JPH0730288B2 - Two-component urethane coating composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a two-component urethane coating composition, and more specifically, it has excellent dispersion stability, and can give a coating film appearance with high gloss and good transparency, and The present invention relates to a two-component urethane coating composition that is extremely dry, has excellent polishing properties and workability, and is extremely useful for repairing automobiles.

2. Description of the Related Art 2 using a curing agent component composed of a compound having an isocyanate group and a film-forming resin component having a hydroxyl group
Liquid urethane paints have been drawing attention in various fields such as automobile repair and woodworking because they do not require baking.

In such a paint, it is desirable that the paint is quick-drying from the viewpoints of shortening the process, saving heat energy, and the like, and various devises have been made in order to provide the two-component urethane paint with quick-drying property. None was satisfactory. For example, in the technique of using an acrylic resin having a high molecular weight or a high glass transition temperature (Tg) as a resin component, the number of coatings increases because the spray solid content is low.
There is a drawback that the appearance is poor, and the technique of compounding cellulose resins such as nitrocellulose and CAB also has the same disadvantages as above.In the technique that uses a large amount of catalyst, the pot life is short and the coating appearance is There are many problems such as badness, and the technique using an aromatic polyisocyanate has not been put into practical use in terms of weather resistance.

By adding suitable three-dimensionally cross-linked so-called gelled resin particles that are substantially insoluble in the solvent to the two-component urethane paint, the pigment filling effect as a plastic pigment, the hard resin effect due to the cross-linked resin, etc. Therefore, it is expected that a quick-drying property can be obtained. Various studies have been made on three-dimensionally crosslinked resin particles, but the conventional one increases the resin solid content in a paint using a solvent-based resin,
It has been developed for the purpose of rheology control in order to compensate for defects such as sagging, cissing and deterioration of weather resistance when obtaining a high solid paint, and normal dry type two-component urethane paint is not considered at all, In fact, even with such three-dimensionally crosslinked resin particles, it was not possible to obtain a two-component urethane paint which is satisfactory in terms of workability, drying property and finished appearance. In particular, when the conventional three-dimensional crosslinked resin particles are used, there is a problem in terms of dispersion stability, and it is not possible to obtain a coated surface having high gloss and good transparency and excellent appearance of the coating film.

Therefore, the present inventors have found that the composite resin particles obtained by grafting the linear acrylic polymer chains on the three-dimensional crosslinked resin particles or the linear acrylic polymer partially penetrates into the three-dimensional crosslinked resin particles, and partly outwards. We have found a two-component urethane coating that can improve the dispersion stability of the particles by using the extended composite resin particles and give a coating surface that is excellent in the appearance of the coating such as gloss and transparency. Sho 61-136966,
61-136964). As a result of further research thereafter, by using a composite resin particle in which a metal element having a catalytic action for the urethanization reaction is supported on a linear acrylic polymer grafted to the three-dimensional crosslinked resin particle in a two-component urethane coating, It was found that the curability and drying properties could be further improved, and a patent application was filed (Japanese Patent Application No. 61-136967). The present invention, like the above-mentioned series of studies, was made for the purpose of obtaining a normally-dried two-component urethane paint which is particularly excellent in workability, drying property and finished appearance.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, the object of the present invention is a two-component urethane coating composition, which can give a coating surface having high gloss and excellent transparency and good dryness. Therefore, it is to obtain a coating composition which is excellent in polishing property, workability, and dispersion stability and is useful for automobile repair and the like. Furthermore, even in a two-component urethane coating composition using three-dimensional crosslinked resin particles having a metal-supported acrylic polymer chain, the appearance tends to slightly deteriorate when the amount of resin particles is increased in order to further improve the drying property. However, there is a problem in that the stability of the metal element loading tends to occur due to the solution of the problem and the change of the coating properties such as basicity and acidity. Therefore, it is also an object of the present invention to achieve more stable metal element loading.

Means for Solving the Problems According to the present invention, the above-mentioned object is a curing agent component comprising a main component (A) consisting of a hydroxyl group-containing film-forming resin, metal element-containing crosslinked resin particles and a solvent, and a compound having an isocyanate group. More preferably, the crosslinked resin particles are composed of two liquids of (B), and the crosslinked resin particles are bonded to the metal element-containing three-dimensional resin particles with a substantially linear polymer, partially invaded, or a combination of a bond and a partially invaded. The composite resin particles which are supported by either of them, and the solid content weight ratio of the hydroxyl group-containing film-forming resin and the composite resin particles is 99/1 to 40/60, and the isocyanate group in the component (B) and the component (A) Equivalent ratio of the hydroxyl groups of the above (the total amount of the hydroxyl groups of the hydroxyl group-containing film-forming resin and the hydroxyl groups when the linear polymer has hydroxyl groups) is 0.5 to 2.0. It is achieved by a coating composition.

The crosslinked resin particles preferably used in the present invention are obtained by carrying a metal element-containing three-dimensional resin particle with a substantially linear polymer bonded, partially penetrating or by a combination of both bonding and partially penetrating. It is a new type of composite three-dimensional resin particles. Incidentally, in the present specification, "metal element" means "a metal element capable of exerting a catalytic action on the urethanization reaction", specifically Zn, Sn, Al, Fe, Zr,
As Ti, GePb, Cr, Mg, Ca, Sr, Li, Na, K and the like, Sn, Zn, Al, Fe, Zr and the like are particularly preferable metal elements.

