Patent Publication Number: US-4839406-A

Title: Fluidity controlling agent for paints

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to a fluidity controlling agent for paints which gives thixotoropic properties to a coating film when it is applied to the paint and hardly produces sagging even in the formation of thick coating film, and more particularly to a fluidity controlling agent useful for heat curing paints. 
     2. Related Art Statement 
     Heretofore, calcium carbonate, organic bentonite, hydrophobic silcia, organic polyamide wax, polyethylene wax and the like have been used as fluidity controlling agents for paints. Recently, compounds having a urea bond have been included in the above known fluidity controlling agents. For example, Japanese Patent laid open No. 49-99,131 discloses a fluidity controlling agent consisting of a urea adduct obtained by reacting (a) a diisocyanate compound, (b) primary and/or secondary polyamine and, if necessary, (c) monofunctional alcohol, oxime, amine and/or alkanol amine at such a ratio that the amount of primary and/or secondary amino group does not stoichiometrically exceed the amount of isocyanate group. 
     Furthermore, U.S. Pat. No. 4,311,622 discloses a fluidity controlling agent consisting of a reaction product of a diisocyanate and a monoamine or hydroxymonoamine of an aliphatic hydrocarbon having a carbon number of 1-5. 
     The fluidity controlling agent having such a urea bond has an advantage in that the effect of preventing sagging is large even in paints containing a large amount of a high polarity solvent such as alcohol, ketone or the like because the intermolecular force of the urea bond is generally strong, and the effect of preventing sagging is hardly lost even when the temperature is increased during curing when it is applied to heat curing paint. However, when such a fluidity controlling agent as disclosed in Japanese Patent laid open No. 49-99,131 is applied to a transparent clear paint containing no pigment, the sagging prevention effect is lowered with passage of time, and the gloss of the coating film is undesirably degraded if the curing is performed at a temperature below 140° C. even after the production of the paint. 
     On the other hand, the fluidity controlling agent made from monoamine or hydroxymonoamine of aliphatic hydrocarbon having a carbon number of 1-5 and diisocyanate, for example, benzylamine and hexametylene diisocyanate as disclosed in U.S. Pat. No. 4,311,622 is high at the melting point of the coating film and has a drawback in that when it is applied to a transparent clear paint containing no pigment, if the curing temperature is lower than 140° C. (a typical baking temperature), the gloss of the coating film is degraded. 
     Under the above circumstances, the inventors have made studies with respect to a means for solving the above problems and found that very high thixotropic properties are obtained by using as a fluidity controlling agent product a reaction between a primary monoamine having an amino group directly bonded to an aromatic ring and aliphatic diisocyanate. The present inventors consequently proposed a fluidity controlling agent containing a component obtained by reacting aniline and aliphatic diisocyanate and a component obtained by reacting oxygen-containing primary monoamine and aliphatic diisocyanate at a particular mixing ratio (Japanese Patent laid open No. 61-97,375). In this case, however, the oxygen-containing primary monoamine is used, so that when the molecular weight of a resin used as an organic binder is small, the water resistance of the coating film undesirably lowers. 
     SUMMARY OF THE INVENTION 
     The invention is based on the unexpected discovery that when a novel product obtained by reacting paratoluidine with hexamethylene diisocyanate at a particular ratio is used as a fluidity controlling agent for paints, in an amount smaller than the amount of the fluidity controlling agent used in U.S. Pat. No. 4,311,622 a high sagging prevention effect is obtained and also the gloss is good after curing at a relatively low temperature below 140° C. even without using the product of reaction between oxygen-containing primary monoamine and aliphatic diisocyanate as disclosed in Japanese Patent laid open No. 61-97,375. 
     According to the invention, there is provided a fluidity controlling agent for paints, comprising a product obtained by reacting paratoluidine and hexamethylene diisocyanate at an equivalent ratio of NH 2  /NCO of 0.8-1.2. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     In the fluidity controlling agent according to the invention, paratoluidine wherein an amino group and a methyl group are bonded to an aromatic ring at symmetrical positions is used as a primary monoamine. 
     When using orthotoluidine and metatoluidine, wherein the bonding positions of amino group and methyl group are not symmetrical, and other primary monoamines wherein an amino group and aliphatic hydrocarbon residue are bonded to an aromatic ring such as 2,3-xylidine, 3,4-xylidine and the like, the high sagging prevention effect is not obtained. 
     On the other hand, hexamethylene diisocyanate is used as an organic polyisocyanate in the fluidity controlling agent according to the invention. The use of other diisocyanates such as tolylene diisocyanate or the like does not provide the high sagging prevention effect and lowers the gloss of the coating film. 
