JPH08269395A - Intermediate coating composition - Google Patents

Abstract

PURPOSE: To obtain an intermediate coating composition for an automobile exhibiting excellent resistance to chipping and excellent appearance. CONSTITUTION: This intermediate coating composition comprises (A) a polyester polyol having 50-400mgKOH/g hydroxyl group value and (B) polycarbonate diol having 500-4000 weight-average molecular weight in a weight ratio of (A) to (B) of (90/10)-(0/100), and further, (C) a polyisocyanate compound blocked its isocyanate group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an intermediate coating composition for automobiles. More specifically, the present invention relates to an automotive intermediate coating composition that exhibits good chipping resistance and is excellent in appearance.

[0002]

2. Description of the Related Art The outer plate of an automobile body collides with flying stones during traveling, so-called "chipping peeling" occurs, which deteriorates the aesthetic appearance, and if the damage caused by flying stones reaches the surface of the steel sheet, the peeling body The steel plate is exposed and rusted, and corrosion progresses. For this reason, serious attention has been paid to measures against "chipping peeling", and research and development of paints having excellent anti-chipping performance have been conducted. For example, as a primer or intermediate coating composition for automobiles as a measure against chipping and peeling off the lower part of a vehicle body outer shell, a coating composition (JP-A-53-45813) which does not reach the base even when scratched by using a specific pigment, isocyanate A coating composition using a compound (JP-A-54-7)
No. 3836, JP-A-57-68176) and the like have been proposed.

[0003]

However, a method of using a composition containing 20 to 50 parts by weight of talc having a particle size of 10 to 20 μm (JP-A-53-45813).
Since the scratches caused by chipping hardly reach the steel plate surface of the base material, rusting of the outer steel plate itself of the vehicle is reduced, but the peeled area of the top coat is large, which has the drawback of impairing the aesthetics.
Further, a method using isocyanate (Japanese Patent Application Laid-Open No. 54-7
No. 3836) has a drawback that the chipping performance is not sufficient, and in the case of a method using a compound obtained by reacting a polybutadiene having a hydroxyl group with an isocyanate group (JP-A-57-68176), Although the chipping performance is good, there is a drawback in that the finished appearance after the top coating is inferior. On the other hand, as another measure, Japanese Patent Publication Sho 61-369.
In Japanese Patent Publication No. 95, the NCO concentration on the undercoat coating film is 0.1 to 0.1
After applying a soft urethane paint containing 5.0 mmol / g of a blocked isocyanate compound and a polyhydroxy compound having an OH concentration of 0.05 to 20 mmol / g as main components, an intermediate paint is applied, dried, and a top coat is applied. A method comprising a baking and drying process has been proposed. In addition, a method of coating a coating composition composed of a soft polyester resin and a melamine resin, a method of coating a coating composition composed of a maleic acid-grafted polyolefin resin, and the like have been proposed, but these methods are commonly used. The problem with the above is that the number of coating steps is increased once compared to the conventional three-layer coating structure consisting of undercoat, intermediate coating and top coating, and the problem remains that productivity in the coating step is reduced. As another means for improving the chipping resistance, there has been proposed a method of increasing the molecular weight of the polyester resin used in the intermediate coating composition to impart toughness to the coating film and improve the chipping resistance. However, in such a method, since the polyester resin having a high molecular weight has a high viscosity, the solid content of the coating at the time of coating is inevitably reduced, so that the opacity of the base is reduced and the smoothness of the intermediate coating surface itself is also lost. It has the disadvantage of being exposed. Under the circumstances as described above, in order to obtain good chipping resistance in painting of the vehicle body, it is the current situation that the chipping-resistant paints corresponding to different chipping strengths are individually applied to each part of the vehicle body. . When applying such chipping-resistant paint, not only the coating process increases and productivity is impaired, but also undercoat, intermediate coat,
Also, the appearance quality is apt to deteriorate as compared with the case of a three-layer coating consisting of a top coat. From such a current situation, a means for improving the chipping resistance without increasing the number of steps and without deteriorating the appearance quality is desired, and as a solution, the chipping resistance of the intermediate coating film can be improved by improving the appearance quality. There has been a long-awaited completion of a paint that can be improved while maintaining it.

