JPH08269394A - 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 polyurethane resin having 2000-20000 weight-average molecular weight 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 and (D) a microgel having 0.2-1.5μm particle diameter.

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, etc.) are 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. For parts such as rocker parts or floor parts of the vehicle body that require severe chipping resistance, a film thickness normally applied as an intermediate coat, for example, 3
If the thickness is 0 μm, the chipping resistance is insufficient, and the chipping may cause scratches that reach the base material, leading to rusting. As a countermeasure against such a situation, a method of coating the film to a thickness of, for example, about 50 μm is conceivable, but in this case, a problem in coating workability such as dripping mainly occurs, and it cannot be said to be an effective method. In order to obtain good chipping resistance in the painting of the vehicle body by the above-mentioned situation, the chipping resistance performance which individually desires the chipping-resistant coating material corresponding to the different chipping strength in each part of the vehicle body is exhibited. The current situation is to paint with a film thickness. When such a chipping-resistant paint is applied, not only the number of painting steps increases and productivity is impaired, but also the appearance quality tends to deteriorate as compared with the case of a three-layer paint consisting of an undercoat, an intermediate coat, and a top coat. From this situation, without increasing the number of steps,
Further, a means for improving the chipping resistance that does not deteriorate the appearance quality is desired, and as a solution, the chipping resistance of the intermediate coating film is improved while maintaining a good appearance quality, and the required chipping resistance is also improved. There has been a long-awaited demand for the completion of a paint that can be applied without causing defects in appearance, such as film thickness sagging, which exhibits performance depending on the degree of property.

[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, the present invention provides (A) a polyurethane resin having a weight average molecular weight of 2000 to 20000, (B) a polycarbonate diol having a weight average molecular weight of 500 to 4000 in a weight ratio of (A) to (B) of 90/10.
It is characterized in that it is contained at a ratio in the range of 0/100, and further comprises (C) a polyisocyanate compound in which an isocyanate group is blocked and (D) a microgel having a particle diameter of 0.2 to 1.5 μm. It is an intermediate coating composition.

The intermediate coating material in the present invention will be described. (A) contained in the intermediate coating used in the present invention
A polyurethane resin having a weight average molecular weight of 2,000 to 20,000 is, for example, a polyhydric alcohol or a polyol.
One or two theoretically hydroxyl group-terminated polyurethane resins synthesized by reacting a compound containing two or more hydroxyl groups in the molecule with a stoichiometrically non-excessive diisocyanate to extend the chain. It is a mixture of the above.

Examples of polyhydric alcohols are Tobacco ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomeric pentanediols, 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. Examples of the polyol include polyether polyol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol. 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 polyester polyols are, for example, one or a mixture of two or more reaction products of a polyhydric alcohol and a less than stoichiometric amount of a polycarboxylic acid and / or their anhydrides. Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomeric pentanediols, isomeric hexanediols or Octanediols such as 2-ethyl-1,3-hexanediol, 1,2-, 1,3- and 1,4-bis (hydroxymethyl) -cyclohexanone, trimethylolpropane, and glycerin can be mentioned. Examples of polycarboxylic acids and polycarboxylic anhydrides include carboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, and itaconic acid. , Trivalent carboxylic acids such as trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, polyvalent carboxylic acid anhydrides such as trimellitic anhydride, dimeric or trimeric fatty acids such as castor oil fatty acid You can give a trimer. Examples of polycaprolactone polyols are compounds obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone in the presence of a polyhydric alcohol such as ethylin glycol described above.