     According to the invention, it is necessary that the ratio of paratoluidine to hexamethylene diisocyanate is such that the equivalent ratio of NH 2  /NCO is within the range of 0.8-1.2. When the equivalent ratio of NH 2  /NCO is less than 0.8, excessive isocyanate groups react with each other to produce high molecular weight substance, resulting in the lowering of film gloss, or excessive isocyanate groups may react with a solvent or an active hydrogen atom of a resin so as not to provide high thixotropic properties. On the contrary, when the equivalent ratio of NH 2  /NCO exceeds 1.2, the color of the coating film changes to yellow or the curing is poor. 
     In the production of the fluidity controlling agent according to the invention, a solution of paratoluidine in an organic solvent is stirred at a temperature of not higher than 60° C., preferably 0°-40° C. in an inert gas atmosphere, to which is slowly added hexamethylene diisocyanate. As the organic solvent for dissolving paratoluidine, the use of an aromatic solvent such as benzene, toluene, xylene or the like is preferable. If necessary, there may be included an ester series solvent such as ethyl acetate, butyl acetate, amyl acetate or the like, a ketone series solvent such as acetone, metyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or the like, an alcohol such as methanol, ethanol, isopropanol, n-butanol or the like, and so on. Moreover, the production of the fluidity controlling agent according to the invention may be carried out in a resin used as an organic binder component for the paint. As the resin, mention may be made of polyester resins, acyrlic resins, vinyl resins, polyurethane resins, polyether resins, petroleum resins and so on. For example, the use of the polyester resin or acrylic resin is preferable when using for applications requiring that the top coat exhibit weather resistance. When the fluidity controlling agent for paint is produced in the resin, it is preferable that the solution of paratoluidine in the organic solvent is mixed with the resin and the resulting mixture is held at a temperature of 0°-40° C., during which hexamethylene diisocyanate is slowly added while stirring at high speed. 
     The concentration of the fluidity controlling agent can be properly selected based on the kind of solvent used or the kind and viscosity of the resin, but it is preferably within a range of 1-10% by weight when produced in the solvent or 0.1-3% by weight when produced in the resin. 
     When a paint is produced using the fluidity controlling agent produced according to the method of this invention, a curing agent (for example, polyisocyanate compounds such as hexamethylene diisocyanate, isophorone diiscocyanate and the like; blocked isocyanate compounds hindering a whole or a part of isocyanate groups contained in the polyisocyanate compound with a blocking agent such as lower alcohol, ε-caprolactam, methyl ethyl ketoxime or the like; amino resins such as melamine resin, urea resin and the like; epoxy resins and so on); a pigment such as organic pigment, inorganic pigment, extender pigment and the like; an additive such as surface adjuster, anti-settling agent, heat and light deterioration preventing agents, pigment dispersing agent and the like, and further a reaction catalyst for promoting reaction may be provided in addition to the resin used as the aforementioned organic binder component. 
     The amount of the fluidity controlling agent according to this invention to be provided in the paint is within a range of 0.05-2% by weight per total weight of the paint, which provides high thixotropic properties and makes it possible to form thick coating films. In order to add the fluidity controlling agent according to this invention into the paint, when the fluidity controlling agent is produced in the organic solvent and is mixed with an organic solvent, it is mixed with the resin used as the organic binder in a mixing and kneading apparatus such as a dissolver, a ball mill, a sand grind mill or the like and then the resulting mixture is added into the paint. On the other hand, when the fluidity controlling agent is produced in the resin used as the organic binder component, it may be added into the paint as it is. 
     The fluidity controlling agent for paint according to the invention is a product obtained by using paratoluidine, wherein an amino group and a methyl group are bonded to an aromatic ring at symmetrical positions, as an organic monoamine and hexamethylene diisocyanate as an organic diisocyanate and reacting them at a particular equivalent ratio of NH 2  /NCO of 0.8-1.2, so that the steric configuration of the molecule is symmetrical and the crystallinity is good. Therefore, it has excellent effects in that the high sagging prevention effect is obtained at a smaller amount as compared with the same type of the conventional fluidity controlling agent, and the hardness, water resistance and solvent resistance are excellent, and the gloss is not degraded and discoloration is not caused by the curing at a lower temperature even when being applied to a transparent clear paint. 
    
    
     The following examples are given in illustration of the invention and are not intended as limitations thereof. Unless otherwise specified, part and percentage are by weight. 
     PRODUCTION EXAMPLE 1 
     Production of acrylic resin varnish 
     Into a reactor provided with an agitator, a thermometer, a reflux condenser and a monomer dropping device was charged 35.0 parts of xylene, which was refluxed by heating at a temperature of 135°-140° C. with stirring. Then, a mixture of the following monomers was placed in the monomer dropping device and added dropwise at an equal speed over 3 hours. 
     styrene: 12.5 parts 
     methyl methacrylate: 12.5 parts 
     butyl methacrylate: 10.0 parts 
     2-ethylhexyl acrylate: 13.5 parts 
     2-hydroxyethyl methacrylate: 10.0 parts 
     methacrylic acid: 2.5 parts 
     Perbutyl Z (trade name of polymerization initiator, made by Nippon Oils &amp; Fats Co., Ltd.): 4.0 parts 
     After the completion of the addition of the monomer mixture, the stirring was further continued under reflux state for 2 hours, whereby an acrylic resin varnish was obtained which had a solid content of 65% and a viscosity of Y-Z as measured at a temperature of 25° C. by means of a foam viscometer (according to JIS K5400 4.2.2). 