[0004]

In view of the above situation, the present inventors have conducted extensive studies to improve the above-mentioned problems,
We have found an intermediate coating composition that is excellent in both chipping resistance and appearance quality, and finally completed the present invention.

That is, according to the present invention, (A) a polyester polyol having a hydroxyl value of 50 to 400 mgKOH / g, and (B) a polycarbonate diol having a weight average molecular weight of 500 to 4000 at a weight ratio of (A) to (B) of 90/10.
An intermediate coating composition containing (C) a polyisocyanate compound in which an isocyanate group is blocked, in an amount of 0/100.

The intermediate coating material in the present invention will be described. (A) contained in the intermediate coating used in the present invention
A polyester polyol having a hydroxyl value of 50 to 400 mgKOH / g means one or more of reaction products of a polyhydric alcohol and a polycarboxylic acid and / or an anhydride thereof in an amount less than a stoichiometric amount. It is a mixture. If the hydroxyl value is lower than 50, chipping resistance, especially at high temperatures,
The chipping resistance after exposure to a deteriorated environment such as a high humidity environment deteriorates, and when it exceeds 400, the chipping resistance also deteriorates, which is not preferable.

Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomeric pentanediols and isomeric hexane. Diols or octane diols such as 2-ethyl-1,3-hexanediol, 1,2-, 1,3- and 1,4-bis (hydroxymethyl) -cyclohexanone, trimethylolpropane, glycerin and the like can be mentioned. it can. Examples of polycarboxylic acids and polycarboxylic anhydrides include oxalic acid, succinic acid, adipic acid,
Sebacic acid, phthalic acid, isophthalic acid, terephthalic acid,
Divalent carboxylic acids such as fumaric acid, maleic acid, itaconic acid, trivalent carboxylic acids such as trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, polycarboxylic acid anhydrides such as trimellitic anhydride And dimers or trimers of fatty acids such as castor oil fatty acid trimers. The polyester polyol can be produced by a known method, and as an example, it is obtained by dehydration condensation of a polyhydric alcohol and a polycarboxylic acid or a polycarboxylic anhydride in a reaction vessel at a temperature of 200 to 230 ° C. To be