As described in detail in the patent application specification of "Composite three-dimensional resin particles and their manufacturing method" dated April 22, 1987 by the same applicant, the resin particles are first made of polyester resin,
Diameter of condensation resin such as epoxy resin and amino resin and polymerization resin such as acrylic resin and vinyl resin.
The main body of the particle is a metal element-containing polymer particles having a three-dimensional structure of about 01 ~ 10μ, for example, by polymerizing a polymerizable monomer containing a metal element-containing polymerizable monomer and a crosslinkable monomer, or a suitable functional group It can be prepared by a method in which a metal compound is introduced into the polymer particles by esterification or transesterification. Therefore, the particle component and the manufacturing method can be appropriately selected by those skilled in the polymer field. More preferably, in the production process of the resin particles, or after production, an addition-polymerizable unsaturated group is carried or introduced on the particle surface, and then an addition-polymerizable ethylene compound is subjected to addition polymerization to graft a linear polymer. Whether the polymerizable ethylene compound is solution-polymerized in the presence of the metal element-containing polymer particles to form an interpenetration type composite particle in which the linear polymer partially penetrates into the particle and partially extends outward Alternatively, by allowing the composite resin particles grafted with the linear polymer as described above to exist in the system during the solution polymerization of the polymerizable ethylene compound, the linear polymer is bonded to the main body of the metal element-containing polymer particles. It is possible to obtain a composite resin particle supported by a combination of both intrusions.

In all of the above, the linear polymer is an acrylic polymer obtained by addition polymerization of an ethylenic saturated compound, but the metal element-containing polymer particles having a three-dimensional structure are caused to retain an appropriate functional group, while It is also possible to chemically bond the linear polymer to the particle main body by reacting the reactive derivative of the linear polymer, and therefore the particle main body and the linear polymer are appropriately selected from any resin, Further, the manufacturing method thereof can be appropriately selected by a person skilled in the art of the polymer. However, in the present invention, since it is the composite three-dimensional resin particles composed of a polymer resin such as acrylic as both the particle main body part and the linear polymer part, which is important from the viewpoint of ease of production and application in the coating field, A method for producing composite three-dimensional acrylic resin particles according to a particularly preferred embodiment of the present invention will be described.

Such composite three-dimensional resin particles can be advantageously produced by the following method. That is, two unsaturated groups having different copolymerizability are used.
Emulsion polymerization of a polyfunctional monomer containing the above and a metal element-containing polymerizable monomer containing a crosslinkable monomer that undergoes a polymerization reaction with one unsaturated group of the polyfunctional monomer, and the other unsaturated group of the polyfunctional monomer is First, the metal element-containing three-dimensional resin particles to be left are made, and then the polymerizable monomer that causes a polymerization reaction with the other unsaturated group described above and, if necessary, other polymerizable monomers are added, and graft polymerization is performed. It is a method of forming a linear polymer graft chain on.

The unsaturated groups having different copolymerizability are monosubstituted ethylene or
As represented by 1,1-di-substituted ethylene bonds and 1,2-di-substituted ethylene or poly-substituted ethylene bonds, those that have no selectivity for the partner monomer and those that are selective, or those that have homopolymerizability. In the present invention, a polyfunctional monomer having two or more unsaturated groups having different copolymerizability in the molecule of the composite three-dimensional resin particles is an unsaturated bond having different reactivity. Advantageously used for synthesis. Particularly preferred polyfunctional monomers are allyl (meth) acrylate, an adduct of allyl glycidyl ether with (meth) acrylic acid, an adduct of monoallylamine or diallylamine with glycidyl (meth) acrylate or an isocyanate having a (meth) acryloyl group,
Addition product of allyl alcohol and isocyanate having (meth) acryloyl group, addition product of maleic acid or fumaric acid and glycidyl (meth) acrylate, monoester of maleic acid or fumaric acid and glycidyl (meth)
An acrylate adduct and an adduct of a fatty acid having an unsaturated group and glycidyl (meth) acrylate. The unsaturated groups contained in acryloyl and methacryloyl in these compounds have no selectivity with respect to the counterpart monomer and react with any polymerizable monomer, but the other allyl group or maleic acid type double bond or unsaturated fatty acid Since the double bond and the like therein selectively react with the polymerizable aromatic compound, it is convenient to use the former for the synthesis of the particle main body and the latter for the synthesis of the linear polymer.

First, a metal element-containing three-dimensional resin particle is prepared by emulsion polymerization using the above-mentioned polyfunctional monomer and another compound having an α, β-ethylenically unsaturated bond, a part of which is a crosslinkable monomer, and a metal element-containing polymerizable monomer. To be As the crosslinkable monomer used at this time, a compound having two or more radically polymerizable ethylenically unsaturated groups in the molecule, for example, a polymerizable unsaturated monocarboxylic acid ester of polyhydric alcohol, polymerization of polybasic acid Unsaturated alcohol ester or a combination of compounds having one or more α, β-ethylenically unsaturated bonds with mutually reactive functional groups such as (meth) acrylic acid and glycidyl (meth) acrylate; hydroxy (meth) acrylate and isocyanate Alkyl (meth) acrylate (blocked); radically polymerizable silane coupling agents such as vinyltrialkoxysilane and (meth) acryloxyalkyltrialkoxysilane are advantageously used. In addition, other α, β-
As the compound having an ethylenically unsaturated bond, any monomer used in the synthesis of an acrylic resin is used, but a polymerizable aromatic compound showing selective reactivity with the maleic acid type double bond is left behind. Compounds should be excluded.

Such monomers are roughly classified into the following groups.

(I) Carboxyl group-containing monomer; for example, acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
Fumaric acid etc.

(II) Hydroxyl group-containing monomer; for example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol and the like.

