obtain sorbic acid ester (B-1). The acid value at the beginning of the reaction is 188.2 mgKOH / g, the epoxy value is 3.24 mmol / g, the acid value after the reaction is 9.0 mgKOH / g, the epoxy value is 0.142 mmol / g, about 95% The reaction rate was.

Production Example 3
In the same manner as in Production Example 2 above, “Epolite 1500NP” (trade name, manufactured by Kyoeisha Chemical Co., Ltd., neopentyl glycol diglycidyl ether, epoxy equivalent 154) was added to a 500 ml round bottom flask equipped with a stirrer, thermometer, air introduction tube and cooling tube 100 g, 72.8 g of sorbic acid, 4.2 g of tetrabutylammonium bromide, and 0.35 g of 2,6-di-tert-butyl-4-methylphenol were added and reacted with stirring at 105 ° C. for 10 hours to obtain a sorbic acid ester (B -2) was obtained. The acid value at the beginning of the reaction is 205.6 mg KOH / g, the epoxy value is 3.66 mmol / g, the acid value after the reaction is 9.8 mg KOH / g, the epoxy value is 0.174 mmol / g, about 95% The reaction rate was.

Production Example 4
In the same manner as in Production Example 2, a 500 ml round bottom flask equipped with a stirrer, thermometer, air introduction tube, and cooling tube was added to “Epiol TMP-100” (trade name, manufactured by NOF Corporation, trimethylolpropane triglycidyl ether, epoxy. Equivalent 135) 100 g, sorbic acid 83 g, tetrabutylammonium bromide 4.7 g, 2,6-di-tert-butyl-4-methylphenol 0.37 g were charged and stirred at 105 ° C. for 10 hours to give a sorbate ester ( B-3) was obtained. The acid value at the beginning of the reaction is 220.8 mgKOH / g, the epoxy value is 3.94 mmol / g, the acid value after the reaction is 10.4 mgKOH / g, the epoxy value is 0.18 mmol / g, about 95% The reaction rate was.

Production of methacrylate ester Production Example 5
The procedure of Production Example 2 was repeated except that 47.7 g of methacrylic acid was used in place of 62.3 g of sorbic acid to obtain a methacrylic acid ester.

Production Examples 1 to 11 and Comparative Examples 1 to 3 of Unsaturated Polyester Resin Composition
Each composition was blended so as to have the blended composition shown in Table 1 below, and stirred uniformly to obtain each unsaturated polyester resin composition. In addition, the amount (part) of unsaturated polyester resin (A), sorbic acid ester (B), and methacrylic acid ester in the table is the amount of solid content.

Putty-based production examples 12-23 and comparative examples 4-6
To 100 parts of the unsaturated polyester resin composition obtained in the above production example, “Nikka octix cobalt 12%” (trade name, manufactured by Nippon Kagaku Sangyo Co., Ltd., cobalt octylate), hydroquinone, “CR-95” (trade name) , Manufactured by Ishihara Sangyo Co., Ltd., titanium oxide), “Crown Talc DR” (trade name, Matsumura Sangyo Co., Ltd., talc) and “EXPART NP-1007” (trade name, manufactured by Toho Pigment Industries Co., Ltd., calcium phosphite / zinc phosphate) Each component was blended and stirred with the blending composition shown in Table 2, 300 ml of this was sampled, and mixed and dispersed for 20 minutes with a high-speed kneader to obtain each putty base.

Coating The surface of “SPCC-SB” (manufactured by Nippon Test Panel Co., Ltd., iron plate) was lightly polished with water-resistant paper # 240, and this was used as the substrate surface. To each putty base obtained above, 2% of “LUC common curing agent” (trade name, main component: cyclohexanone peroxide, manufactured by Kansai Paint Co., Ltd.) was added, and the putty composition uniformly mixed on each base material surface The test plate was coated with a spatula and then applied to a thickness of 2 mm and subjected to the following evaluation test. The results are shown in Table 2.

Evaluation test Each putty composition obtained above was tested according to the following evaluation methods and standards. The results are shown in Table 2.

Spatability A mixture of each putty base and a curing agent is used to spat the test piece with a spatula. Nobi, spatula cut, and spatula were examined at that time (◯: good, Δ: slightly bad, x: bad).

Dryability Each test coated plate was allowed to stand at room temperature (20 ° C.) for 40 minutes, and then the tack of the surface of each test plate and the degree of internal curing were examined by finger touch (◯: good, ○ Δ: slightly tacky on the surface, (Triangle | delta): The surface is a little tacky and the inside is also slightly hardened | cured, X: The surface has a tack and the inside is also hardened | cured poorly.

Pot life Gelation time at room temperature (20 ° C) after blending the curing agent.

Skin property Each 20 g of putty base was put on a dish of about 5 cm in diameter such as aluminum and left for 10 days in an atmosphere of 40 ° C. (open system), and the degree of skin on the putty surface was examined (○: good without skin, △ : Slight skinning, somewhat poor, ×: poor skinning).

Water resistance adhesion After the test coating plate was left to dry at room temperature (20 ° C.) for 6 hours, the coated surface was lightly polished with # 400 water resistant paper, and “Letane PG80 White Base” (trade name, acrylic urethane resin-based topcoat) A coating material (manufactured by Kansai Paint Co., Ltd.) was spray-coated to a dry film thickness of 50 μm and dried at 60 ° C. for 30 minutes to obtain each coated plate. Each coated plate was immersed in water at 80 ° C. for 1 day, then taken out from the water, bent from the center, and the coating state of the bent portion was observed (◯: good, Δ: coating between steel plate and putty) X: The coating film is completely peeled from between the steel plate and the putty).

  The present invention is industrially useful because it provides a coating composition having excellent coating storage stability and coating surface drying properties.

Claims (9)

A coating composition containing an unsaturated polyester resin (A), a compound (B) having a structural unit represented by formula (1), and a polymerizable unsaturated compound (C) other than component (A) and component (B) Then, based on the total mass of component (A), component (B) and component (C), (A) is 20 to 90% by mass, (B) is 1 to 70% by mass, and (C) is 5 to 5%. A coating composition characterized by containing in a range of 75% by mass.

(In formula (1), R ¹ and R ² may be the same or different and each represents a hydrogen atom or an organic group having 1 to 10 carbon atoms)   The coating composition according to claim 1, wherein the compound (B) is a compound derived from a carboxylic acid compound having a conjugated double bond conjugated to a carbonyl moiety of a carboxyl group.   The compound (B) is a reaction product obtained by reacting a carboxylic acid compound having a conjugated double bond conjugated to a carbonyl moiety of a carboxyl group and an epoxy group-containing compound. Paint composition.   The coating composition of any one of Claims 1-3 in which a compound (B) has 2 or more of structural units represented by Formula (1) in a molecule | numerator.   The polymerizable unsaturated compound (C) includes a hydroxyalkyl (meth) acrylate and / or a dicyclopentenyl group-containing polymerizable unsaturated compound as a part of the component thereof. Paint composition.   The coating composition according to any one of claims 1 to 5, further comprising a rust inhibitor.   The coating composition according to any one of claims 1 to 6, further comprising an aromatic amine.   The coating method which coats the base material surface with the coating composition of any one of Claims 1-7.   The coating method which coats the base material surface after coating the coating composition of any one of Claims 1-7 on top.