Next, the (B) polycarbonate diol having a weight average molecular weight of 500 to 4000 contained in the intermediate coating material used in the present invention is one or two selected from the group consisting of alkylene carbonate, diaryl carbonate and dialkyl carbonate. It is a polycarbonate diol obtained by reacting one or more compounds with diols and / or polyether polyols. Examples of alkylene carbonate include ethylene carbonate,
Examples include 1,2-propylene carbonate and 1,2-butylene carbonate. Examples of the diaryl carbonate include diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate,
4,4'-dimethyl-diphenyl carbonate, 4,4
Examples thereof include'-diethyl-diphenyl carbonate and 4,4'-dipropyl-diphenyl carbonate.
Examples of dialkyl carbonates are dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-te.
rt. -Butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate and the like can be mentioned. As a co-reacting substance for these carbonates, examples of diols include ethylene glycol and 1,2-
Propanediol, 1,3-Propanediol, 1,3
-Butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-methyl-pentanediol, 3-methyl-pentanediol, 2,2,4-trimethyl-1, 6-hexanediol, 2,3,5-trimethylpentanediol and the like can be mentioned. Examples of polyether polyols include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and alkylene oxide adducts of diols. Examples of the diols used here include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomers pentanediols, isomers. Hexanediols or octanediols such as 2-ethyl-1,
3-hexanediol, 1,2-, 1,3- and 1,
4-bis (hydroxymethyl) -cyclohexanone and the like can be mentioned, and examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,
2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin and the like can be mentioned, and it is also possible to use a mixture of two or more thereof. The weight average molecular weight of these polyether polyols is not particularly limited,
The range of 2000 is preferred. This is because when it is in the range of 300 to 2000, good coating workability is obtained, and thus a good coating appearance having excellent smoothness is easily obtained.
The above-mentioned diols and polyether polyols may be used alone or in combination of two or more. Any of these can react with the above-mentioned carbonates, that is, one or more compounds selected from alkylene carbonates, diaryl carbonates, and dialkyl carbonates to form a polycarbonate diol by a known method. As an example of the reaction method, an example using dialkyl carbonate will be described in detail. For the reaction, a catalyst usually used for transesterification can be used, and for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium,
Metals such as zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, and cerium, and alkoxides thereof can be used. Also, as another suitable catalyst, carbonates of alkali and alkaline earth metals, zinc borate, zinc oxide, lead silicate, lead carbonate, antimony trioxide, germanium dioxide,
Examples include cerium trioxide and aluminum isopropoxide. Particularly useful and preferred catalysts are organometallic compounds such as metal salts of the organic acids magnesium, calcium, cerium, barium, zinc, tin, titanium and the like. The amount of the catalyst used is 0.0 with respect to the total weight of the starting materials.
001% to 1.0%, preferably 0.001% to 0.2
% Is a proper amount. The reaction temperature is preferably 80 ° C. to 220 ° C., the reaction is carried out near the boiling point of the dialkyl carbonate in the initial stage of the reaction, and the temperature is gradually raised as the reaction proceeds, and the reaction is further advanced. An apparatus capable of separating the produced diol compound and the raw material dialkyl carbonate is usually a reactor equipped with a distillation column, which carries out the reaction while refluxing the dialkyl carbonate, and distills the alcohol produced as the reaction proceeds. When the dialkyl carbonate and the alcohol distilled at this time are partly azeotropically dissipated and dissipated, it is a good idea to estimate this dissipated amount when the raw materials are calculated and charged. Theoretically, the diol compound (n +
1) Although the theoretical equivalence ratio is obtained by charging in a molar ratio, it is actually preferable that the charging molar ratio of the dialkyl carbonate / diol compound is 1.1 to 1.3 of the theoretical molar ratio. The reaction can be carried out at normal pressure, but the reaction can be accelerated in the latter half of the reaction under reduced pressure, for example, at 1 mmHg to 200 mmHg. The weight average molecular weight of the polycarbonate diol of the present invention is 5
The range is from 00 to 4000, preferably from 1000 to 3000. If it is less than 500, the chipping resistance is lowered,
If it exceeds 4000, the appearance of the coating film may be unfavorably deteriorated or wrinkled. Precisely obtaining a polycarbonate diol having a desired molecular weight is achieved by changing the reaction molar ratio of the raw material diol compound and the carbonate diol.

The above-mentioned (A) hydroxyl value 50 to 400 mgK
The blending ratio of the OH / g polyester polyol and (B) the polycarbonate diol having a weight average molecular weight of 500 to 4000 is 90, preferably 70, with respect to the weight ratio of polyester polyol 90 to carbonate diol 10.
The ratio of 0 to polyester polyol 0 preferably 30 to carbonate diol 100, preferably 70, and when the amount of (B) carbonate diol is less than 10 parts in 100 parts of the total amount of (A) and (B), chipping resistance is obtained. descend.

