JPH073110A - Cold-setting resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition having good touch and excellent in resistance to alcohol by incorporating metal chelate compounds into a specified block copolymer having both polyurethane segments and vinyl polymer segment. CONSTITUTION:The composition is obtained by incorporating a six-coordinate organoaluminum chelate compound, an eight-coordinate organozirconium compound and/or an organotitanium chelate compound into a carboxylated and/or hydroxylated block copolymer having both polyurethane segments and vinyl polymer segments. This composition is excellent in pigment dispersion and provides a highly tough and resilient coating film; therefore, when used for architectural exterior and interior finish, plastic coating, wood coating, metal coating, etc., it can provide a coating film excellent in drying characteristics, hardness, stain resistance outdoors, low-temperature flex resistance, adhesion, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful room temperature curable resin composition. More specifically, the present invention relates to a specific block copolymer obtained by polymerizing a polymerizable unsaturated bond-containing compound in the presence of the specific compound in a form containing an azo bond and a urethane bond in the main chain. Particularly, the present invention relates to a room temperature curable resin composition mainly for plastic coating, which is obtained by blending a metal chelate compound with a polymer, has a good feel, and is also excellent in alcohol resistance.

[0002]

2. Description of the Related Art Up to now, a lacquer type paint containing a fiber system has various uses in addition to its performance such as drying property and solvent resistance, and its simple usage. Spans.

Above all, a paint composed of an acrylic resin and nitrocellulose is used in a large amount for painting a plastic molded product.

However, the plastic coated articles up to now have not been sufficient in terms of so-called abrasion resistance such as scratches and exposed base material during packaging. Therefore, utilizing the abrasion resistance of the urethane resin, acrylic resin having a hydroxyl group, in combination with polyisocyanate, or a method of blending the acrylic resin and the polyurethane resin is also performed, the former, polystyrene In terms of adhesion to the molded plate, pot life, use of strong solvent, etc., workability is not sufficient, and the latter is completely compatible with each other.
What is obtained by the polymer blend is that the gloss is poor and the storage stability is extremely poor, and in particular, the durability to polar solvents such as alcohol is not sufficient.

[0005]

As described above, as long as the conventional technique is followed, the present invention aims at, in particular, that the tactile feel is good and the alcohol resistance is excellent, which is extremely practical. Obtaining a room temperature curable resin composition has been extremely difficult.

However, in view of the various drawbacks of the prior art as described above, the present inventors have earnestly started research in order to expand the field of application as described above.

Therefore, the problem to be solved by the present invention is, in particular, that the tactile feeling is good,
Moreover, it is to provide a room temperature curable resin composition having extremely high practicality, which is also excellent in alcohol resistance.

[0008]

Therefore, the present inventors have
Focusing on the problems to be solved by the invention as described above, as a result of intensive and repeated studies, a polymer having a polyurethane bond in its main chain, which is obtained by blocking it with an acrylic resin, is the original polyurethane resin. A urethane-acrylic block copolymer having a carboxy group and / or a hydroxyl group, which has both excellent characteristics and original characteristics of an acrylic resin, has a 6-coordinate organoaluminum chelate compound and an 8-coordinate organozirconium compound. It has been found that a desired resin for plastic coating can be obtained by adding an organic titanium chelate compound and / or the present invention, and the present invention has been completed here.

That is, the present inventors first obtain, for example, by reacting a compound having at least one diazo bond and at least two hydroxyl groups in one molecule with a polyisocyanate compound, A so-called polyurethane polyazo initiator having a specific molecular weight is synthesized, and then a polymerizable unsaturated bond-containing compound having a carboxy group and / or a hydroxyl group is polymerized in the presence of the specific polyurethane polyazo initiator. A resin composition in a form obtained by blending a 6-coordinate organoaluminum chelate compound, an 8-coordination organozirconium compound and / or an organotitanium chelate compound with a specific block copolymer obtained by , Gloss, solvent resistance, abrasion resistance, flexibility, adhesion and spray workability Which on in, extends to find that it is well balanced coating resin of balance, finally, we were led to the completion of the present invention.