(III) Nitrogen-containing alkyl acrylate or methacrylate; for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and the like.

(IV) Polymerizable amides such as acrylic acid amide and methacrylic acid amide.

(V) Polymerizable nitriles such as acrylonitrile and methacrylonitrile.

(VI) alkyl acrylate or methacrylate;
For example, methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and the like.

(VII) Glycidyl (meth) acrylate.

(VIII) α-olefins such as ethylene and propylene.

(IX) Vinyl compound; for example, vinyl acetate, vinyl propionate and the like.

(X) Diene compound; for example, butadiene and isoprene.

(XI) A compound obtained by reacting a compound having a functional group that chemically reacts with the above-mentioned monomer; for example, a reaction product monomer of a hydroxyl group-containing monomer (II) and an isocyanate compound, or a carboxyl group-containing monomer (I) and glycidyl Monomers produced by reaction with group-containing compounds.

These monomers are used alone or in combination.

The metal element-containing polymerizable monomer is a compound having a metal element having a catalytic action in the urethanization reaction and a polymerizable unsaturated group, and more specifically, the following compounds are conveniently used.

As the metal element-containing polymerizable monomer, acrylic acid, methacrylic acid, itaconic acid, a metal ester of a polymerizable organic acid such as maleic acid, a metal salt or a vinyl metal, and a still metal can be used, and the metal is It may have a hydroxyl group, an organic acid residue, a (substituted) alkyl group, and the like.
For example, zinc may be zinc mono (meth) acrylate, zinc di (meth) acrylate, tin may be tributyltin (meth) acrylate, dibutyltin di (meth) acrylate, and aluminum may be dihydroxyaluminum (meth) acrylate, hydroxyaluminum diacrylate. (Meth) acrylate, ferrocene (meth) acryloylferrocene and furyl (meth) acryloylferrocene, zirconium (meth) acryloxyzirconium octate, (meth) acryloxyzirconium laurate, etc. (Meth) acryloyldiisostearoyl titanate, isopropyldi (meth) acryloylisostearoyl titanate, etc. Data) acrylate, styryl triethyl germane, vinyl triethyl germane, as the lead include diphenyl Namariji (meth) acrylate, styryl triethyl Pb, general formula _{(CH 2 = CH) xMnRn -} x; (CH 2 = CHC 6 H ₄ ) xMnRn _- x; (CH ₂ = CR'COO) xMnRn _- x; (wherein M is a metal element, R is a (substituted) alkyl or (substituted) phenyl or hydroxyl, R'is H or methyl, and n is a metal. The valence of the element, x is an integer smaller than n), and the like.

Further, as described above, a known metal introduction method may be used as a method for introducing the metal element by a chemical reaction in the post-treatment after forming the particle main body without using the metal element-containing polymerizable monomer, but preferably a metal compound It is an esterification reaction or a transesterification reaction between and. Metal compounds used in this method include magnesium chloride, calcium oxide, chromium chloride, zinc oxide, tributyltin oxide, dibutyltin oxide, triethyltin chloride, tribenzyltin chloride, diethylaluminum chloride, metal oxides such as aluminum hydroxide, Metal halides and metal hydroxides are preferred. These compounds can be easily esterified or transesterified with the carboxyl group or neutralized carboxyl group of the particle body by a known method to introduce the metal element. Alkali metal elements such as sodium, potassium and calcium and alkaline earth metal elements can be introduced by ionic bond with the carboxyl group of the particle body simply by adding hydroxide.

In the polymerization of the polyfunctional monomer, the other compound having an α, β-ethylenically unsaturated bond, and the polymerizable monomer containing a metal element, a usual polymerization initiator is used, and three-dimensional particles are prepared according to a conventional method. , As described in JP-A-58-129066. It is particularly preferable to use as the emulsifier a resin having a group represented by (R is a C ₁ -C ₆ alkylene or phenylene group, and Y is —COO or SO ₃ ).

The reaction solution containing the metal element-containing three-dimensional resin particles obtained in this manner is then added with a polymerizable aromatic compound such as styrene, α-methylstyrene, vinyltoluene, or t-butylstyrene, if necessary. Are added together with the monomers of 1 to produce a substantially linear polymer chain by graft polymerization.

By the above method, composite resin particles having a substantially linear polymer chemically bonded to the metal element-containing three-dimensional resin particles can be obtained. In the present invention, the metal element-containing three-dimensional resin particles and the substantially linear polymer do not necessarily have to be chemically bonded, and as described above, a part of the linear polymer is a part of the particle main body. It may be a partly interstitial type of carrier that invades into the core and partly extends outward, or may be a carrier of a combination of both a chemical bond and partly invader. As described in Japanese Patent Application No. 59-267019 filed by the same applicant, the partially interstitial composite resin particles are prepared by adding addition-polymerizable ethylene compounds in the presence of metal-containing three-dimensional resin particles in a non-alcoholic organic solvent. When polymerized, a resin varnish containing partially interstitial composite resin particles dispersed and contained in the vinyl resin solution in which the addition-polymerizable ethylene compound is polymerized is obtained, and in this case, at least a part of the addition-polymerizable ethylene compound is added. By using a hydroxyl group-containing monomer, in the system comprising a hydroxyl group-containing film-forming resin and crosslinked resin particles, the crosslinked resin particles partially penetrate the linear hydroxyl group-containing polymer chain into the metal-containing three-dimensional resin particle body. The resin varnish thus obtained can be conveniently used as it is for the purpose of the present invention.
When the linear polymer is supported on the particle body by a combination of both chemical bonding and partial penetration, the above-mentioned combination method, that is, the linear polymer is chemically bonded to the three-dimensional resin particles containing the metal element. The composite resin particles thus prepared may be prepared, and solution polymerization of the addition-polymerizable ethylene compound may be carried out in the presence of the particles. Of course, also in this case, by selecting the hydroxyl group-containing ethylene compound, the produced resin varnish can be used as it is as the film-forming resin and the crosslinked resin particles.