Next, the (C) isocyanate group-blocked polyisocyanate compound contained in the intermediate coating composition of the present invention means that the isocyanate group of the polyisocyanate compound is blocked with a commonly used blocking agent. One or a mixture of two or more compounds,
Examples of polyisocyanate compounds include 2,4- and / or 2,6-diisocyanatotoluene, 2,4
-Diisocyanate-dixirohexyl methane, 4,4
-Diisocyanate-dixlohexylmethane, hexamethylene diisocyanate, 1-isocyanate-3,
Diisocyanates such as 3,5-trimethyl-5-isocyanatomethylcyclohexane, and these diisocyanates and polyhydric alcohols in less than equivalent amounts such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol. , 1,4-butanediol, trimethylolpropane, an adduct formed by reaction with glycerin, or the like, a burette trimer of the above diisocyanate, an isocyanurate trimer of the above diisocyanate, and the like. It is obtained by reacting an equivalent amount or an equivalent amount or more of a blocking agent. Examples of such blocking agents include phenol, p-tert. -P-substituted phenols such as butylphenol, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s
ec-butyl alcohol, tert. -Alcohols such as butyl alcohol, n-amyl alcohol and isoamyl alcohol, lactams such as ε-caprolactam, methyl ethyl ketoxime, diethyl ketoxime, methyl isobutyl ketoxime, ketoxime such as diisobutyl ketoxime, and acetone oxime are known. However, various selections are possible. The amount of the polyisocyanate compound in which the isocyanate group is blocked is not particularly limited, but the free isocyanate group generated after the blocking agent is dissociated has the above-mentioned (A) hydroxyl value of 50 to 400 mgKOH / g.
Polyester polyol, and (B) weight average molecular weight 5
It is preferable that the molar ratio is 0.5 to 1.5 with respect to the hydroxyl group content of the polycarbonate diol of 00 to 4000.

The intermediate coating composition of the present invention may optionally contain various polyols in addition to the above resin components. Examples of polyols include polyether polyols and polycaprolactone polyols. Examples of the polyether polyol include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and alkylene oxide adduct of polyhydric alcohol. Examples of the polyhydric alcohol used here include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomeric pentanediols, and isomers. Hexanediols or octanediols such as 2-ethyl-1,
3-hexanediol, 1,2-, 1,3- and 1,
4-bis (hydroxymethyl) -cyclohexanone, trimethylolpropane, glycerin and the like can be mentioned, and examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide. , Tetrahydrofuran, styrene oxide, epichlorohydrin and the like, and it is also possible to use a mixture of two or more thereof. Examples of polycaprolactone polyols include ε
A compound obtained by ring-opening polymerization of a lactone such as -caprolactone or γ-valerolactone in the presence of a polyhydric alcohol such as the above-mentioned ethylene glycol.

The intermediate coating composition of the present invention comprises, in addition to the above-mentioned components, if desired, coloring agents such as carbon black and pigments such as titanium dioxide, curing catalysts such as tertiary amines and organotin compounds, and fluidity. Various additives such as regulators and defoamers, hydrocarbons such as toluene, xylene and solvent naphtha, esters such as ethyl acetate, butyl acetate and amyl acetate, ketones such as methyl ethyl ketone, methyl butyl ketone, phorone and isophorone The organic solvent can be included. The content of these pigments, additives, solvents and the like is not particularly limited, but when a remarkably large amount of pigment is used, the gloss of the finish coating film may decrease, so that It is desirable that the content is usually 120 parts by weight or less based on 100 parts by weight of the total amount of the resin components.

In the present invention, an automobile body is usually subjected to electrodeposition coating as an undercoat, and then the above-mentioned intermediate coating composition is applied by a conventional coating method, for example, air spray, airless spray, electrostatic coating, spin coating. It is applied by means such as atomization coating and dip coating. The coating film thickness of the intermediate coating material is 10 μm to 80 μm, preferably 20 to 40 μm as a dry film thickness.
Is. When the thickness is less than 10 μm, there is no problem with respect to the coating film physical properties such as adhesion, but the finished appearance, particularly the smoothness, deteriorates. If it is thicker than 80 μm, cohesive failure of the coating film may occur after the deterioration test, and external defects such as sagging and armpit are likely to occur, which is not preferable.