That is, the present invention is basically based on the general formula

[0011]

[Chemical 5]

[Wherein R ₁ is an alkylene group, a cyclic alkylene group, an alkylene group having an ester group, a benzene ring, or an alkylene group containing a benzene ring,
R ₂ and R ₂ 'may be the same or different and each is an alkylene group, an alkylene group containing a cyano group, an alkylene group containing an amide bond, or an alkylene group having both an amide bond and a hydroxyl group. Shall represent a group. ] And the structural unit

[0013]

[Chemical 6]

[In the formula, R ₃ represents a polyol residue. ] The number average molecular weight which has at least 1 in a molecule and the structural unit shown by these is 1,500-
In the presence of 2 to 95% by weight of a compound within the range of 50,000 (hereinafter, this is also referred to as a polymeric azo initiator),
Provided is a block copolymer resin for coating, which is obtained by polymerizing 98 to 5% by weight of a polymerizable unsaturated bond-containing monomer, and is particularly excellent in drying property, hardness, elongation and stain resistance. Finally, it is intended to provide a room temperature curable resin composition mainly for plastic coating, which is obtained by blending a metal chelate compound with the specific block copolymer thus obtained. It is what

Here, the so-called high molecular weight azo initiator having a number average molecular weight of 1,500 to 50,000, which has both a urethane bond and a diazo bond in one molecule, is as described above. [I] Formula and [I]
I] is a compound represented by the formula, each having a specific structural unit.

Various azobisalkanol compounds such as azobiscyanopropanol, azobiscyano-n-butanol, azobisisobutanol or azobiscyanopentanol; or "VA-080, VA-0.
82 or VA-086 "(product of Wako Pure Chemical Industries, Ltd.), such as various azoamide polyols, having at least one diazo bond and at least two hydroxyl groups in one molecule. For example, those obtained by reacting various compounds with a polyisocyanate compound.

That is, first of all, to exemplify particularly representative ones of such polymer azo initiators, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, Various diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate), 1,3-di (isocyanatomethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylcyclohexane diisocyanate, tolylene diisocyanate or xylene diisocyanate;

Alternatively, each of these diisocyanates, and various polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol or dipentaerythritol, or a functional group capable of reacting with an isocyanate group, For example, having a number average molecular weight of about 500 to 2,000,
Various polyisocyanate compounds such as adducts with extremely low molecular weight polyester compounds (including oil-modified types),

Ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polyhexamethylene glycol, neopentyl glycol,
Various di- or polyols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol or hydrogenated bisphenol A, or bisphenol A, and

As described above, it can be obtained by addition-condensing a ternary component of a compound having at least one diazo bond and at least two hydroxyl groups in one molecule.

As the synthesizing method at that time, first, a method in which these three components are simultaneously charged and reacted, or an isocyanate group-containing polyurethane intermediate (that is, a so-called urethane prepolymer) is prepared, and then this is prepared. There is a method of reacting a compound having at least one diazo bond and at least two hydroxyl groups in one molecule, but the synthesis method is not particularly limited.

In the reaction of these di- or polyol compounds with the di- or polyisocyanate compounds, ethylenediamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, bisaminopropylamine are used as chain extenders. Alternatively, it is needless to say that various polyamine compounds such as 4-aminomethyl-1,8-diaminooctane may be used.

Then, as a method for synthesizing the polyurethane polyester polyazo initiator, as described above, a di- or polyol compound, isophthalic acid, terephthalic acid, phthalic anhydride, (hydro) tetrahydrophthalic acid,
(Anhydrous) hexahydrophthalic acid, trimellitic anhydride,
Hydroxyl group-containing polyester resin in a form obtained by dehydration condensation with various di- or polycarboxylic acids (anhydrides) such as pyromellitic acid, fumaric acid, maleic acid, succinic acid or adipic acid (including oil-modified types .) And / or ε-caprolactone or valerolactone, a hydroxyl group-containing polyester resin in the form obtained by ring-opening polymerization of various lactone compounds,

As described above, a method in which various di- or polyisocyanate compounds are subjected to an addition reaction with a compound having at least one diazo bond and at least two hydroxyl groups in one molecule as described above. Is mentioned.

In such a case, it goes without saying that various polyamine compounds as described above and / or various di- or polyol compounds as described above may be used as the chain extender.