Since there is no restriction on the radical-polymerizable monomer used when synthesizing the linear polymer chain, the linear polymer chain can be designed freely. As such a monomer, a monomer having a group having active hydrogen, for example, a hydroxyl group, an amino group, etc .; a monomer having an acidic group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a basic group such as an amino group, ammonium; urea, urethane It is possible to incorporate various functional groups into a linear polymer by using a monomer having a group having an atomic group with high cohesive energy such as acid amide.

In the present invention, the three-dimensional crosslinked resin particles are usually a solid content weight ratio of the hydroxyl group-containing film-forming resin 1/99 to 60
/ 40 It is preferably mixed in a ratio of 5/95 to 30/70. The reason is that if the composite resin particles are less than 1% in the resin solid content of the main component, the contribution to the drying property is too small to obtain the quick drying property, and if it exceeds 60%, the leveling property is deteriorated and the appearance is deteriorated. Because it gets worse.

When a linear polymer is supported on three-dimensional cross-linked resin particles, it prevents the particles from approaching each other and helps to evenly disperse the particles in the system, and the compatibility with the hydroxyl group-containing resin is good and the coating film appearance When the pigment is present, it has the function of wrapping around the pigment and stabilizing it, helping to stabilize the dispersion, and having a film-forming ability, giving a coating film with excellent gloss and transparency. You can Further, since the resin particle main body is three-dimensionally cross-linked, it is possible to obtain excellent quick-drying and polishing properties due to the hard resin effect in addition to the pigment filling effect.

Further, the linear polymer of the composite resin particles has a group containing an active hydrogen such as a hydroxyl group or an amino group, an acidic group or a basic group to improve the reactivity of the particles or the reactivity in the vicinity of the particles. The drying property can be improved.
That is, hydroxyl groups, amino groups, etc. react with the isocyanate groups of the curing agent and the particles themselves react, so their immobilization, high molecular weight, and increase in crosslink density directly contribute to the improvement of drying properties, and carboxyl groups, dialkyl Amino or the like accelerates the urethane reaction in the vicinity of the particles by a catalytic effect, and the resin around the particles reacts, and apparently crosslinks, whereby the drying property can be improved.

Furthermore, a linear polymer such as urea, urethane, or acid amide is preferably a group having high cohesive energy, preferably
When a group having a cohesive energy of 6500 cal / mol or more is present, the glass transition temperature (Tg) is increased and the initial drying property is improved, and hydrogen bonds are easily generated between particles-particles and particles-binder. Particles, comparable to weakly cross-linked structures
Since the binder becomes difficult to work, the initial drying property is improved,
Good scratch resistance and polishability.

Further, the metal element-containing crosslinked resin particles of the present invention has a metal element having a catalytic action for the urethanization reaction carried on the particle main body, so that the hydroxylation of the hydroxyl group-containing film-forming resin and the crosslinking agent are carried out particularly near the particles. It can catalyze the reaction, improve the curability, and improve the drying property.
When the amount of such resin particles is increased to improve the drying property more often, the coating film appearance tends to deteriorate, which is often a problem, and the metal element is stably supported on the particle main body to improve curability. It can be prevented by improving surely,
The contradictory requirements of quick-drying property and appearance of the two-component urethane paint can be excellently satisfied. The metal content of the crosslinked resin particles is difficult to specify because the catalytic ability varies depending on the metal species, and may be a catalytically effective amount of the urethanization reaction, for example, in the case of Sn, per particle solid content.
The optimum Sn content is about 0.1 to 2%. However, the catalytic effect is 5
You can expect from 0ppm.

Thus, in the present invention, by using the novel three-dimensional resin particles, it is possible to obtain a coated surface which is quick-drying, has excellent polishing properties and workability, and is excellent in gloss and transparency and has a good coating appearance. A two-part urethane coating composition which can be given can be given.

As the curing agent component, a compound having a normal isocyanate group or a prepolymer thereof is conveniently used, but at this time, the isocyanate group in the curing agent component and the hydroxyl group in the main component resin (the hydroxyl group in the hydroxyl group-containing resin, and When the linear polymer of the composite resin particle has a hydroxyl group, the total amount of the hydroxyl group) is 0.5 to 0.5 in terms of practical equivalent ratio.
It can be appropriately selected and used within the range of 2.0.

The hydroxyl group-containing film-forming resin, the solvent, and the compound having an isocyanate group may be any materials usually used in urethane paints, and the main component and the curing agent component are both normal two-component urethane type paints. Any additives and auxiliaries used in the above can be added, for example, an ultraviolet absorber, a pigment, a catalyst, a solvent and the like.

The coating composition of the present invention has a pot life suitable for air spray coating after mixing the curing main component (A) and the curing component (B) and adjusting the viscosity with a thinner or the like, and has excellent workability and coating. It has a fast drying property, shortens the time required for polishing, and can give a smooth, high-gloss and excellent-appearance coating film, which is especially useful for automobile repair. It is expected to have a wide range of uses in various fields such as prevention and construction.

Hereinafter, the present invention will be described with reference to examples.