     PRODUCTION EXAMPLE 2 
     Production of 20% paratoluidine solution 
     Paratoluidine was dissolved by warming at a temperature of 40°-50° C., which was made into a 20% solution according to the following recipe: 
     xylene: 80.0 parts 
     paratoluidine: 20.0 parts 
     EXAMPLE 1 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     20% paratoluidine solution of Production Example 2: 5.7 parts 
     The mixture of the above components was charged into a reactor provided with an agitator, a thermometer and a dropping funnel and then cooled to a temperature of 10° C. with stirring. Thereafter, 0.9 parts hexamethylene diisocyanate and 0.9 parts xylene were placed into the dropping funnel, which were added dropwise at an equal speed over 30 minutes. After the completion of the addition, the stirring was further continued at a temperature of 10°-15° C. for 30 minutes, whereby an opaque acrylic resin varnish containing 2% per total weight of a fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 1.0 (ratio of the moles of paratoluidine to 2 times the moles of hexamethylene diisocyanate) and having thixotropic properties was obtained. The acrylic resin varnish containing the fluidity controlling agent was used according to the following compounding recipe to prepare a paint: 
     acrylic resin varnish containing fluidity controlling agent: 10.0 parts 
     acrylic resin varnish of Production Example 1: 56.0 parts 
     Super Beckamin L-116-70 (trade name of butylated melamine resin, made by Dainippon Ink Chemicals Industries, Ltd.): 27.0 parts 
     xylene: 4.0 parts 
     n-butyl alcohol: 3.0 parts 
     The resulting paint was diluted with a mixed solution of 90 parts xylene and 30 parts n-butyl alcohol of to a viscosity of 30 seconds as measured at a temperature of 20° C. through Ford Cup No. 4, which was applied by spraying to a vertical test plate (Bonderite #3004, trade name of phosphated steel sheet, made by Nippon Perkalizing Co., Ltd.) and cured at a temperature of 120° C. for 30 minutes. As a result, sagging was not caused and the gloss was good when the thickness of coating film reached up to 49 μm. A 
     EXAMPLE 2 
     An acrylic resin varnish containing 2% of a fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 0.8 was produced according to the following compounding recipe in the same manner as in Example 1: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     20% paratoluidine solution of Production Example 2: 5.0 parts 
     hexamethylene diisocyanate: 1.0 parts 
     xylene: 1.5 parts 
     This acrylic resin varnish containing the fluidity controlling agent was used to prepare a paint in the same manner as in Example 1, which was then applied in the same manner as in Example 1. As a result, when the thickness of the coating film reached up to 47 μm, sagging was not caused and the gloss of the film was good. 
     EXAMPLE 3 
     An acrylic resin varnish containing 2% of a fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 1.2 was produced according to the following compounding recipe in the same manner as in Example 1: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     20% paratoluidine solution of Production Example 2: 6.0 parts 
     hexamethylene diisocyanate: 0.8 part 
     xylene: 0.7 part 
     This acrylic resin varnish containing the fluidity controlling agent was used to prepare a paint in the same manner as in Example 1, which was then applied in the same manner as in Example 1. As a result, when the thickness of coating film reached up to 48 μm, sagging was not caused and the gloss of the film was good. 
     PRODUCTION EXAMPLE 3 
     Production of polyester resin varnish 
     Into a reactor provided with an agitator, a reflux condenser attached with a distilled water separating device, a thermometer and an inert gas supply tube were charged the following components: 
     neopentyl glycol: 25.3 parts 
     trimethylol propane: 6.0 parts 
     adipic acid: 25.9 parts 
     isophthalic acid: 14.3 parts 
     These components were heated to a temperature of 120° C., stirred and then heated to a temperature of 200° C. to further conduct the reaction, during which a small amount of the content was sometimes taken out to measure the acid value. When the acid value reached 15, the reaction product was cooled and then diluted with the following components: 
     xylene: 18.0 parts 
     Solveso 150 (trade name of high boiling aromatic solvent, made by Esso Chemicals Co., Ltd.): 10.5 parts 
     The amount of distilled water in the reaction was 18 parts. Thus, there was obtained a polyester resin varnish having a solid content of 65% and a viscosity of X-Y as measured at a temperature of 25° C. by means of a foam viscometer (according to JIS K5400 4.2.2). 