The number average molecular weight of the thus obtained compound represented by the general formulas [I] and [II], which has the respective structural units and has both the urethane bond and the diazo bond, is as follows: 1,500-50,
000, preferably in the range of 2,000 to 20,000, is suitable because it has particularly good solubility in various polymerizable unsaturated monomers and solvents as described below. is there.

When it is less than 1,500, the introduction rate of diazo bond is inevitably low, and therefore various coating film characteristics which are the characteristics of the resin of the present invention cannot be exhibited. If it exceeds 000, the solubility of the solvent is inevitably deteriorated, and uniform block copolymerization cannot be carried out. Therefore, either case is not preferable.

The vinyl-based monomer may be polymerized in the presence of the polymer azo initiator thus obtained. Of these vinyl-based monomers, first, a carboxy group-containing monomer is used. As such, various carboxy group-containing vinyl monomers such as (meth) acrylic acid, monobutyl maleate, monobutyl fumarate, crotonic acid, maleic acid, fumaric acid or itaconic acid can be used.

As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybryl (meth) acrylate or 4-hydroxybryl (meth) acrylate can be used. Various types of hydroxyl group-containing (meth) acrylic acid esters can be used.

As only other typical vinyl-based monomers copolymerizable with the vinyl-based monomer containing a carboxy group and / or a hydroxyl group, methyl (meth) acrylate, ethyl ( (Meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2
-Various (meth) acrylic acid esters such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate;

Dialkyl esters of various unsaturated dibasic acids, such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate or dimethylitaconate; (meth) acrylamide, N, N-dimethylacrylamide, N -Alkoxymethyl (meth)
Acrylamide, diacetone (meth) acrylamide,
Alternatively, various carboxylic acid amide group-containing vinyl monomers such as N-methylolacrylamide;

Vinyl monomers containing various sulfonamide groups such as p-styrenesulfonamide, N-methyl-p-styrenesulfonamide or N, N-dimethyl-p-styrenesulfonamide; (meth) acrylonitrile Various cyano group-containing vinyl monomers; or various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters such as the above-mentioned (meth) acrylic acid hydroxyalkyl esters, etc. And various phosphoric acid ester bond-containing vinyl monomers, which are condensation products of phosphoric acid or phosphoric acid esters;

Such as p-styrene sulfonic acid or 2-acrylamido-2-methyl-propane sulfonic acid,
Vinyl monomers containing various sulfonic acid groups; vinyl acetate,
Various vinyl esters such as vinyl benzoate or "Veoba" (vinyl ester manufactured by Shell in the Netherlands); "Viscoat 8F, 8FM, 3F or 3F"
M ”(fluorine-containing (meth) acrylic monomers manufactured by Osaka Organic Chemical Industry Co., Ltd.) or perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or N-isopropyl perfluorooctanesulfonamidoethyl (meth) acrylate Like,
Various (per) fluoroalkyl group-containing vinyl monomers;

Various halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride or chlorotrifluoroethylene; or of styrene, α-methylstyrene, p-tert-butylstyrene or vinyltoluene. As described above, various aromatic vinyl monomers are used.

In order to prepare the above urethane block copolymer by using various monomers as listed above, 0.5 of the above vinyl group-containing carboxy group monomer is used. To 100% by weight, preferably 1 to 50% by weight, and 99.5 to 0% by weight of the other vinyl-based monomer copolymerizable with the carboxy group-containing vinyl-based monomer,
Preferably, it is copolymerized with 99 to 50% by weight,

The hydroxyl group-containing vinyl monomer of 0.
5 to 100% by weight, preferably 1 to 50% by weight, and 99.5 to 0% by weight of the other vinyl-based monomer copolymerizable with the hydroxyl group-containing vinyl-based monomer, preferably 99.
˜50% by weight, or a carboxy group-containing vinyl-based monomer and a hydroxyl group-containing vinyl-based monomer may be used in combination for copolymerization.

The above-mentioned polymerization reaction in which the polymerizable unsaturated bond-containing monomer is block-polymerized in the presence of the so-called polymeric azo initiator as described above, may be carried out by a conventional method. .

That is, although various methods can be adopted as the polymerization method, the solution radical polymerization method is preferable because it is simple and the polymerization temperature is usually 60 to 1
The temperature within the range of 40 ° C. is suitable, and the polymerization time is
About 6 to 20 hours is appropriate.