Reference Example 1: Preparation of hydroxyl group-containing polymer Stirrer, temperature control device, dropping funnel, nitrogen inlet tube, charged with 50 parts of xylene, 50 parts of butyl acetate in a reactor equipped with a condenser for cooling, in a nitrogen atmosphere , Heated to 120 ° C., 30 parts of styrene, 33.7 parts of methyl methacrylate, 0.5 parts of methacrylic acid, 19.6 parts of n-butyl acrylate,
A mixed solution of 16.2 parts of 2-hydroxyethyl methacrylate and 2 parts of tert-butyl peroxyoctoate was added dropwise over 3 hours. After the dropping was completed, the same temperature was maintained for 3 hours to complete the reaction. The obtained solution is hereinafter abbreviated as Varnish A. This product has a nonvolatile content of 50%, an OH value of 70 mgKOH / Solid, and an acid value of 3 mgKOH / So.
It was a clear solution on the lid.

Reference Example 2: Preparation of dispersion stabilizer Stirrer, temperature control device, nitrogen introduction tube, decanter, 1500 parts of 12-hydroxystearic acid was charged to a reactor equipped with a condenser for heating, and the mixture was stirred at 72 ° C. Was started, and the temperature was further raised to 220 ° C. for esterification. Water generated by the reaction was removed, and when the acid value reached 35, the mixture was cooled to room temperature. Furthermore, 126 parts of glycidyl methacrylate, 3 parts of hydroquinone, 3 parts of 2-methylimidazole, and 775 parts of butyl acetate are added to the same container, and the mixture is stirred for 150 times.
The temperature is raised to ℃ and the reaction is performed at the same temperature for about 1 hour.
An intermediate (a) having 67% and an acid value of 0.3 was obtained.

Separately, 180 parts of xylene was charged into a reactor equipped with a stirrer, a temperature control device, a nitrogen introducing pipe, a condenser for cooling, and a dropping funnel, and the temperature was raised to 110 ° C under stirring in a nitrogen atmosphere, and the intermediate was maintained at the same temperature. (A) 150 parts, methyl methacrylate 4
A mixture consisting of 7.5 parts, 2.5 parts of acrylic acid, and 5.5 parts of tert-butylperoxyoctoate was added dropwise over 3 hours, and the mixture was kept at the same temperature for 3 hours after completion of the addition to give a nonvolatile content of 40%.
% Dispersion stabilizer was obtained.

Reference Example 3: Preparation of cross-linked resin particle-containing dispersion containing metal element A reactor similar to Reference Example 1 was charged with 223 g of Shellzol 340 (a mixture of aliphatic hydrocarbons manufactured by Showa Shell Sekiyu KK) and stirred in a nitrogen atmosphere. The temperature was raised to 100 ° C. At the same temperature, 80.5 parts of methyl methacrylate, 6 parts of glycidyl methacrylate, 6 parts of methacrylic acid, 0.5 parts of diphenyllead dimethacrylate, 17.5 parts of the dispersion stabilizer obtained in Reference Example 2, azobisisobutyronitrile 4 parts of a mixture consisting of 1 part
Dropped over time. After the dropping was completed, 1 part of 2-methylimidazole was further charged and the temperature was raised to 120 ° C. The reaction was carried out at the same temperature for 8 hours to obtain a dispersion liquid of metal-containing crosslinked resin particles having a nonvolatile content of 30%.

The obtained metal-containing crosslinked resin particle dispersion is abbreviated as particle dispersion a. Lead concentration in solid content is 17,000p by X-ray fluorescence analyzer
It was pm.

Reference Example 4: Preparation of Resin Particle-Containing Polymer A reactor similar to Reference Example 1 was charged with 50 parts of particle dispersion a, 50 parts of xylene, and 15 parts of butyl acetate in a nitrogen atmosphere.
The temperature is raised to 120 ° C., 25.5 parts of styrene, 28.6 parts of methyl methacrylate, 0.4 parts of methacrylic acid, 16.7 parts of n-butyl acrylate, 1 part of 2-hydroxyethyl methacrylate.
A mixed solution of 3.8 parts and 2 parts of tert-butyl peroxyoctoate was added dropwise over 3 hours. After the dropping was completed, the same temperature was maintained for 3 hours to complete the reaction, and a resin particle-containing polymer was obtained.
The obtained solution is hereinafter abbreviated as Varnish B.

Reference Example 5: Preparation of dispersion stabilizer 2 Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, decanter, bishydroxyethyl taurine 134 parts, neopentyl glycol 130 parts, azelaic acid 236 parts, phthalic anhydride Charge 186 parts and xylene 27 parts and raise the temperature. Water generated by the reaction is removed by azeotropic distillation with xylene. The temperature is brought to 190 ° C. over about 2 hours from the start of reflux, and stirring and dehydration are continued until the acid value corresponding to the carboxylic acid becomes 145, and then cooled to 140 ° C. Then 140
While maintaining the temperature of ° C, 314 parts of "CARDURA E10" (versic acid glycidyl ester manufactured by Shell Co.) is added dropwise over 30 minutes, and then stirring is continued for 2 hours to complete the reaction.
The resulting polyester resin has an acid value of 59 and a hydroxyl value of 9
It was 0 and Mn = 1054.

Reference Example 6: Synthesis of dispersion stabilizer Using the same apparatus as in Reference Example 5, sodium salt of taurine
Charge 73.5 parts, 100 parts of ethylene glycol, 200 parts of ethylene glycol monomethyl ether, and heat with stirring to raise the temperature to 120 ° C. After the contents reached a uniform dissolved state, Epicoat 1001 (Shell Chemical Co.,
A solution consisting of 470 parts of a glycidyl ether type epoxy resin of bisphenol A, an epoxy equivalent of 470) and 400 parts of ethylene glycol monomethyl ether is added dropwise over 2 hours. After the dropping, stirring and heating are continued for 20 hours to complete the reaction. The reaction product was purified and dried to obtain 518 parts of modified epoxy resin. The acid value of this resin by KOH titration is 49.4, and the fluorescence X
The sulfur content by line analysis was 2.8%.

