JPH0735495B2 - Two-component urethane coating composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a two-component urethane coating composition, and more particularly, it can provide a coating film having excellent dispersion stability, high gloss, and good transparency, and is particularly fast. The present invention relates to a two-component urethane coating composition which is extremely dry and has excellent polishing properties and workability and which is extremely useful for repairing automobiles and the like.

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
Since liquid urethane paint does not require baking, it is drawing attention in various fields such as automobile repair and woodworking.

In such a paint, it is preferable that it is quick-drying from the viewpoints of process shortening, heat energy saving, etc., and various devises have been made in order to impart quick-drying property to the two-component urethane paint. None was satisfactory.

For example, in the technology using an acrylic resin having a high molecular weight or a high glass transition temperature (Tg) as a resin component,
Since the sprayed solid content is low, the number of coatings increases and the appearance is poor.Therefore, the technology of blending cellulose resin such as nitrocellulose and CAB has the same drawbacks as above. Has a short pot life,
There are many problems such as poor appearance of the coating film, and the technique using aromatic polyisocyanate has not been put to practical use in terms of weather resistance.

If two-component urethane paint is blended with suitable three-dimensionally cross-linked so-called gelled resin particles that are substantially insoluble in the solvent, the pigment filling effect as a plastic pigment and the hard resin effect due to the cross-linked resin will result in faster speed. It is expected that dryness will be obtained. Various studies have been made on such three-dimensionally crosslinked resin particles, but the conventional one is to increase the resin solid content in a coating using a solvent-based resin to obtain a highly solid coating, which is dripping, cissing or weather resistance. It has been developed for the purpose of controlling the rheology in order to compensate for the drawbacks such as the decrease of the temperature, and the normal dry type two-component urethane paint is not considered at all, and in fact, even if such three-dimensional crosslinked resin particles are used. 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 an excellent appearance of the coating film.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Therefore, a two-component urethane coating composition is capable of providing a coating surface having high gloss and good transparency and having an excellent appearance. Particularly, it is quick-drying and has excellent polishing property and workability. It is an object of the present invention to obtain a coating composition which is excellent in dispersion stability and is useful for automobile repair and the like.

Means for Solving the Problems According to the present invention, the above object is to provide a main component (A) consisting of a hydroxyl group-containing film-forming resin, crosslinked resin fine particles and a solvent, and a curing agent component (B) consisting of a compound having an isocyanate group. 2) The crosslinked resin fine particles are three-dimensional resin particles and substantially linear metal-containing polymers are graft-bonded to the three-dimensional resin particles, which are solid resin of the hydroxyl group-containing film-forming resin and the composite resin particles. The weight-to-weight ratio is 99/1 ~
40/60 of the isocyanate group in the component (B) and the hydroxyl group in the component (A) (the total amount of the hydroxyl groups of the hydroxyl group-containing film-forming resin and the hydroxyl groups of the linear polymer). This can be achieved by a two-component urethane coating composition characterized in that the equivalent ratio is 0.5 to 2.0.

The crosslinked resin particles used in the present invention are a novel type of composite three-dimensional resin particles in which a substantially linear metal-containing polymer is bonded to the three-dimensional resin particles. As described in the patent application (Japanese Patent Application No. 61-090828) "Composite three-dimensional resin particles and a method for producing the resin particles", the resin particles are polyester resin, Polymer particles having a three-dimensional structure with a diameter of 0.01μ to 10μ, which are composed of condensation resins such as epoxy resins and amino resins and polymerization resins such as acrylic resins and vinyl resins. Alternatively, it can be easily carried by carrying or introducing an addition-polymerizable unsaturated group inside, and then addition-polymerizing a metal-containing addition-polymerizable ethylene compound and optionally another addition-polymerizable ethylene compound to form a linear polymer. Be manufactured in. It is also possible to synthesize an organic metal compound into a linear polymer chain by an esterification reaction or transesterification reaction after synthesizing three-dimensional resin particles in which a linear polymer is chemically bonded. Furthermore, it is also possible to carry an appropriate functional group on a polymer particle having a three-dimensional structure and to react it with a reactive derivative of a metal-containing linear polymer to chemically bond the linear polymer to the particle main body. Therefore, both the particle main body part and the linear polymer part can be made of any resin, and the manufacturing method thereof can be appropriately selected by a person skilled in the art of the polymer field.