Next, as an example of the diisocyanate,
2,4- and / or 2,6-diisocyanatotoluene, 2,4-diisocyanato-dixlohexylmethane, 4,4-diisocyanato-dixlohexylmethane, hexamethylene diisocyanate, 1-isocyanate -3,3,5-Trimethyl-5-isocyanatomethylcyclohexane and the like can be mentioned. These can be used alone or in combination of two or more. In the present invention, a weight average molecular weight of 2000
In the synthesis of the polyurethane resin of 20000 to 20000, the polyhydric alcohol or polyol and the diisocyanate are heated and mixed in the presence or absence of a catalyst. Examples of catalysts include organometallic compounds such as organic tin compounds such as dibutyltin dilaurate, tertiary amines such as triethylamine, carboxylates such as calcium naphthenate, naphthenates such as tin naphthenate, cobalt octylate and lead octylate. Octylates such as The mixing ratio of the polyhydric alcohol or polyol and the diisocyanate is 1: 0.50 when the ratio of the total hydroxyl value of the polyhydric alcohol or polyol to the isocyanate value of the diisocyanate is represented by their molar ratio. ˜1: 0.90. With such a ratio, the molecular weight of the generated polyurethane resin can be kept within the above range.
In addition, theoretically, a hydroxyl group is present at the terminal of the generated polyurethane resin, and it is possible to obtain a strong cured coating film which is coated with polyisocyanates in which isocyanate groups described below are reacted and reacts during drying, which is rich in durability. . The reaction process is usually performed in the presence of a diluent such as an organic solvent at 60 ° C to 140 ° C.
It completes in 2 to 4 hours at ℃. When a part or all of a trifunctional compound containing 3 or more hydroxyl groups in one molecule is used as the polyhydric alcohol or polyol, the obtained polyurethane resin has a branched structure, while the bifunctional compound has a branched structure. When only is used, the obtained polyurethane resin has a linear structure. All are compounds that can be effectively used in the present invention, and the starting compound can be selected as desired. If the weight average molecular weight is lower than 2000, the chipping resistance is lowered, and even if it exceeds 20000, the chipping resistance is lowered especially after being exposed to a deteriorated environment such as a high temperature and high humidity environment. And since the finished appearance loses smoothness,
Not preferred.

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, such as di-n-amyl carbonate and diisoamyl carbonate. As a co-reacting substance for these carbonates, first, examples of diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-propanediol.
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. 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, 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. The molecular weight of these polyether polyols is not particularly limited, but a range of 300 to 2000 is preferable. 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 reaction can be used, and for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum,
Metals such as titanium, cobalt, germanium, tin, lead, antimony, arsenic, and cerium, and alkoxides thereof can be used. Other suitable catalysts include alkali and alkaline earth metal carbonates, zinc borate, zinc oxide, lead silicate, lead carbonate, antimony trioxide, germanium dioxide, 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 0.0001% to 1.0 based on the total weight of the starting materials.
%, Preferably 0.001% to 0.2% is an appropriate amount.
The reaction temperature is preferably 80 ° C to 220 ° C, and the reaction is carried out near the boiling point of the dialkyl carbonate in the initial stage of the reaction,
As the reaction progresses, the temperature is gradually raised to further advance the reaction. 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 theoretical equivalence ratio can be obtained by charging the diol compound (n + 1) mol with respect to the dialkyl carbonate n mol. It is better to set it to 1.1 to 1.3. The reaction can be carried out at atmospheric pressure, but under reduced pressure in the latter half of the reaction,
For example, the reaction can be performed at 1 mmHg to 200 mmHg to accelerate the progress. The polycarbonate diol of the present invention has a weight average molecular weight of 500 to 400.
0, preferably in the range of 1000 to 3000, 50
When it is less than 0, the chipping resistance is deteriorated, and when it exceeds 4000, the appearance of the coating film is unfavorably deteriorated or wrinkled. To accurately obtain a polycarbonate diol having a desired molecular weight, a raw material diol compound and
This is accomplished by varying the reaction molar ratio of carbonate diol.