Reference Example 7: Preparation of Dispersion Stabilizer 140 parts of ethylene glycol monomethyl ether and 140 parts of xylene are placed in 1 Kolben equipped with a stirrer, a nitrogen introducing tube, a temperature control device, and a condenser for cooling, and the temperature is raised to 120 ° C. Monomer mixture of 5 parts of azobisisobutyronitrile dissolved in a separately prepared mixture of 74 parts of methyl methacrylate, 70 parts of 2-ethylhexyl acrylate, 24 parts of 2-hydroxyethyl methacrylate and 12 parts of methacrylic acid, and ethylene 150 parts of glycol monomethyl ether with N- (3-sulfopropyl) -N-methacryloyloxyethyl-N, N
A solution in which 20 parts of dimethyl-ammonium betaine was dissolved was added dropwise to Kolben over 3 hours. After dropping 30
Separately, 0.4 part of t-butylperoxy-2-ethylhexanoate is added to ethylene glycol monomethyl ether 8 parts.
The solution dissolved in 1 part was added and aged at the same temperature for 1 hour to complete the reaction. The solvent was removed to obtain a zwitterionic group-containing acrylic resin having a nonvolatile content of 92%.

Reference Example 8: Synthesis of Monomer Having Unsaturated Group with Different Copolymerizability Mono-butyl maleate 430 in 1 Kolben equipped with stirrer, nitrogen inlet tube, temperature controller, condenser for cooling
And 1.6 parts of hydroquinone were added and the temperature was raised to 150 ° C. Then 373 parts of glycidyl methacrylate was added dropwise over 20 minutes,
It was kept at the same temperature for 60 minutes. After confirming that the acid value was 3 KOHmg / g or less, the reaction was confirmed and terminated.

Reference Example 9: Preparation of metal element-containing composite three-dimensional resin particles Deionized water 306 in one Kolben equipped with a stirrer, temperature control device, dropping funnel, nitrogen introduction tube, condenser for cooling
Part, and the temperature was raised to 80 ° C. Next, an aqueous solution of a dispersion stabilizer consisting of 30 parts of the amphoteric ion group-containing polyester resin obtained in Reference Example 5, 3 parts of dimethylethanolamine and 170 parts of deionized water was prepared and stirred with a disper, 40 parts of methyl methacrylate and acryl. 4 parts of n-butyl acidate, 48 parts of ethylene glycol dimethacrylate, 20 parts of monomers having unsaturated groups having different copolymerizability of Reference Example 4, and 8 parts of tributyltin methacrylate were gradually added to prepare a pre-emulsion solution. Had made. Separately from this, azobiscyanovaleric acid 2
Parts, 1.2 parts of dimethylethanolamine, and 40 parts of deionized water were prepared.

The aqueous solution prepared in this manner was added dropwise over 80 minutes, and the pre-emulsion was added over 60 minutes from 10 minutes after the start of the addition of the aqueous solution. After standing at the same temperature for 30 minutes, a mixed monomer solution of 32 parts of styrene, 24 parts of methyl methacrylate, 12.8 parts of n-butyl acrylate and 11.2 parts of 2-hydroxyethyl methacrylate, 1.0 part of azobiscyanovaleric acid, dimethylethanolamine A mixed aqueous solution of 0.6 parts and 20 parts of deionized water was added dropwise over 40 minutes and then aged for 1 hour to complete the reaction.

Water was removed from this emulsion resin liquid using a freeze dryer to obtain composite three-dimensional resin particles having a tin element. Hereinafter, this is abbreviated as gelled particles b. When the tin concentration was quantified with a fluorescent X-ray analyzer, it was 11,000 ppm in the solid content.

Reference Example 10: Preparation of composite three-dimensional resin particles containing metal element Composite three-dimensional resin particles were obtained in exactly the same manner as in Reference Example 9 except that 8 parts of tributyltin methacrylate was changed to 3.5 parts. Hereinafter, this is abbreviated as gelled particles c. When the tin concentration was quantified with a fluorescent X-ray analyzer, the solid content was 5000 ppm.

Reference Example 11: Preparation of composite three-dimensional resin particles containing metal element Using the same apparatus as in Reference Example 1, deionized water was added to Kolben.
6 parts were added and the temperature was raised to 80 ° C. Then, an aqueous solution of a dispersion stabilizer consisting of 30 parts of the amphoteric ion group-containing polyester resin obtained in Reference Example 5, 3 parts of dimethylethanolamine, and 190 parts of deionized water was prepared. While stirring this with a disper, 80 parts of methyl methacrylate were prepared. A pre-emulsion was prepared by gradually adding a mixed monomer solution consisting of 18 parts of n-butyl acrylate, 80 parts of ethylene glycol dimethacrylate, 2 parts of methacrylic acid and 20 parts of allyl methacrylate. Separately from this, 2 parts of azobiscyanovaleric acid and dimethylethanolamine 1.
An aqueous solution consisting of 2 parts and 40 parts deionized water was prepared.

The aqueous solution thus prepared was added dropwise over 80 minutes, and the pre-emulsion was added over 60 minutes from 10 minutes after the start of the addition of the aqueous solution, followed by aging at the same temperature for 1 hour to complete the reaction.