However, in the present invention, what is important in terms of easiness of production and application in the field of paints in particular is the composite three-dimensional resin particles in which both the particle main body portion and the linear polymer portion are made of a polymer resin such as acrylic resin.

The above-mentioned composite three-dimensional resin particles according to a particularly preferred embodiment can be advantageously produced by the following method. That is, the polyfunctional monomer containing two or more unsaturated groups having different copolymerizability and a polymerizable monomer containing a crosslinkable monomer that undergoes a polymerization reaction with one unsaturated group of the polyfunctional monomer are emulsion-polymerized to produce the polyfunctional monomer. A three-dimensional resin particle in which the other unsaturated group of the functional monomer remains is first made, and then a polymerizable monomer that polymerizes with the other unsaturated group, a metal-containing monomer, and, if necessary, Is a method in which another polymerizable monomer is added and graft-polymerized to form a substantially linear metal-containing polymer chain.

Further, in the above production method, when forming the linear polymer, the linear polymer is formed without using the metal-containing polymerizable monomer, and then the organometallic compound is esterified or transesterified with the polymer. A method of reacting is also used.

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 is a unsaturated three-dimensional resin particle of a composite three-dimensional resin particle. Advantageously used for synthesis. Particularly preferred polyfunctional monomer is allyl (meth)
Having an 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, an allyl alcohol and a (meth) acryloyl group Isocyanate adducts, maleic acid or fumaric acid and glycidyl (meth) acrylate adducts, maleic acid or fumaric acid monoester and glycidyl (meth) acrylate adducts, and fatty acids having unsaturated groups and glycidyl (meth) It is an adduct of acrylate.
Unsaturated groups contained in acryloyl and methacryloyl in these compounds have no selectivity for the counterpart monomer and react with any polymerizable monomer, but the other allyl group or maleic acid type double bond or unsaturated Since the double bond in the fatty acid selectively reacts 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.

Three-dimensional resin particles are first 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. 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 a polyhydric alcohol or a polybasic acid polymerizable Combinations of unsaturated alcohol esters or 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. Further, as the other compound having an α, β-ethylenically unsaturated bond, any monomer used in the synthesis of an acrylic resin is used, but it leaves a maleic acid type double bond, so that a selective monomer Reactive polymerizable aromatic 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 ( Monomers produced by reaction of I) with a glycidyl group-containing compound.

These monomers are used alone or in combination.

In emulsion polymerization, ordinary polymerization initiators and emulsifiers are used to form three-dimensional particles according to a conventional method.
In the molecule as described in No. 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 liquid containing the three-dimensional resin particles thus obtained is then added with a polymerizable aromatic compound, such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc., if necessary. Is added together with the graft polymerization to form a substantially linear polymer chain.

In the present invention, the metal-containing polymerizable monomer is allowed to coexist at this time to form a substantially linear metal-containing polymer chain. The metal-containing polymerizable monomer does not contain B, Si, As, Te, At in the long-period periodic table, and is polymerizable with metals selected from the elements to the left of the line connecting these (hereinafter referred to as the metal element) Compounds having an unsaturated group, more specifically, the following compounds are conveniently used.

That is, as the metal element-containing polymerizable monomer, acrylic acid,
Any metal ester of a polymerizable organic acid such as methacrylic acid, itaconic acid, maleic acid, a metal salt, a vinyl metal, or a styryl metal can be used, and the metal is a hydroxyl group, an organic acid residue, or (substituted) alkyl. It may have a group. 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, styrene triethyl germane, vinyl triethyl germane, as the lead diphenyl Namariji (meth) acrylate,
Styryl triethyl Pb, include styryl triphenyl lead, general formula _{(CH 2 = CH) xMnRn -} x; (CH 2 = CHC 6 H 4) xMnRn - x; (CH 2 = CR'COO) xMnRn - x; ( In the formula, M is a metal element, R is a (substituted) alkyl or (substituted) phenyl or hydroxyl, R'is H or methyl, n is a valence of the metal element, and x is an integer smaller than n).