The intermediate coating composition of the present invention is applied by the above-mentioned means and then dried by heating. An example of heat drying conditions is 100 to 140 ° C. for 3 to 30 minutes.
The cured coating film formed from the intermediate coating composition of the present invention,
Glass transition temperature is -20 ° C to 0 ° C, elongation is 10 to 100% at temperature 20 ° C, 1 to 50% at temperature -20 ° C, and tensile strength is 40 at temperature 20 ° C.
It will be in the range of 0 to 700 Kgf / cm ² . 400-70
The tensile strength in the range of 0 Kg / cm ² is effective in preventing damage and breakage of the coating film due to stone splash, and exerts sufficient chipping resistance. Also, at a temperature of 20 ° C., 10 to 10
By having an elongation of 0 to 50% at a temperature of −20 ° C., sufficient adhesion of the chipping resistant coating material to the substrate can be maintained, and chipping peeling can be prevented. In addition, the environment in which the car body is used is approximately -20 ° C.
It is -40 ° C, and it is necessary to set the glass transition point in the range of -20 to 0 ° C in order to maintain constant physical properties under such an environment. In the coating step using the intermediate coating composition of the present invention, a desired coated article can be obtained by usually applying an intermediate coating followed by applying a top coating and drying. The top-coat paint is not particularly limited, and a conventionally used top-coat paint can be used. As an example,
For example, a one-component baking type paint containing an amino resin such as melamine resin or benzoguanamine resin as a curing agent or 1
Examples include liquid or two-component polyurethane resin paints. The coating conditions for the topcoat paint are defined as the coating conditions for the paint used, and are not particularly limited.
Further, if desired, another coating material may be repeatedly applied between the intermediate coating material and the top coating material, or after the top coating material is applied.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the description, “parts” means “parts by weight” unless otherwise specified.

[0016]

【Example】

(Production Example 1) Production of polyester polyol for intermediate coating material A round bottom four-necked flask equipped with a thermometer, a stirrer, and a water separator is placed in a round-bottomed four-necked flask, 350 parts of phthalic anhydride, 171 parts of adipic acid, and 335 parts of neopentyl glycol. Then, 144 parts of trimethylolpropane were charged, the temperature was raised to 230 ° C., and the mixture was maintained under stirring for 6 hours to carry out an esterification reaction while separating and removing water flowing out. After cooling, 269 parts of xylene and 269 parts of propylene glycol monomethyl ether acetate were added to obtain a polyester polyol having a nonvolatile content of 65% and a hydroxyl value of 170 mgKOH / g.

(Production Example 2) Production of Polycarbonate Diol for Intermediate Coating Paint A round-bottomed four-necked flask equipped with a thermometer, a stirrer and a distillation column was charged with 620 parts of dimethyl carbonate and 740 parts of 1,6-hexanediol. 640 parts of polytetramethylene glycol having a molecular weight of 800 and 0.30 part of tetrabutyl titanate as a catalyst were charged, the reaction was carried out under normal pressure at the boiling point of dimethyl carbonate, and the methanol flowing out was distilled off. The temperature of the reaction product was gradually raised to 200 ° C., and when the distillation of methanol was hardly observed, the depressurization operation was started, and the unreacted product was distilled off under the final decompression of 20 mmHg to obtain the reaction product. It was The weight average molecular weight of the obtained polycarbonate diol was 1,900.

Production Example 3 Production of Polycarbonate Diol for Intermediate Coating Paint A round-bottomed four-necked flask equipped with a thermometer, a stirrer, and a distillation column was placed in 620 parts of dimethyl carbonate and 740 parts of 1,6-hexanediol. 640 parts of polypropylene glycol having a molecular weight of 750 and 0.25 part of tetrabutyl titanate as a catalyst were charged, the reaction was carried out under normal pressure at the boiling point of dimethyl carbonate, and the outflowing methanol was distilled off.
The temperature of the reaction product was gradually raised to 200 ° C., and when the distillation of methanol was hardly observed, the depressurization operation was started, and the unreacted product was distilled off under the final decompression of 20 mmHg to obtain the reaction product. It was The weight average molecular weight of the obtained polycarbonate diol was 2,000.