383 parts of the obtained crosslinked particle emulsion, 3.5 parts of tributyltin oxide, 200 parts of butyl acetate were placed in an eggplant-shaped flask, and while stirring at 70 ° C., stirring was continued until dehydration disappeared with an evaporator, and the reaction was completed. A butyl acetate dispersion was obtained.

Next, using the same device as in Reference Example 1, the Kolben was added with a nonvolatile content of 40%.
% Butyl acetate dispersion 296 parts, butyl acetate 117 parts, styrene 10 parts, methyl methacrylate 10 parts, and n-butyl acrylate 10 parts were added and the temperature was raised to 110 ° C. Then t-butyl peroxy 2-ethylhexanoate 1 part, butyl acetate 50
Part of the initiator solution was added dropwise over 30 minutes and aged for 3 hours to complete the reaction to obtain a butyl acetate dispersion liquid having a nonvolatile content of 30% of composite three-dimensional resin particles having tin element. Hereinafter, this is abbreviated as gelled particles d. When the tin concentration was quantified by a fluorescent X-ray analyzer, it was 9,200 ppm based on the solid content.

Reference Example 12: Preparation of composite three-dimensional resin particles containing metal element Using the same apparatus as Reference Example 1, deionized water 292 in Kolben was used.
Then, the temperature was raised to 80 ° C. Next, an aqueous solution of a dispersion stabilizer consisting of 24 parts of the amphoteric ion group-containing epoxy resin obtained in Reference Example 6, 2.4 parts of dimethylethanolamine and 170 parts of deionized water was prepared, and 40 parts of methyl methacrylate was stirred with a disper. , 2 parts of n-butyl acrylate, 70 parts of 1,6-hexanediol dimethacrylate, 20 parts of monomers having unsaturated groups having different copolymerizability of Reference Example 8 and 8 parts of zinc monomethacrylate were gradually added to a mixed monomer solution. In addition, a pre-emulsion was prepared. Apart from this, azobiscyanovaleric acid 2
Parts, 1.2 parts of dimethylethanolamine and 40 parts of deionized water were prepared.

The aqueous solution thus prepared was added dropwise over 70 minutes, and the pre-emulsion was added over 50 minutes from 10 minutes after the start of the addition of the aqueous solution. After standing at the same temperature for 30 minutes, mixed monomer liquid of 20 parts of styrene, 20 parts of methyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate and 15 parts of n-butyl acrylate, 1.0 part of azobiscyanovaleric acid, dimethylethanolamine
A mixed aqueous solution of 0.6 parts and 20 parts of deionized water was added dropwise over 30 minutes, followed by aging for 1 hour to complete the reaction.

Water was removed from the emulsion resin liquid using a spray dryer to obtain composite three-dimensional resin particles containing zinc element. Hereinafter, this is abbreviated as gelled particles e. Quantitative determination of zinc concentration by X-ray fluorescence analyzer showed 15,000 pp in solid content.
It was m.

Reference Example 13: Preparation of composite three-dimensional resin particles containing metal element Using the same apparatus as in Reference Example 1, deionized water 292 in Kolven was used.
Then, the temperature was raised to 80 ° C. Next, an aqueous solution of a dispersion stabilizer consisting of 24 parts of the amphoteric ion group-containing acrylic resin obtained in Reference Example 7, 2.4 parts of dimethylethanolamine, and 170 parts of deionized water was prepared. While stirring this with a disper, 20 parts of methyl methacrylate was prepared. , 12 parts of n-butyl acrylate, 60 parts of 1,6-hexanediol dimethacrylate, 20 parts of monomers having unsaturated groups having different copolymerizability of Reference Example 8, and 8 parts of methacryloxyzirconium octate as a mixed monomer liquid. It was gradually added to prepare a pre-emulsion. Separately from this, 2 parts of azobiscyanovaleric acid and 1.2 of dimethylethanolamine
Parts, and an aqueous solution consisting of 40 parts of deionized water was prepared.

The aqueous solution prepared in this manner was added dropwise over 80 minutes, and the pre-emulsion was added over 60 minutes from 10 minutes after the start of the addition of the aqueous solution. After standing at the same temperature for 30 minutes, mixed solution of 24 parts of styrene, 24 parts of methyl methacrylate, 32 parts of n-butyl acrylate and 1.0 part of azobiscyanovaleric acid, 0.6 parts of dimethylethanolamine, 20 parts of deionized water. Was added dropwise over 30 minutes and then aged for 1 hour to complete the reaction.

Water was removed from this emulsion resin liquid using a spray dryer to obtain composite three-dimensional resin particles having zirconium element. Hereinafter, this is abbreviated as gelled particles f. When the zirconium concentration was quantified with a fluorescent X-ray analyzer,
It was 10,000 ppm in the solid content.

Reference Example 14: Preparation of crosslinked resin particle dispersion A crosslinked resin particle dispersion was obtained in exactly the same manner as in Reference Example 3 except that 0.5 part of diphenyllead dimethacrylate was changed to 0.5 part of ethyl acrylate. Hereinafter, this is abbreviated as particle dispersion g. Moreover, this thing did not contain the metal element.

Reference Example 15: Preparation of crosslinked resin particles 306 parts of deionized water were placed in the same apparatus as in Reference Example 9 and heated to 80 ° C.
The temperature was raised to. Then, an aqueous solution of a dispersion stabilizer consisting of 30 parts of the amphoteric ion group-containing polyester resin obtained in Reference Example 5, 3 parts of dimethylethanolamine and 170 parts of deionized water was prepared, and 40 parts of methyl methacrylate and n-acrylic acid were added thereto. 4 parts of butyl and 48 parts of ethylene glycol dimethacrylate were gradually added to prepare a pre-emulsion. Separately, an aqueous solution containing 2 parts of azobiscyanovaleric acid, 1.2 parts of dimethylethanolamine and 40 parts of deionized water was prepared.