Further, in the method of forming a linear polymer without using the metal-containing polymerizable monomer as described above and then introducing the metal into the linear polymer by an esterification reaction or a transesterification reaction with the polymer, for example, a linear polymer is used. In order to react with the hydroxyl groups contained in the polymer, the metal compounds are magnesium chloride, calcium oxide, chromium chloride, zinc oxide, tributyltin oxide, dibutyltin oxide, triethyltin chloride, tribenzyltin chloride, diethylaluminum chloride, and hydroxide. A metal oxide such as aluminum, a metal halide and a metal hydroxide are preferable. These compounds can be easily esterified or transesterified with a carboxyl group or a neutralized carboxyl group in the linear polymer by a known method to introduce a metal element into the linear polymer. Alkali metal elements such as sodium, potassium and calcium and alkaline earth metal elements can be introduced by ionic bond with the carboxyl group in the linear polymer simply by adding hydroxide.

When the present inventors use such a new composite resin particle,
Since the resin particle main body is three-dimensionally cross-linked, it is possible to obtain a two-component urethane paint that has a fast drying property and a good polishing property due to the hard resin effect in addition to the pigment filling effect, and the linear polymer prevents the particles from approaching each other. Helps to evenly disperse the particles in the system, excellent compatibility with hydroxyl-containing resin,
A coating with good appearance can be obtained, and when pigment is present, it has the function of wrapping around the pigment to stabilize it and has good dispersion stability. It also has a film-forming ability and has a glossy and transparent appearance. In addition, the metal contained in the linear polymer chain is extremely effective as a urethanization catalyst, and when tin, zinc, etc. are supported, the effect is remarkable. It was found that the urethane formation reaction between the hydroxyl groups of the hydroxyl group-containing resin around the particles or the active hydrogen groups contained in the particles and the isocyanate groups is promoted, the crosslinking density becomes large and the drying property becomes extremely good, which is the basis of the present invention. It is a thing.

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

As described above, in the present invention, by using the novel composite three-dimensional resin particles, the coating film is quick-drying, particularly excellent in drying property, polishing property, workability, and gloss and transparency. It is possible to obtain a two-component urethane coating composition that can give a coated surface having an excellent appearance.

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

The hydroxyl group-containing film-forming resin, the solvent and the compound having an isocyanate group may be any materials usually used in urethane coatings, and both the main component and the curing agent may be used as ordinary two-component urethane type coatings. Any additives and auxiliaries used, such as UV absorbers, pigments, catalysts, solvents, etc., can be contained.

The coating composition of the present invention is prepared by mixing the curing agent component (A) and the main component (B), adjusting the viscosity with a thinner or the like, and having an appropriate pot life for air spray coating and excellent workability. It has fast drying property, shortens the time until polishing, and can provide a smooth, high-gloss and excellent-appearance coating film, which is useful for automobile repairs, etc.
It is expected to have wide applications in various fields such as plastic parts, woodworking, heavy duty protection, and construction.

The present invention will be described below with reference to examples.

Reference Example 1: Preparation Example of Hydroxyl Group-Containing Polymer Stirrer, thermometer, 100 parts of xylene was charged to a reactor equipped with a nitrogen inlet tube and a reflux condenser, and 120 in a nitrogen atmosphere.
The temperature was raised to 0 ° C., and a mixture of 40 parts of styrene, 24 parts of n-butyl methacrylate, 16.9 parts of methyl methacrylate, 0.5 parts of methacrylic acid, 18.6 parts of 2-hydroxyethyl methacrylate and 2.1 parts of tert-butyl peroxyoctoate was added thereto. It was added dropwise over 3 hours, and the reaction was continued by keeping the same temperature for 3 hours after the completion of the addition. Nonvolatile content (NV) 50% Gardner color 1 or less, Mn about 8000, Tg70
At 0 ° C., a polymer solution of OHV80 per solid, AV3.3 per solid was obtained. Hereinafter this is referred to as acrylic resin A.

Reference Example 2: Synthesis 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 of acid and 27 parts of xylene 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 refluxing, 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" (glycidyl ester of versatic acid 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, a hydroxyl value of 90, and Mn.
= 1054.