     EXAMPLE 4 
     (1) Production of polyester resin varnish containing fluidity controlling agent (1) 
     polyester resin varnish of Production Example 3: 98.2 parts, 
     20% paratoluidine solution of Production Example 2: 1.4 parts 
     The mixture of the above components was charged into a reactor provided with an agitator, a thermometer and a dropping funnel and then cooled to a temperature of 10° C. with stirring. Thereafter, 0.2 part of hexamethylene diisocyanate and 0.2 part of xylene were placed in the dropping funnel and added dropwise at an equal speed over 30 minutes. After the completion of the addition, the stirring was further continued at a temperature of 10°-15° C. for 30 minutes. Thus, there was obtained a slightly opaque polyester resin varnish containing 0.5% per total weight of a fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 1.0 and having thixotropic properties. 
     (2) Production and application of white paint containing fluidity controlling agent 
     polyester resin varnish of Production Example 3: 13.4 parts 
     titanium dioxide (JR-602, trade name, made by Teikoku Kako Co., Ltd.): 29.0 parts 
     xylene: 4.4 parts 
     ethylene glycol monoethyl ether acetate: 4.4 parts 
     The mixture of the above components was dispersed by means of a glass bead mill for 1 hour. After the removal of glass beads by filtration, the following components were added with stirring: 
     polyester resin varnish of Production Example 3: 7.2 parts 
     polyester resin varnish containing the fluidity controlling agent (1): 20.0 parts 
     Super Beckamin L-116-70: 16.0 parts 
     BYK-300 (trade name of silicon resin additive, made by BYK Chemie Gmbh): 0.1 part 
     Solveso 150: 2.5 parts 
     n-butyl alcohol: 3.0 parts 
     This paint was diluted and applied by spraying in the same manner as in Example 1. As a result, when the thickness of coating film reached 60 μm, sagging was not caused and the gloss was good. 
     EXAMPLE 5 
     (1) Production of polyester resin varnish containing fluidity contolling agent (2) 
     A polyester resin varnish containing 3.0% of fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 1.0 was produced according to the following compounding recipe in the same manner as in item (1) of Example 4: 
     polyester resin varnish of Production Example 3: 88.9 parts 
     20% paratoluidine solution of Production Example 2: 8.5 parts 
     hexamethylene diisocyanate: 1.3 parts 
     xylene: 1.3 parts 
     (2) Production and application of white paint containing fluidity controlling agent 
     polyester resin varnish of Production Example 3: 13.4 parts 
     titanium dioxide: 29.0 parts 
     xylene: 4.4 parts 
     ethylene glycol monoethyl ether acetate: 4.4 parts 
     The mixture of the above components was dispersed and filtered in the same manner as in the item (2) of Example 4, to which were added the following components: 
     polyester resin varnish of Production Example 3: 21.0 parts 
     polyester resin varnish containing the fluidity controlling agent (2): 6.5 parts 
     Super Beckamin L-116-70: 15.7 parts 
     BYK-300: 0.1 part 
     Solveso 150: 2.5 Parts 
     n-butyl alcohol: 3.0 parts 
     This paint was diluted and applied by spraying in the same manner as in Example 1. As a result, when the thickness of the coating film reached 65 μm, sagging was not caused and the gloss was good. 
     EXAMPLE 6 
     The following components were mixed: 
     acrylic resin varnish of Production Example 1: 50.0 parts 
     acrylic resin varnish containing the fluidity controlling agent of Example 1: 25.0 parts 
     ethylene glycol momoethyl ether acetate: 5.0 parts 
     butyl acetate: 7.5 parts 
     The resulting mixture was added with 12.5 parts of polyisocyanate (Desmodule N-75, trade name, made by Bayer AG, heating residue: 75%) as a curing agent. 
     The thus produced paint capable of curing with polyisocyanate was diluted with a mixed solvent of 70 parts butyl acetate and 30 parts cyclohexanone to a viscosity of 30 seconds as measured at a temperature of 20° C. through Ford Cup No. 4 and then applied by spraying in the same manner as in Example 1. As a result, when the thickness of the coating film reaching 50 μm, sagging was not caused and the gloss was good. 
     EXAMPLE 7 
     (1) Production of fluidity controlling agent in solvent 
     xylene: 81.6 parts 
     20% paratoluidine solution: 14.0 parts 
     The mixture of the above components was charged into a reactor provided with an agitator, a thermometer and a dropping device, to which was added dropwise a mixture of 2.2 parts of hexamethylene diisocyanate and 2.2 parts of xylene from the dropping device with stirring over 2 hours. In this case, the temperature was maintained so as not to exceed 40° C. After the completion of the addition, the stirring was further continued for 1 hour. Thus, there was obtained a white waxy mixture of fluidity controlling agent and xylene containing 5% of the fluidity controlling agent with a equivalent ratio of NH 2  /NCO of 1.0. 