Further, for example, the solution radical polymerization described above will be described in more detail. Various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; methyl acetate, ethyl acetate, butyl acetate or acetic acid. Various ester systems such as amyl; various ketone systems such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone;

Various organic solvents such as various nitrogen-containing systems such as N-methylpyrrolidone; or various alcohols such as methanol or butanol are used, and if necessary, azobisisobutyronitrile and the like. Various radical polymerization initiators such as various well-known and commonly-used azo-based compounds; or various well-known and commonly-used peroxides such as benzoyl peroxide, etc. Number average molecular weight of 1,50 having both structural units represented by formulas (I) and (II)
It can be performed in combination with a compound of 0 to 50,000,

Furthermore, if necessary, lauryl mercaptan, octyl mercaptan, 2 may be used as a molecular weight regulator.
It is also possible to use various known and commonly used chain transfer agents represented by mercaptoethanol or thioglycolic acid.

In carrying out such a polymerization reaction, the polymer azo initiator and the polymerizable unsaturated bond-containing monomer are used in amounts of 2
˜95% by weight, preferably 5 to 90% by weight, while the polymerizable unsaturated group-containing monomer is 98% by weight.
-5% by weight, preferably 95-10% by weight is suitable.

In particular, the amount of the polymeric azo initiator used has a great influence on the coating film performance of the coating resin of the present invention, and when it is less than 2% by weight, the polymerizable monomer amount is inevitable. No matter how you change the composition of the body and devise it, you will not be able to obtain something with sufficient coating film performance, on the other hand,
If it exceeds 95% by weight, the polyurethane polyol, polyester polyol, etc. constituting the initiator inevitably have poor solubility in a solvent and cause turbidity, and also contain a diazo bond. Since the ratio becomes too high, it becomes impossible to increase the molecular weight of the copolymer portion based on the block-copolymerizable polymerizable monomer, and as a result, the drying property and flexibility of the coating film, It becomes extremely low, so it is not preferable in any case,

Moreover, the amount of the initiator used is 95% by weight.
When it exceeds, it is easy to run only for the coupling between the initiators, and in such a re-coupling state, the initiation of the polymerization cannot be accomplished at all, and therefore the copolymer based on the polymerizable monomer Polyurethane polyol, polyester polyol, etc., in which no portion is introduced at all, are present in the system in a large amount, and a clear coating film is not provided, either of which is not preferable.

The block copolymer thus obtained is
Since the coating resin of the present invention is excellent in pigment dispersibility and gives a coating film having toughness and elasticity as coating film properties, the coating resin of the present invention is used for building exteriors and interiors. When used as a coating, plastic coating, wood coating, metal coating, etc., it is necessary to provide a coating film that has excellent dryness, hardness, outdoor stain resistance, low temperature bending resistance, and adhesion, among others. It will be possible.

The various organometallic chelate compounds described above will be described. First, if only representative examples of hexacoordinate organoaluminum chelate compounds are given, general formula

[0047]

[Chemical 7]

[Wherein at least one of R ₄ , R ₅ or R _{6 in} the formula represents a C _{1 to} C ₁₃ alkoxy group or a C _{3 to} C ₁₀ alkoxyalkoxyl group, and the remainder is assumed to represent C ₁ -C ₆ becomes an alkyl group, an aryl group, an alkenyl group or substituted by a mercapto group or an amino group, and C1 -C6 consisting alkyl. ] An organoaluminum compound represented by the above formula can be obtained by treating it with various chelating agents as described below.

As specific examples of such chelating agents, various lower alkanolamines such as triethanolamine or diethanolamine; various diketones such as diacetone alcohol; ethylene glycol. Such as various glycols; various oxycarboxylic acids such as tartaric acid; dicarboxylic acids or their esters; or acetoacetic acid esters, among which lower alkanolamines, oxycarboxylic acids or diketones, etc. Use is desirable.

As the organoaluminum chelate compounds, only representative ones are exemplified, such as aluminum isopropylate, aluminum sec-butyrate or aluminum tert-butyrate, and also aluminum tris (ethylacetoacetonate), Aluminum such as trisethylacetoacetato aluminum, tris (n-propylacetoacetato) aluminum, tris (iso-propylacetoacetato) aluminum, trissalicylaldehyde aluminum or tris (acetoacetonato) aluminum.