Reference Example 3: Synthesis of dispersion stabilizer 1 Kolben equipped with a stirrer, a temperature controller, a dropping funnel, and a condenser for cooling a nitrogen introducing tube was charged with 140 parts of ethylene glycol monomethyl ether and 140 parts of xylene.
The temperature was raised to 0 ° C. Separately prepared methyl methacrylate 74
Part, 2-ethylhexyl acrylate 70 parts, 2-hydroxyethyl methacrylate 24 parts, methacrylic acid 12 parts 5 parts azobisisobutyronitrile dissolved in a monomer mixture liquid and ethylene glycol monomethyl ether 150 parts N A solution in which 20 parts of-(3sulfopropyl) -N-methacryloyloxyethyl-N, N-dimethyl-ammonium betaine was dissolved was separately added dropwise to Kolben over 3 hours.
Thirty minutes after the completion of the dropwise addition, a solution prepared by dissolving 0.4 part of t-butylperoxy-2-ethylhexanoate in 8 parts of ethylene glycol monomethyl ether was added, and the reaction was completed by aging at the same temperature for 1 hour. The solvent is removed to remove the nonvolatile content of 92
% Of the zwitterionic group-containing acrylic resin was obtained.

Reference Example 4: Synthesis of Monomer Having Unsaturated Group with Different Copolymerizability 1 Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, cooling condenser 430 of monobutyl maleate
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. The reaction was terminated after confirming that the acid value was 3 KOHmg / g or less.

Reference Example 5: Synthesis of composite three-dimensional resin particles 330 parts of deionized water was charged into one Kolben equipped with a stirrer, a temperature controller, a dropping funnel, and a condenser for cooling a nitrogen introducing tube, and the temperature was raised to 80 ° C. Next, an aqueous dispersion of a dispersion stabilizer comprising 12 parts of the zwitterionic group-containing polyester resin obtained in Reference Example 2, 1.2 parts of dimethylethanolamine and 104 parts of deionized water was prepared, and 66 parts of methyl methacrylate was stirred with a disper. 60 parts of n-butyl acrylate, 14 parts of allyl methacrylate, ethylene glycol dimethacrylate
A pre-emulsion was prepared by gradually adding 40 parts of the mixed monomer solution. Separately, an aqueous solution containing 2 parts of azobiscyanovaleric acid, 1.3 parts of dimethylethanolamine and 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, a mixed solution of 12 parts of styrene, 2 parts of methyl methacrylate, 4 parts of 2-hydroxyethyl methacrylate and 2 parts of zinc monomethacrylate, 0.8 parts of azobiscyanovaleric acid, 0.6 parts of dimethylethanolamine,
After dropping a mixed aqueous solution of 20 parts of deionized water over 20 minutes,
The reaction was completed after aging for 1 hour.

Water was removed from the synthesized emulsion resin liquid by using a freeze dryer to obtain composite three-dimensional resin particles containing zinc element. The zinc concentration measured by a fluorescent X-ray analyzer was 4000 ppm with respect to the solid content, and the particle size in the emulsion state was 150 nm.

Hereinafter, this is referred to as gelled particle a.

Reference Example 6: Synthesis of composite three-dimensional resin particles Using the same apparatus as in Reference Example 5, 330 parts of deionized water was charged and the temperature was raised to 80 ° C. Then, an aqueous solution of a dispersion stabilizer consisting of 23 parts of the amphoteric ion group-containing polyester resin obtained in Reference Example 2, 4 parts of dimethylethanolamine and 160 parts of deionized water was prepared, and 30 parts of methyl methacrylate and n-butyl methacrylate were added thereto. An emulsion was prepared by adding 40 parts, 14 parts of the monomer of Reference Example 4 and 56 parts of ethylene glycol dimethacrylate. Separately, an aqueous solution containing 2 parts of azobiscyanovaleric acid, 1.3 parts of dimethylethanolamine and 40 parts of deionized water was prepared. This aqueous solution was added dropwise over 65 minutes. 10 minutes after the start of dropping of the aqueous solution, the above emulsion was dropped over 45 minutes. After the dropwise addition of the aqueous solution, hold at the same temperature for 20 minutes, and then add 20 parts of a mixed aqueous solution of 0.8 part of azobiscyanovaleric acid and 0.6 part of dimethylethanolamine deionized water.
It dripped over minutes. 10 minutes after the start of dropping of this aqueous solution, a mixture of 18 parts of styrene, 8 parts of methyl methacrylate, 23 parts of n-butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate and 1 part of tributyltin methacrylate was added dropwise over 20 minutes. did. Hold the same temperature for 90 minutes after the dropping,
The reaction was completed.