     (2) Production of paint 
     The mixture containing 5% of the fluidity controlling agent was mixed with the acrylic resin varnish of Production Example 1 at the following mixing ratio and dispersed in a ball mill for 24 hours: 
     mixture containing 5% of fluidity controlling agent: 20.0 parts 
     acrylic resin varnish of Production Example 1: 20.0 parts 
     After the dispersion, balls were removed by filtering through a wire net, and then the following components were mixed to obtain a paint containing 1% per total weight of the fluidity controlling agent: 
     acrylic resin varnish of Production Example 1: 33.6 parts 
     Super Beckamin L-116-70: 26.5 parts 
     This paint had thixotropic properties, which was diluted and applied by spraying in the same manner as in Example 1. As a result, when the thickness of the coating film reached 61 μm, sagging was not caused and the gloss of the film was good. 
     EXAMPLE 8 
     (1) Production of fluidity controlling agent in solvent 
     xylene: 63.2 parts 
     20% paratoluidine solution: 28.0 parts 
     The mixture of the above components was charged in the same reactor as in Example 7 and the following mixture was added dropwise thereto from the dropping device over 4 hours with stirring: 
     hexamethylene diisocyanate: 4.4 parts 
     xylene: 4.4 parts 
     During the addition of the mixture, the temperature was maintained so as not to exceed 40° C. After completion of the addition, the stirring was further continued for 1 hour. In this way, there was obtained a white waxy mixture of fluidity controlling agent and xylene containing 10% of the fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 1.0. 
     (2) Production of paint 
     The above mixture containing 10% of the fluidity controlling agent was mixed with the acrylic resin varnish at the following compounding recipe and dispersed through a ball mill for 24 hours: 
     mixture containing 10% of fluidity controlling agent: 20.0 parts 
     acrylic resin varnish of Production Example 1: 20.0 parts 
     After the dispersion, balls were removed by filtering through a wire net and then the following components were mixed to obtain a paint containing 2% fluidity controlling agent per total weight: 
     acrylic resin varnish of Production Example 1: 33.6 parts 
     Super Beckamin L-116-70: 26.7 parts 
     This paint had thixotropic properties, and was diluted and applied by spraying in the same manner as in Example 1. As a result, when the thickness of the coating film reached 60 μm, sagging was not caused and the gloss of the film was good. 
     EXAMPLE 9 
     polyester resin varnish of Production Example 3: 12.4 parts 
     mixture containing 5% of fluidity controlling agent in Example 7: 1.0 part 
     titanium dioxide: 29.0 parts 
     ethylene glycol monoethyl ether acetate: 4.4 parts 
     xylene: 4.4 parts 
     The mixture of the above components was dispersed through a ball mill for 24 hours and then balls were removed by filtering through a wire net. Thereafter, the following components were mixed with stirring: 
     polyester resin varnish of Production Example 3: 27.2 parts 
     Super Beckamin L-116-70: 16.0 parts 
     BYK-300: 0.1 part 
     Solveso 150: 2.5 parts 
     n-butyl alcohol: 3.0 parts 
     This paint was diluted and applied by spraying in the same manner as in Example 1. As a result, when the thickness of the coating film reached 50 μm, sagging was not caused and the gloss was good. 
     COMPARATIVE EXAMPLE 1 
     An acrylic resin varnish containing 2% of fluidity controlling agent with an equivalent ratio of NH 2  /NCO of 0.6 was produced according to the following compounding recipe in the same manner as in Example 1: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     20% paratoluidine solution: 4.3 parts 
     hexamethylene diisocyanate: 1.1 parts 
     xylene: 2.1 parts 
     This acrylic resin varnish containing the fluidity controlling agent was low in thixotropic properties. This varnish was used to prepare a paint in the same manner as in Example 1. When the thickness of coating film reached 29 μm by applying the resulting paint, sagging was caused and the gloss of the film was poor. 
     COMPARATIVE EXAMPLE 2 
     An acrylic resin varnish containing 2% of fluidity controlling agent with equivalent ratio of NH 2  /NCO of 1.4 was prepared according to the following compounding recipe in the same manner as in Example 1: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     20% paratoluidine solution: 6.4 parts 
     hexamethylene diisocyanate: 0.7 part 
     xylene: 0.4 part 
     A paint was prepared by using the acrylic resin varnish containing the fluidity controlling agent in the same manner as in Example 1. When the thickness of the coating film reached 45 μm, sagging was not caused, but the color of the film was changed into yellow. Further, the water resistance, solvent resistance and hardness were poor as tested according to the film performance test mentioned below. 