Among these organoaluminum chelate compounds, only those in which a hydroxyl group, an alkoxy group or the like is directly bonded to an aluminum atom have poor storage stability of the resin composition containing them. Therefore, it can be said that it is not preferable.

Next, among the organometallic chelate compounds, only typical ones as the 8-coordinate organozirconium compound will be exemplified.

[0053]

[Chemical 8]

However, at least two of R ₇ , R ₈ , R ₉ or R _{10 in} the formula represent an alkoxy group consisting of C _{1 to} C ₁₂ or an alkoxyalkoxyl group consisting of C _{3 to} C _10. and things, and the remainder are substituted with such C ₁ -C ₆ becomes an alkyl group, an aryl group, an alkenyl group or a mercapto group or amino group, C ₁ -C6
Represents an alkyl group and the like. ] The organozirconium compound represented by the formula [1] is obtained by treating it with a chelating agent.

Among the above chelating agents, only the representative ones are the same as those in the above-mentioned organoaluminum chelating compound. Specific examples of the organic zirconium chelate compounds are tetrakis (ozalic acid) zirconium, tetrakis (acetylacetone) zirconium, tetrakis (n-propylacetoacetato) zirconium or tetrakis (salicylaldehyde) zirconium. However, of course, a partial condensate obtained by using these compounds as monomers, preferably,
Dimers to 10-mers are also used.

Further, among the metal chelate compounds,
As the organic titanium chelate compound, only typical ones are exemplified, such as tetramethyl titanate, tetraethyl titanate, tetra n-propyl titanate, tetraisopropyl titanate, tetra n-butyl titanate or tetra tert-butyl titanate. Including various monomers,

Partially condensed forms of tetraisopropyl titanate, tetra n-butyl titanate, tetraisobutyl titanate or tetra-tert-butyl titanate dimers to 10-mers and the like.

Next, the amount of the above-mentioned organometallic chelate compound used as a cross-linking curing agent is 1 for the carboxy group and / or the hydroxyl group, respectively, present in the resin composition.
With respect to the equivalent, 0.5 to 2 equivalents, preferably 0.8 to
The ratio is within the range of 1.2 equivalents, and the compounding ratio may be such a ratio.

In addition to organic or inorganic pigments, various well-known and conventional additives such as flow regulators, color separation inhibitors, ultraviolet absorbers, and antioxidants are added to the composition of the present invention. Agents; or various fibrin derivatives such as nitrocellulose or cellulose acetate butyrate; or various resins such as chlorinated polyethylene, chlorinated polypropylene, petroleum resin, chlorinated rubber, acrylic beads or urethane beads It is also possible to add a kind.

[0060]

EXAMPLES Next, the present invention will be explained more specifically with reference to Production Examples, Examples and Comparative Examples. In the following, all parts and percentages are by weight unless otherwise specified. It shall be the standard.

Production Example 1 (Preparation Example of Polymer Azo Initiator) In a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 1,500 parts of methyl ethyl ketone, 424 parts of dipropylene glycol and di-n were added. -Butyltin dilaurylate (0.2 parts) was charged, and the mixture was heated to 80 ° C with stirring, and then 532 of hexamethylene diisocyanate was added.
Parts were added dropwise over 2 hours, and further maintained at 80 ° C. for 5 hours to continue the reaction.

The number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the isocyanate group-containing polyurethane thus obtained was 3,700.

However, after the treatment of reacting this isocyanate group with diethyleneamine, G
It is used for measurement by PC.

Then, 2,456 parts of this isocyanate group-containing polyurethane was charged into a reaction vessel similar to the above, and 44 parts of azobisisopropanol was added to the polyurethane under ice cooling, The temperature was raised to 30 ° C., and the temperature was maintained for 10 hours to carry out the reaction.

The number average molecular weight of the polyurethane high molecular weight azo initiator thus obtained was 22,500, and therefore it is known that it has an average of 6.1 diazo bonds in one molecule. .

The initiator solution had a nonvolatile content of 40
%, And the Gardner viscosity at 25 ° C. (hereinafter the same) was Z ₂ .