The obtained emulsion was freeze-dried to obtain tin element-containing composite three-dimensional resin particles. The tin concentration measured by a fluorescent X-ray analyzer was 1400 ppm with respect to the solid content.

Hereinafter, this is referred to as gelled particle b.

Reference Example 7: Synthesis of Composite Three-Dimensional Resin Particles Using exactly the same equipment and method as in Reference Example 6, the zwitterionic group-containing acrylic resin of Reference Example 3 was used instead of 23 parts of the zwitterionic group-containing polyester resin of Reference Example 2 as a dispersion stabilizer. Tin element-containing composite three-dimensional resin particles were obtained in exactly the same manner except that 40 parts of the resin and 10 parts of 2-hydroxytyl methacrylate were changed to 10 parts of n-butyl methacrylate. The tin concentration measured by a fluorescent X-ray analyzer was 1300 ppm based on the solid content.

Hereinafter, this is referred to as gelled particle c.

Reference Example 8: Synthesis of Composite Three-Dimensional Resin Particles Using the same apparatus as in Reference Example 5, deionized water in Kolben 33
0 part was added and the temperature was raised to 80 ° C. Then, an aqueous solution of a dispersion stabilizer consisting of 16 parts of the amphoteric ion group-containing polyester resin obtained in Reference Example 2 and 1.6 parts of dimethylethanolamine and 104 parts of deionized water was prepared, and this was stirred with a disper and 14 parts of methyl methacrylate and acryl. A pre-emulsion was prepared by gradually adding a mixed monomer solution of 28 parts of n-butyl acidate, 18 parts of allyl methacrylate and 60 parts of 1,6-hexanediol dimethacrylate. Separately, an aqueous solution containing 1.6 parts of azobiscyanovaleric acid, 1.1 parts of dimethylethanolamine and 40 parts of deionized water was prepared.

The aqueous solution thus prepared was added dropwise over 50 minutes. Five minutes after the start of dropping of this aqueous solution, the pre-emulsion prepared above was dropped over 35 minutes. After dropping the former aqueous solution,
Aged at the same temperature for 30 minutes. Then, a mixed aqueous solution of 1 part of azobiscyanovaleric acid, 0.7 part of dimethylethanolamine and 30 parts of deionized water was added dropwise over 45 minutes.
Five minutes after the start of the dropping of the aqueous solution, a monomer mixture liquid of 28 parts of styrene, 16 parts of methyl methacrylate, 33 parts of n-butyl methacrylate, 3 parts of methacrylic acid and 3.2 parts of dimethylethanolamine was added dropwise over 30 minutes. After dropping the former aqueous solution,
The reaction was completed by aging for 60 minutes at the same temperature.

After removing water from this using a freeze dryer,
60 parts of the obtained particle powder was placed in a 500 ml eggplant flask, and 180 parts of xylene was added. The particle powder was dispersed in xylene in an evaporator while maintaining the temperature at 70 ° C., 4.3 parts of dibutyltin oxide was added, and the stirring of the evaporator was continued. After about 20 minutes, when the dehydration was stopped, the reaction was terminated, and the nonvolatile content was adjusted to 30% with xylene. The tin concentration measured by a fluorescent X-ray analyzer was 8500 ppm with respect to the solid content.

Hereinafter, this is referred to as gelled particles d.

Reference Example 9: Synthesis of composite three-dimensional resin particles In the same apparatus and method as in Reference Example 5, 10 parts of styrene and 4 parts of n-butyl acrylate were used as monomers to be reacted in the second step.
Calcium element-containing composite three-dimensional resin particles were obtained in exactly the same manner except that a mixed solution of 4 parts of 2-hydroxyethyl methacrylate and 2 parts of calcium diacrylate were replaced with a monomer aqueous solution prepared by dissolving 18 parts of deionized water. The calcium concentration measured by an X-ray analyzer was 1800 ppm based on the solid content.