     COMPARATIVE EXAMPLE 3 
     An acrylic resin varnish containing 3% of fluidity controlling agent was produced by using orthotoluidine as a primary monoamine according to the following compounding recipe: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     orthotoluidine: 1.7 parts 
     xylene: 3.2 parts 
     That is, the above mixture was charged into the same reactor as in Example 1 and cooled to a temperature of 10° C. with stirring. Then, 1.3 parts of hexamethylene diisocyanate and 1.3 parts of xylene were placed in the dropping device and added dropwise at an equal speed over 30 minutes. After completion of the addition, the stirring was further continued at a temperature of 10°-15° C. for 30 minutes. The thus obtained acrylic resin varnish containing 3% of the fluidity controlling agent was used to prepare a paint having the following compounding recipe: 
     acrylic resin varnish containing the fluidity controlling agent: 33.3 parts 
     acrylic resin varnish of Production Example 1: 32.7 parts 
     Super Beckamin L-116-70: 27.0 parts 
     xylene: 4.0 parts 
     n-butyl alcohol: 3.0 parts 
     When this paint was applied in the same manner as in Example 1, sagging was caused at a thickness of 22 μm. 
     COMPARATIVE EXAMPLE 4 
     An acrylic resin varnish containing 3% of fluidity controlling agent was produced by using 3,4-xylidine as a primary monoamine according to the following compounding recipe: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     3,4-xylidine: 1.8 parts 
     xylene: 3.3 parts 
     That is, the above mixture was charged into the same reactor as in Example 1 and cooled to a temperature of 10° C. with stirring. Then, 1.2 parts of hexamethylene diisocyanate and 1.2 parts of xylene were placed in the dropping device and added dropwise at an equal speed over 30 minutes. After the completion of the addition, the stirring was further continued at a temperature of 10°-15° C. for 30 minutes. The thus obtained acrylic resin varnish containing 3% of the fluidity controlling agent was used to prepare a paint according to the following compounding recipe: 
     acrylic resin varnish containing fluidity controlling agent: 33.3 parts 
     acrylic resin varnish of Production Example 1: 32.7 parts 
     Super Beckamin L-116-70: 27.0 parts 
     xylene: 4.0 parts 
     n-butyl alcohol: 3.0 parts 
     When the resulting paint was applied in the same manner as in Example 1, sagging was caused at a thickness of 25 μm. 
     COMPARATIVE EXAMPLE 5 
     acrylic resin varnish of Production Example 1: 94.4 parts 
     aniline: 1.4 parts 
     hexamethylene diisocyanate: 1.4 parts 
     xylene: 2.8 parts 
     An acrylic resin varnish containing a fluidity controlling agent derived from aniline was produced according to the above compounding recipe in the same manner as in Example 1. Separately, an acrylic resin varnish containing a fluidity controlling agent derived from an oxygen-containing primary monoamine was produced according to the following compounding recipe in the same manner as described above: 
     acrylic resin varnish of Production Example 1: 94.4 parts 
     monoethanolamine: 1.1 parts 
     hexamethylene diisocyanate: 1.7 parts 
     xylene: 2.8 parts 
     A paint was prepared by using these two acrylic resin varnishes according to the following compounding recipe: 
     acrylic resin varnish of Production Example 1: 40.2 parts 
     acrylic resin varnish containing the fluidity controlling agent derived from aniline: 17.9 parts 
     acrylic resin varnish containing the fluidity controlling agent derived from monoethanolamine: 17.9 parts 
     Super Beckamine L-116-70: 24.0 parts 
     When the resulting paint was applied in the same manner as in Example 1, sagging was not caused at a thickness up to 42 μm and the gloss of the film was good, but the water resistance was poor. 
     COMPARATIVE EXAMPLE 6 
     An acrylic resin varnish containing 3% of fluidity controlling agent derived from benzylamine was produced according to the following compounding recipe in the same manner as in Example 1: 
     acrylic resin varnish of Production Example 1: 92.5 parts 
     benzylamine: 1.7 parts 
     hexamethylene diisocyanate: 1.3 parts 
     xylene: 4.5 parts 
     A paint was prepared using the acrylic resin varnish containing the fluidity controlling agent according to the following compounding recipe: 
     acrylic resin varnish of Production Example 1: 32.7 parts 
     acrylic resin varnish containing the fluidity controlling agent: 33.3 parts 
     Super Beckamin L-116-70: 27.0 parts 
     xylene: 4.0 parts 
     n-butyl alcohol: 3.0 parts 
     When the resulting paint was applied in the same manner as in Example 1, sagging was caused at a thickness of 32 μm and the gloss of the film was poor. 
     The film performance test was made with respect to the test plates coated with each paint of Examples 1-9 and Comparative Examples 1-5 according to the following evaluation methods to obtain results as shown in the following Table 1. 
     Evaluation methods 
     Gloss: measured by means of a Dorigon meter made by Hunter Laboratories, and represented by a gloss value (Rs) reflected at 30°. 
     Discoloration: visual observation. 
     Hardness: according to a pencil scrubbing test of JIS K5400 6.14 
     Water resistance: discoloration and softening of the film were measured after the immersion in water at 80° C. for 3 hours. 