The above-mentioned (A) weight average molecular weight 2000 to 2
The mixing ratio of the polyurethane resin of 0000 to the polycarbonate diol (B) having a weight average molecular weight of 500 to 4000 is 90% by weight of polyurethane resin, preferably 70% by weight.
10 to carbonate diol 10 preferably 30 to polyurethane resin 0, preferably 30 to carbonate diol 10
The ratio is preferably in the range of 0, and the ratio of (B) carbonate diol is 10 in 100 parts of the total amount of (A) and (B).
If it is less than the area, the chipping resistance is reduced.

Next, (C) the 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 above-mentioned 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) weight average molecular weight of 2000 to 20000.
Polyurethane resin, and (B) weight average molecular weight of 500 to
The amount is preferably 0.5 to 1.5 in molar ratio with respect to the hydroxyl group content of 4000 polycarbonate diol.

(D) Particle size used in the present invention 0.2 to 1.
The 5 μm microgel is used for the following purposes. That is, by containing a microgel having a particle diameter of 0.2 to 1.5 μm, it is possible to impart thixotropic properties to a coating material and obtain a material that can be coated without causing dripping even in a thick film coating of 30 μm or more. . Usually, in order to improve the sagging limit, fine particle calcium carbonate,
Although a method of adding particulate anhydrous silica or the like is adopted, chipping resistance is often deteriorated by these means, which is not preferable. On the other hand, when microgel is used, a coating material having a good balance of coating workability such as sagging property and chipping resistance can be obtained without causing such problems. For such purposes,
The particle size of the microgel is 0.2 to 1.5 μm, preferably 0.4 to 1.0 μm. Particle size is 0.
If the thickness is less than 2 μm or exceeds 1.5 μm, the thixotropic property of the coating material is not suitable for thick film coating.
The coating property of a thick film of 0 μm or more is deteriorated, and defects such as sagging, armpits, cracks, and peeling are likely to occur, and as a result, chipping resistance may be deteriorated. For this purpose, the microgel having a particle size of 0.2 to 1.5 μm contained in the coating composition means one or two of acrylic or vinyl monomers having one ethylenically unsaturated double bond in the molecule. After suspension polymerization of one or more species and one or more species of crosslinkable monomers having two or more ethylenically unsaturated double bonds in the molecule, the resulting gel particles have a particle size of 0. It is a fraction of 2 to 1.5 μm. Examples of acrylic or vinyl monomers having one ethylenically unsaturated double bond in the molecule used are methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, vinyltoluene, vinyl acetate, acyl-modified acrylate, acyl-modified methacrylate and the like can be mentioned. Further, examples of the crosslinkable monomer having two or more ethylenically unsaturated double bonds in the molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate,
Trimethylolpropane triacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol tetramethacrylate, etc. Can be given. The ratio of acrylic or vinyl monomer to crosslinkable monomer is 99: 1 to 0: 100, preferably 95: 5 to 70:30. 1 crosslinkable monomer
The following is not preferable because the microgel dissolves in the paint. The content of such microgel is not particularly limited, but the above-mentioned (A) weight average molecular weight of 200
0.1 to 20.% with respect to the total amount of the polyurethane resin of 0 to 20000, (B) the polycarbonate diol having a weight average molecular weight of 500 to 4000, and (C) the polyisocyanate compound in which the isocyanate group is blocked.
The range of 0% is preferable.

The intermediate coating composition of the present invention may optionally contain various polyols in addition to the above resin components. Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol and the like. Polyester polyols are, for example, one or more mixtures of reaction products of polyhydric alcohols with less than stoichiometric amounts of polycarboxylic acids and / or their anhydrides. Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomeric pentanediols, isomeric 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. Examples of polycarboxylic acids and polycarboxylic anhydrides include carboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, and itaconic acid. , Trivalent carboxylic acid such as trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride,
Examples thereof include polyhydric carboxylic acid anhydrides such as trimellitic anhydride, dimeric or trimeric fatty acids such as a trimer of castor oil fatty acid. 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 as an example of alkylene oxide, 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. Examples of polycaprolactone polyols are compounds obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone in the presence of a polyhydric alcohol such as ethylin glycol described above. The molecular weight of these polyols is not particularly limited, but if it exceeds 2,500, the coating workability may be deteriorated and eventually the smoothness of the coating film may be lost.
It is preferably set to 00 or less.