Hereinafter, this is referred to as gelled particle e.

Reference Example 10: Synthesis of three-dimensional resin particles Using the same apparatus as in Reference Example 5, 330 parts of deionized water was charged and the temperature was raised to 80 ° C. Then azobiscyanovaleric acid 2
Part, dimethylethanolamine 1.3 parts, and deionized water 40 parts were added dropwise over 80 minutes. Furthermore, 10 minutes after the start of dropping the aqueous solution, the dispersion stabilizer obtained in Reference Example 3
40 parts, dimethylethanolamine 1.2 parts, deionized water 104
Parts, methyl methacrylate 95 parts, n-butyl acrylate 75
And 30 parts of ethylene glycol dimethacrylate were added dropwise over 60 minutes. After the completion of dropping the aqueous solution, hold the same temperature for 90 minutes to complete the reaction.
A 160 nm emulsion was obtained. Water was removed from this emulsion using a spray dryer to obtain three-dimensional resin particles.

Hereinafter, this is referred to as gelled particle f.

Reference Example 11: Synthesis of three-dimensional resin particles The amount of methyl methacrylate shown in Reference Example 10 was changed to 60 parts, the amount of n-butyl acrylate was changed to 60 parts, and the amount of ethylene glycol dimethacrylate was changed to 80 parts. Except for this, three-dimensional resin particles were obtained in the same manner as in Reference Example 10.

Hereinafter, this is referred to as gelled particle g.

Examples 1 to 7, Comparative Examples 1 to 3 Acrylic resin A obtained in Reference Example 1, gelled particles a to g obtained in Reference Examples 5 to 11, and mixed solvent I shown below
Mix it in the mixing ratio shown in the table to make it a paint,
Further, the curing agent components shown in the same table were mixed and the spray viscosity was adjusted with the following mixed solvent I to obtain each coating material of Examples 1 to 7 and Comparative Examples 1 to 3.

The above paint was applied on a mild steel plate having a thickness of 0.8 mm so that the film thickness would be about 50 to 60 μm, and was left to dry under the condition of a temperature of 20 ° C. and a humidity of 75%, and subjected to each test. The results are shown in Table 2.

(Note) * 1: HMDI prepolymer manufactured by Nippon Polyurethane Co., Ltd. * 2: JIS K 5400 5.8 * 3: JIS K 5400 5.8 * 4: 2 cc of pure water was spotted 16 hours after making the coated plate, and wiped off after 8 hours. Make an evaluation.

○: No abnormality ×: Luster, water marks, etc. are observed * 5: JIS K 5400 6.14 Evaluation 48 hours after making a coated plate.

* 6: JIS K 5400 6.7 * 7: ○: No turbidity observed ×: Turbidity recognized

 ─────────────────────────────────────────────────── ─── 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 62-246970 (JP, A) JP 62-292863 (JP, A)

Claims (3)

[Claims] 1. A main agent component (A) consisting of a hydroxyl group-containing film forming resin, crosslinked resin fine particles and a solvent, and a curing agent component (B) consisting of a compound having an isocyanate group.
A composite resin particle consisting of a liquid, in which crosslinked resin particles are graft-bonded to a three-dimensional resin particle with a substantially linear metal-containing polymer, and the solid content weight of the hydroxyl group-containing film-forming resin and the composite resin particle. The ratio is 99 / 1-40 / 60, (B)
The isocyanate group in the component and the hydroxyl group in the component (A) (when the hydroxyl group of the above-mentioned hydroxyl group-containing film forming resin and the above-mentioned linear polymer contain a hydroxyl group, the hydroxyl group and the hydroxyl group of the film forming resin are Equivalent ratio of (total amount)
A two-component urethane coating composition, which is 0.5 to 2.0. 2. The composition according to claim 1, wherein the three-dimensional resin particles are acrylic or methacrylic resin particles, and the substantially linear metal-containing polymer is an acrylic or methacrylic resin. 3. The metal is Zn, Sn, Al, Fe, Zr, Ti, Ge, P of the periodic table.
The composition according to claim 1 or 2, which is selected from b, Cr, Mg, Ca, Sr, Li, Na and K.