[Example 1] Production of intermediate coating material-A 50 parts of the above polyester polyol resin, 50 parts of polycarbonate diol, 74.3 parts of xylene, 25 parts of titanium dioxide, and 0.2 parts of carbon black were prepared using a sand mill. After kneading, 80.0 parts of Barnock DB-980K (theoretical isocyanate content: 10.5%, solid content: 75%, manufactured by Dainippon Ink and Chemicals, Inc.) was mixed as a blocked isocyanate, and the intermediate coating composition of the present invention- A
(Polyester polyol / polycarbonate diol = 40/60, hydroxyl group to isocyanate group molar ratio = 1.
0 / 1.0, nonvolatile content 60%) was produced.

[Examples 2 to 6] Production of intermediate coating materials B to F In the same manner as in Example 1, the intermediate coating materials B to F of the present invention were produced with the formulations shown in Table 1.

Test Example 1 On a steel sheet which had been subjected to a chemical conversion treatment and which had been subjected to cationic electrodeposition coating, an intermediate coating composition-A was spray-coated to a dry film thickness of 30 μm and baked at 140 ° C. for 20 minutes. Furthermore, a polyester / melamine resin-based white top coating composition was applied by spray coating to a dry film thickness of 30 μm, and baked at 140 ° C. for 20 minutes. When the obtained test plate was subjected to various coating film performance tests, the results were good as shown in Table 2, and it was confirmed that a good finished appearance with good chipping resistance and smoothness was obtained. .

Test Examples 2 to 6 Using the intermediate coating materials-B to F, test plates were prepared in the same manner as in Test Example 1 and a coating film performance test was conducted. The results were all good as shown in Table 2.

Comparative Test Example 1 As a comparative example, a test plate was prepared by coating in the same manner as in Test Example 1 except that the intermediate coating material-G containing no polycarbonate diol (see Table 3 for the composition) was used. A membrane performance test was carried out, but as shown in Table 3, the test results were poor and could not be put to practical use.

Comparative Test Examples 2 to 4 Comparative Examples 2 to 4 in Table 3 are test plates prepared by applying the same coating as in Test Example 1 using an intermediate coating material outside the scope of the present invention. All of them had problems in chipping resistance or finished appearance and could not be put to practical use.

Various tests were carried out under the test conditions described below. (1) Appearance Visually observe the coating film after top coating, and check for smoothness, sag, armpit,
Check for defects such as pinholes and uneven gloss. (2) Chipping resistance A chipping resistance test was carried out as follows as a test condition for reproducing chipping in a steel plate for vehicle body. Using a stepping stone tester (JA-400 type, manufactured by Suga Test Instruments Co., Ltd.), a coating test plate was obliquely attached to the sample holder of the tester at an angle of 30 ° from the horizontal and cooled to a temperature of -20 ° C Maintaining this temperature, 500g of basalt crushed stone (diameter 4.8mm-8.0mm) was 4.0K under the pressure of the same tester.
It is jetted at an air pressure of g / cm ² and collided. After that, the test plate was washed with water and dried, the coating film that was lifted up by chipping was removed with an adhesive tape, and the degree of peeling scratch was evaluated. (3) Adhesion 100 cross hatches having a width of 2 mm are cut with a cutter knife, and a peeling test is performed using an adhesive tape. The case where there is no peeling and all 100 cross-cuts remain is passed. (4) Water resistance The test plate was immersed in warm ion-exchanged water at 40 ° C for 240 hours,
Immediately after the removal, the water droplets are wiped off to check whether or not there is an abnormality in the appearance, and 100 cross hatches with a width of 2 mm are cut with a cutter knife, and a peeling test is performed using an adhesive tape. The case where there is no peeling and all 100 cross-cuts remain is passed.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

By using the intermediate coating composition of the present invention,
In automobile coating, it is possible to improve the chipping resistance of the intermediate coating film while maintaining good appearance quality, and it does not increase the number of steps and does not deteriorate the appearance quality. Improvement can be realized.

Claims (1)

[Claims] 1. (A) Hydroxyl value 50 to 400 mg KOH
/ G polyester polyol (B) Polycarbonate diol having a weight average molecular weight of 500 to 4000 at a weight ratio of (A) to (B) of 90/10.
An intermediate coating composition comprising a polyisocyanate compound (C) having an isocyanate group blocked, in an amount of 0/100.