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 coated by a conventional coating method such as air spraying, airless spraying, electrostatic coating or rotation. 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 50 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 coated with 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 process 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.

[0019]

【Example】

(Production Example 1) Production of polyurethane resin for intermediate coating paint 200 parts of polycaprolactone polyol (trade name: Praxel 305, manufactured by Daicel Chemical Industries, Ltd., hydroxyl value 310) in a 4-necked flask equipped with a stirrer and a thermometer. Then, 100 parts of toluene was added, the mixture was heated and dissolved, and further refluxed to remove contained water. This solution was kept at 80 ° C., a mixture of 61 parts of hexamethylene diisocyanate and 40.5 parts of methyl isobutyl ketone was added dropwise over 30 minutes, 0.02 parts of dibutyltin dilaurate was mixed as a catalyst, and the mixture was stirred for 2 hours. A polyurethane for coating material was obtained. The obtained polyurethane resin has a weight average molecular weight of 8
It was 000.

Production Example 2 Production of Polyurethane Resin for Intermediate Coating Paint Polypropylene glycol (molecular weight 400, hydroxyl value 280) 200 in a 4-neck flask equipped with a stirrer and a thermometer.
Parts and 100 parts of xylene were charged and dissolved by heating, and further refluxed to remove contained water. This solution was maintained at 80 ° C., a mixture of 96 parts of isophorone diisocyanate and 59.4 parts of methyl isobutyl ketone was added dropwise over 30 minutes, and then 0.04 of dibutyltin dilaurate was used as a catalyst.
This was mixed and stirred for 2 hours to obtain a polyurethane resin for intermediate coating composition. The weight average molecular weight of the obtained polyurethane resin was 12,000.

Production Example 3 Production of Polycarbonate Diol for Intermediate Coating Paint A round bottom four-necked flask equipped with a thermometer, a stirrer, and a distillation column was placed in a 620 parts portion 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 4 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-mentioned polyurethane resin, 50 parts of polycarbonate diol, 72.5 parts of xylene, and titanium dioxide 2
5 parts, 0.2 parts of carbon black, 2.6 parts of Grandol PP-2000S (acrylostyrene microgel powder particle size 0.3-0.4 μm manufactured by Dainippon Ink and Chemicals, Inc.) as a microgel in a sand mill. After kneading using, Barnock D as blocked isocyanate
B-980K (theoretical isocyanate content 10.5%,
75% solids, manufactured by Dainippon Ink and Chemicals, Inc.) 6
The intermediate coating composition-A of the present invention (polyurethane / polycarbonate diol = 40/60, molar ratio of hydroxyl group to isocyanate group = 1.0 / 1.0, nonvolatile content 60%) was prepared by mixing 6.0 parts.

[Examples 2 to 6] Production of intermediate coating materials B to F Intermediate coating materials B to F of the present invention were produced in the same manner as in Example 1 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 so that a dry film thickness was 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 coating film performance tests were 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 an intermediate coating material-G containing no polycarbonate diol (see Table 3 for 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 coating with an intermediate coating material outside the scope of the present invention in the same manner as in Test Example 1. 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 to make it smooth, dripping, aside,
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.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

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) Weight average molecular weight of 2000 to 200
No. 00 polyurethane resin (B) a polycarbonate diol having a weight average molecular weight of 500 to 4000 in a weight ratio of (A) to (B) of 90/10 to
It is characterized in that it is contained at a ratio in the range of 0/100, and further comprises (C) a polyisocyanate compound in which an isocyanate group is blocked and (D) a microgel having a particle diameter of 0.2 to 1.5 μm. Intermediate coating composition.