The aqueous solution thus prepared was added dropwise over 80 minutes, and the pre-emulsion was added dropwise over 60 minutes from 10 minutes after the start of the addition of the aqueous solution. After the dropping was completed, the same temperature was maintained for 30 minutes to complete the reaction.

Water was removed from the obtained emulsion using a freeze dryer to obtain crosslinked resin particles. Hereinafter, this is abbreviated as gelled particles h. This product contained no metal element.

Reference Example 16: Preparation of polymer containing resin particles A reactor similar to Reference Example 1 was charged with 15 parts of gelled particles b, 50 parts of xylene and 50 parts of butyl acetate in a nitrogen atmosphere.
The temperature is raised to 120 ° C., 25.5 parts of styrene, 28.6 parts of methyl methacrylate, 0.4 parts of methacrylic acid, 16.7 parts of n-butyl acrylate, 1 part of 2-hydroxyethyl methacrylate.
A mixed solution of 3.8 parts and 2 parts of tert-butyl peroxyoctoate was added dropwise over 3 hours. After the dropping was completed, the same temperature was maintained for 3 hours to complete the reaction. The obtained solution is hereinafter abbreviated as Varnish C.

Reference Example 17: Preparation of Polymer Containing Resin Particles A reactor similar to that of Reference Example 1 was charged with 30 parts of gelled particles b, 50 parts of xylene and 50 parts of butyl acetate and placed in a nitrogen atmosphere.
The temperature was raised to 120 ° C and 21 parts of styrene and 2 parts of methyl methacrylate were added.
3.5 parts, 0.4 parts of methacrylic acid, of n-butyl acrylate
13.7 parts, 11.4 parts of 2-hydroxyethyl methacrylate,
A mixture of 2 parts of tert-butyl peroxyoctoate was added dropwise over 3 hours. After the dropping was completed, the same temperature was maintained for 3 hours to complete the reaction. The obtained solution is hereinafter abbreviated as Varnish D.

Reference Example 18: Preparation of Polymer Containing Resin Particles A reactor similar to Reference Example 1 was charged with 5 parts of gelled particles b, 50 parts of xylene and 50 parts of butyl acetate in a nitrogen atmosphere.
The temperature is raised to 120 ° C., 28.5 parts of styrene, 32 parts of methyl methacrylate, 0.5 part of methacrylic acid, 18.6 parts of n-butyl acrylate, 15.4 parts of 2-hydroxyethyl methacrylate.
Part, and a mixed solution of 2 parts of tert-butyl peroxyoctoate were added dropwise over 3 hours. After the dropping was completed, the same temperature was maintained for 3 hours to complete the reaction. The resulting solution is hereinafter abbreviated as Varnish E.

Varnishes A to E obtained in Examples 1 to 10 and Comparative Examples 1 to 3 and Reference Examples 1 to 18, particle dispersion a,
First, a mixed solvent S consisting of g, gelled particles b to f, h, 40 parts of toluene, 30 parts of n-butyl acetate, 20 parts of xylene and 10 parts of Solvesso # 100 (a mixture of aromatic hydrocarbons manufactured by Exxon) is used. The main ingredient was made into a paint at the compounding ratios shown in the table, and further Coronate EH (isocyanate prepolymer manufactured by Nippon Polyurethane Co.) was compounded at the ratio shown in Table 1 and sprayed with the mixed solvent S. The viscosity was adjusted to obtain the coating materials of Examples 1 to 10 and Comparative Examples 1 to 3. The above paint has a thickness of 50 mm on a mild steel plate with a thickness of 0.8 mm.
It was painted so as to have a thickness of about 60μ, dried under conditions of a temperature of 20 ° C and a humidity of 75%, and subjected to each test. The results are shown in Table 2.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Kashihara 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Tadafumi Miyazono 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Incorporated (56) References JP 56-98266 (JP, A) JP 56-110717 (JP, A) JP 50-10891 (JP, A)

Claims (5)

[Claims] 1. A base component (A) comprising (a) a hydroxyl group-containing film-forming resin, (b) a metal element-containing crosslinked resin particle and (c) a solvent, and a curing agent component (B) comprising an isocyanate group-containing compound. And (b) a solid content weight ratio of (a) a hydroxyl group-containing film-forming resin and (b) a metal element-containing crosslinked resin particle in the component (A) is 99/1 to 40/60, The equivalent ratio of the isocyanate group in the component and the hydroxyl group in the component (A) is
A two-component urethane coating composition, which is 0.5 to 2.0. 2. The (a) hydroxyl group-containing film-forming resin of the main agent component (A) and the (b) metal element-containing crosslinked resin particles,
The mixture prepared by the method (b) of polymerizing a hydroxyl group-containing film-forming resin-constituting monomer in the presence of a metal element-containing crosslinked resin particle (a) to obtain a hydroxyl group-containing film-forming resin. The coating composition described. 3. The coating composition according to claim 1, wherein the metal element-containing crosslinked resin particles are acrylic or methacrylic resin particles. 4. The coating composition according to claim 2, wherein the hydroxyl group-containing film forming resin is an acrylic or methacrylic resin, and the metal element-containing crosslinked resin particles are acrylic or methacrylic resin particles. 5. The metal element is Zn, Sn, Al, Fe, Zr, Ti, Ge, Pb, Cr, M.
The coating composition according to claim 1 or 2, which is selected from g, Ca, Sr, Li, Na and K.