Production Example 2 (same as above) A reaction vessel similar to that of Production Example 1 was charged with 1,500 parts of methyl ethyl ketone, 46 parts of azobiscyanopropanol and 0.1 part of di-n-butyltin dilaurylate and stirred. 552 parts of hexamethylene diisocyanate were added dropwise to the flask under ice cooling over 2 hours, and then,
The temperature was raised to 20 ° C., the temperature was maintained at the same temperature for 2 hours to continue the reaction, and then ice cooling was performed again.

Then, 347 of dipropylene glycol was used.
Parts and 55 of 3-methyl-1,5-pentanediol
Then, the temperature was raised to 30 ° C., and the temperature was kept at the same temperature for 10 hours to continue the reaction.

The polyurethane high molecular weight azo initiator obtained here had a number average molecular weight of 18,500 and a viscosity of YZ.
And the nonvolatile content was 40%.

To determine other characteristic values for this polymeric azo initiator, for 20 parts of the initiator,
1.0 part of hydroquinone and 20 parts of n-butanol were added and heating was continued at 100 ° C. for 10 hours to decompose the initiator.

The number average molecular weight of the decomposed product obtained here was 4,100, and it was found that the objective polymer azo initiator had an average of 4.5 diazo bonds in one molecule.

Production Example 3 (same as above) A reaction vessel equipped with a thermometer, a stirrer and an air condenser was charged with 614 parts of adipic acid, 438 parts of neopentyl glycol and 698 parts of isophthalic acid, and heated at 140 ° C. for 1 hour. After reacting for a period of time, it took 2 hours to gradually raise the temperature to 220 ° C, and at the same temperature, 6
After reacting for a period of time, the acid value is 2 and the hydroxyl value is 7
A polyester resin having a number average molecular weight of 8 and a number average molecular weight of 1,400 was obtained.

Then, in the same reaction vessel as in Production Example 1, 837 parts of the above polyester resin, 27 parts of azobiscyanopropanol, 0.1 part of di-n-butyltin dilaurylate and 1,500 parts of methyl ethyl ketone were placed. Then, 134 parts of hexamethylene diisocyanate was added dropwise over 2 hours under ice cooling.

After the dropping, the temperature was raised to 30 ° C., and the temperature was kept at the same temperature for 10 hours to continue the reaction.
A solution of the desired polyurethane polymer azo initiator having a number average molecular weight of 28,000, a viscosity of W-X and a nonvolatile content of 40% was obtained.

With respect to 20 parts of this polyurethane polymer azo initiator, 1.0 part of hydroquinone and n were used.
-Add 20 parts of butanol and add 10 parts at 100 ° C.
When the polymer azo initiator was decomposed by continuing heating for a period of time, the decomposed product had a number average molecular weight of 4,500.

Therefore, it was found that this polyurethane polymer azo initiator has 6.2 diazo bonds in one molecule.

Production Example 4 (Preparation Example of Polyurethane-Acrylic Resin Block Copolymer) A four-necked flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 30 parts of toluene, 30 parts of n-butanol and methyl ethyl ketone. 30 parts were charged and the temperature was raised to 80 ° C., and 10 parts of methacrylic acid, 20 parts of methyl methacrylate and 30 parts of n-butyl methacrylate were added thereto, and the polyurethane polymer azo obtained in Production Example 1 was started. A mixture of 100 parts of the agent was added dropwise over 4 hours, and the polymerization reaction was continued by maintaining the same temperature for 10 hours after the completion of the addition, resulting in a polyurethane-acrylic resin having a number average molecular weight. The block copolymer has a nonvolatile content of 4
A 0% solution with a viscosity of UV was obtained.

Production Examples 5 to 7 (same as above) Using a polymerization solvent, an initiator and a polymerizable unsaturated bond-containing monomer as shown in Table 1, and under the polymerization conditions as shown in the same table. Various block copolymers and random copolymers were obtained in the same manner as in Production Example 1 except that the above procedure was changed.

Example 1 250 parts of the resin obtained in Production Example 4 and 5 parts of carbon black were blended and kneaded in a sand mill for 1 hour, then 12.5 parts of aluminum triacetylacetonate was added. In addition, methyl ethyl ketone / isopropyl alcohol / n-butanol / methyl isobutyl ketone / diacetone alcohol = 40/10/20
After diluting with 100 parts of thinner consisting of / 10/20 (weight ratio), various test plates were coated with air spray.