     Solvent resistance: the discoloration and softening of the film were measured after the immersion in a mixture of 90%/10% of petroleum benzine/methyl alcohol at room temperature for 1 hour. 
     
                                           TABLE 1                                 
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                 Example                                                  
                 1   2   3   4   5   6   7   8   9                        
__________________________________________________________________________
Fluidity controlling agent                                                
Production method                                                         
                 varnish                                                  
                     varnish                                              
                         varnish                                          
                             varnish                                      
                                 varnish                                  
                                     varnish                              
                                         solvent                          
                                             solvent                      
                                                 solvent                  
(reaction solvent)                                                        
Concentration in production (%)                                           
                 2   2   2   0.5 3   2   5   10  5                        
equivalent ratio of NH.sub.2 /NCO                                         
                 1.0 0.8 1.2 1.0 1.0 1.0 1.0 1.0 1.0                      
Compounding recipe for paint                                              
Acrylic resin varnish of                                                  
                 56.0                                                     
                     56.0                                                 
                         56.0                                             
                             --  --  50.0                                 
                                         33.6                             
                                             33.6                         
                                                 --                       
Production Example 1                                                      
Acrylic resin varnish containing                                          
                 10.0                                                     
                     10.0                                                 
                         10.0                                             
                             --  --  25.0                                 
                                         40.0                             
                                             40.0                         
                                                 --                       
fluidity controlling agent.sup.(1)                                        
Polyester resin varnish of                                                
                 --  --  --  20.6                                         
                                 34.4                                     
                                     --  --  --  39.6                     
Production Example 3                                                      
Polyester resin varnish containing                                        
                 --  --  --  20.0                                         
                                 6.5 --  --  --  1.0                      
fluidity controlling agent.sup.(2)                                        
Super Beckamin L-116-70.sup.(3)                                           
                 27.0                                                     
                     27.0                                                 
                         27.0                                             
                             16.0                                         
                                 15.7                                     
                                     --  26.4                             
                                             26.4                         
                                                 16.0                     
Desmodule-N-75.sup.(4)                                                    
                 --  --  --  --  --  12.5                                 
                                         --  --  --                       
JR-602.sup.(5)   --  --  --  29.0                                         
                                 29.0                                     
                                     --  --  --  29.0                     
BYX-300.sup.(6)  --  --  --  0.1 0.1 --  --  --  0.1                      
xylene           4.0 4.0 4.0 4.4 4.4 --  --  --  4.4                      
Ethylene glycol monoethyl                                                 
                 --  --  --  4.4 4.4 5.0 --  --  4.4                      
ether acetate                                                             
Solveso 150.sup.(7)                                                       
                 --  --  --  2.5 2.5 --  --  --  2.5                      
n-butyl alcohol  3.0 3.0 3.0 3.0 3.0 --  --  --  3.0                      
butyl acetate    --  --  --  --  --  7.5 --  --  --                       
total            100.0                                                    
                     100.0                                                
                         100.0                                            
                             100.0                                        
                                 100.0                                    
                                     100.0                                
                                         100.0                            
                                             100.0                        
                                                 100.0                    
Content of fluidity controlling                                           
                 0.2 0.2 0.2 0.1 0.2 0.5 1.0 2.0 0.05                     
agent (%).sup.(8)                                                         
Sagging limit thickness (μm).sup.(9)                                   
                 49  47  48  60  65  50  61  60  50                       
Film performances                                                         
Gloss            92  90  91  91  87  94  89  87  90                       
Discoloration    none                                                     
                     none                                                 
                         none                                             
                             none                                         
                                 none                                     
                                     none                                 
                                         none                             
                                             none                         
                                                 none                     
Hardness         H   H   H   H   H   F   H   H   H                        
Water resistance good                                                     
                     good                                                 
                         good                                             
                             good                                         
                                 good                                     
                                     good                                 
                                         good                             
                                             good                         
                                                 good                     
Solvent resistance                                                        
                 good                                                     
                     good                                                 
                         good                                             
                             good                                         
                                 good                                     
                                     good                                 
                                         good                             
                                             good                         
                                                 good                     
__________________________________________________________________________
                           Comparative Example                            
                           1   2    3   4   5   6                         
__________________________________________________________________________
          Fluidity controlling agent                                      
                           varnish                                        
                               varnish                                    
                                    varnish                               
                                        varnish                           
                                            varnish                       
                                                varnish                   
          Production method                                               
          (reaction solvent)                                              
          Concentration in production (%)                                 
                           2   2    3   3   2.8 3                         
          equivalent ratio of NH.sub.2 /NCO                               
                           0.6 1.4  1.0 1.0 1.0 1.0                       
          Compounding recipe for paint                                    
          Acrylic resin varnish of                                        
                           56.0                                           
                               56.0 32.7                                  
                                        32.7                              
                                            40.2                          
                                                32.7                      
          Production Example 1                                            
          Acrylic resin varnish containing                                
                           10.0                                           
                               10.0 33.3                                  
                                        33.3                              
                                            35.8                          
                                                33.3                      
          fluidity controlling agent.sup.(1)                              
          Polyester resin varnish of                                      
                           --  --   --  --  --  --                        
          Production Example 3                                            
          Polyester resin varnish containing                              
                           --  --   --  --  --  --                        
          fluidity controlling agent.sup.(2)                              
          Super Beckamin L-116-70.sup.(3)                                 
                           27.0                                           
                               27.0 27.0                                  
                                        27.0                              
                                            24.0                          
                                                27.0                      
          Desmodule-N-75.sup.(4)                                          
                           --  --   --  --  --  --                        
          JR-602.sup.(5)   --  --   --  --  --  --                        
          BYX-300.sup.(6)  --  --   --  --  --  --                        
          xylene           4.0 4.0  4.0 4.0 --  4.0                       
          Ethylene glycol monoethyl                                       
                           --  --   --  --  --  --                        
          ether acetate                                                   
          Solveso 150.sup.(7)                                             
                           --  --   --  --  --  --                        
          n-butyl alcohol  3.0 3.0  3.0 3.0 --  3.0                       
          butyl acetate    --  --   --  --  --  --                        
          total            100.0                                          
                               100.0                                      
                                    100.0                                 
                                        100.0                             
                                            100.0                         
                                                100.0                     
          Content of fluidity controlling                                 
                           0.2 0.2  1.0 1.0 1.0 1.0                       
          agent (%).sup.(8)                                               
          Sagging limit thickness (μm).sup.(9)                         
                           29  45   22  25  42  32                        
          Film performances                                               
          Gloss            67  87   86  87  86  62                        
          Discoloration    none                                           
                               change                                     
                                    none                                  
                                        none                              
                                            none                          
                                                none                      
                               into                                       
                               yellow                                     
          Hardness         H   B    H   H   F   H                         
          Water resistance good                                           
                               opaque                                     
                                    good                                  
                                        good                              
                                            opaque                        
                                                opaque                    
          Solvent resistance                                              
                           good                                           
                               softening                                  
                                    good                                  
                                        good                              
                                            good                          
                                                softening                 
__________________________________________________________________________
 
    
     Note: 
     (1) acrylic resin varnish containing the fluidity controlling agent produced in each of Examples 1-3, 6-8 and Comparative Examples 1-6 
     (2) polyester resin varnish containing the fluidity controlling agent produced from each of Examples 4, 5, 9 
     (3) trade name of butylmelamine resin, made by Dainippon Ink Chemical Industries Ltd., heating residue: 68% 
     (4) trade name of polyisocyanate, made by Bayer AG, heating residue: 75% 
     (5) trade name of titanium dioxide, made by Teikoku Kako Co., Ltd. 
     (6) trade name of silicon resin additive, made by BYK Chemie Gmbh 
     (7) trade name of high boiling aromatic solvent, made by Esso Chemicals Ltd. 
     (8) content of fluidity controlling agent in total paint weight before dilution of paint 
     (9) sagging limit thickness (μm) after the paint diluted to 30 seconds (20° C.) through Ford Cup No. 4 was applied by spraying to a vertical test plate (Bonderite #3004, made by Nippon Perkalizing Co., Ltd., trade name of phosphated steel sheet) and then cured at a temperature of 120° C. at a vertical position for 30 minutes 
     As seen from the above results, the paints using the fluidity controlling agent according to the invention in Examples 1-9 can be applied at a greater thickness, and exhibit good gloss even after curing at a temperature of 120° C., and exhibit good film performance such as discoloration, hardness, water resistance, solvent resistance and the like. 
     On the other hand, in case of Comparative Example 1 wherein the equivalent ratio of NH 2  /NCO is less than 0.8, the sagging prevention effect is insufficient and the gloss of the film is poor. In Comparative Example 2 wherein the equivalent ratio of NH 2  /NCO exceeds 1.2, the color of the film is changed into yellow during the curing, and the curing is poor at a curing temperature of 120° C., and the hardness, water resistance and solvent resistance are also poor. In Comparative Examples 3 and 4 wherein orthotoluidine and 3,4-xylidine are used as a primary monoamine, even when the fluidity controlling agent is compounded in an amount of 1% per total weight of the paint, the sagging prevention effect is poor. In Comparative Example 5 according to Japanese Patent laid open No. 61-97,375, the hardness and water resistance are poor at a curing temperature of 120° C. In Comparative Example 6 according to U.S. Pat. No. 4,311,622, even when the fluidity controlling agent is compounded in an amount of 1% per total weight of the paint, the sagging prevention effect is poor, and the gloss of the film cured at a temperature of 120° C. is poor, and also the water resistance and solent resistance are poor.