The evaluation results of various properties of the coating film were obtained by drying the coating film at 60 ° C. for 30 minutes and then allowing it to stand at 25 ° C. for 5 days with respect to the contents shown in Table 2. Is.

Examples 2 to 4 and Comparative Examples 1 and 2 The composition as shown in Table 2 was used to prepare a coating composition having the same composition as in Example 1, and various performances were evaluated.

[0082]

[Table 1]

<< Footnote of Table 1 >> "MMA" ... Abbreviation of methyl methacrylate "n-BMA" ... Abbreviation of n-butyl methacrylate "n-BA" ... Abbreviation of n-butyl acrylate

"MAI of Production Example 1" ... Abbreviation of Polymer Initiator Obtained in Production Example 1 "MAI of Production Example 2" ... Abbreviation of Polymer Initiator Obtained in Production Example 2 MAI of Production Example 3 "... Abbreviation of Polymer Initiator Obtained in Production Example 3

"BPO" ... Abbreviation of benzoyl peroxide

[0086]

[Table 2]

[0087]

[Table 3]

<< Footnote of Table 2 >>"ATAA" .... Abbreviation of aluminum triacetylacetonate "ZTAA" .... Abbreviation of zirconium tetraacetylacetonate "TIBT" .... Abbreviation of tetraisopropyl titanate

[0089]

[Table 4]

[0090]

The room temperature curable resin composition of the present invention obtained as described above is particularly highly practicable in that it has a good tactile sensation and is excellent in alcohol resistance. is there.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C08G 18/83 NGV

Claims (4)

[Claims] 1. A block copolymer containing a carboxyl group and / or a hydroxyl group, which has both a polyurethane segment and a vinyl polymer segment, and a 6-coordinate organoaluminum chelate compound, an 8-coordinate organozirconium compound and / or A room temperature curable resin composition comprising an organic titanium chelate compound. 2. A carboxy group- and / or hydroxyl group-containing block copolymer having both the above-mentioned polyurethane segment and vinyl polymer segment, which has a carboxy group and / or a hydroxyl group in the presence of a urethane resin having an azo group. The room temperature curable resin composition according to claim 1, which is obtained by polymerizing a polymerizable unsaturated monomer containing the vinyl monomer as an essential component. 3. A block copolymer having the above-mentioned polyurethane segment and vinyl polymer segment together, wherein at least one block copolymer in one molecule has the general formula: [Wherein R ₁ is an alkylene group, a cyclic alkylene group, an alkylene group having an ester group, a benzene ring, or an alkylene group containing a benzene ring, and R ₂ and R ₂ 'are the same. May represent different alkylene groups, alkylene groups containing cyano groups, alkylene groups containing amide bonds, or alkylene groups having both amide bonds and hydroxyl groups. ] And a general formula: [However, R ₃ in the formula represents a polyol residue. ] It is obtained by polymerizing a polymerizable unsaturated monomer containing a vinyl monomer having a carboxy group and / or a hydroxyl group as an essential component in the presence of a compound having a structural unit represented by The room temperature curable resin composition according to claim 1. 4. A block copolymer having the above-mentioned polyurethane segment and vinyl polymer segment together, wherein at least one block copolymer in one molecule has the general formula: embedded image [Wherein R ₁ is an alkylene group, a cyclic alkylene group, an alkylene group having an ester group, a benzene ring, or an alkylene group containing a benzene ring, and R ₂ and R ₂ 'are the same. May represent different alkylene groups, alkylene groups containing cyano groups, alkylene groups containing amide bonds, or alkylene groups having both amide bonds and hydroxyl groups. ] And the general formula: [However, R ₃ in the formula represents a polyol residue. ] The structural unit shown by these, and 1,500
~ 2 of compounds having a number average molecular weight of 50,000
It is obtained by polymerizing a polymerizable unsaturated monomer containing 98 to 5 parts by weight of a vinyl monomer having a carboxy group and / or a hydroxyl group as an essential component in the presence of 95 parts by weight. Item 4. The room temperature curable resin composition according to item 1, 2 or 3.