WO1998005722A1 - Coating composition, method for coating with the same, and article coated by said method - Google Patents

Abstract

A coating composition comprising a polymercapto compound, such as a polymercaptocarboxylic ester of an aliphatic polyhydric alcohol, a particular polyisocyanate compound of a carbodiimide, aliphatic polyhydric alcohol adduct, isocyanurate or other type, and optionally a polyol; and a coating method using the above composition which can rapidly cure even at room temperature in the presence of a gaseous amine catalyst and can yield an even coating by electrostatic coating or the like. The resultant coating possesses an excellent anticorrosive property, is less likely to be separated even under very cold or very hot conditions, and is useful for heavy-duty protection and other applications. A coating method using a plastic as a substrate can provide coated foams possessing excellent water resistance and other properties.

Description

 Itoda Coating composition, coating method, and coated article coated by the method

¾ ^% field '

 The present invention relates to a rapidly curable coating composition suitable for heavy-duty corrosion prevention and other uses, a method for applying the same, and a coated article coated by the method. A coating composition, a coating method, and a coating method capable of rapidly curing an uncured coating film formed by spray coating on a vapor-phase amine catalyst to form a uniform coating film. Pertaining to painted products. Background technology

 Among conventional coating film curing methods (coating methods), an uncured coating film is formed by spray coating a coating composition on a substrate such as an iron plate, and then the coating film is converted to a vapor-form amine catalyst. There is a method in which the coating composition is cured rapidly by contact, or a method in which the coating composition is spray-coated on a substrate such as an iron plate and rapidly cured in the presence of a vapor-form amine catalyst. In these methods, a coating composition is used in which the vapor-form amide catalyst penetrates into the inside of the coating film to cure the coating film.

For example, Japanese Patent Publication No. 3-4111 / 1991 discloses a coating composition comprising a polymercapto compound and a polyisocyanate curing agent, which is used at room temperature in the presence of a tertiary amine catalyst in vapor form. Paints that can cure quickly It has been disclosed.

 In addition, Japanese Patent Application Laid-Open No. 3-163718 discloses a coating film curing method (coating method). In this method, a polyol, a mercapto compound, and an isopropyl compound are used. (Curing agent) as an essential component is used. The coating film curing method disclosed in this publication discloses a method of coating a coating composition containing a polyol and a polyisocyanate compound as a mist to be applied to a substrate such as an iron plate or on a substrate such as an iron plate. In a method of obtaining a cured coating film by applying a vaporized tertiary amine catalyst to the applied coating film as it is, the coating composition is formed by a reaction between a mercapto compound and an isocyanate compound. It is characterized in that it is cured in the presence of a resin compound.

 For example, especially (heavy) anticorrosive paint films are required to have not only water resistance but also resistance such as acid resistance and alkali resistance. However, with the conventional coating composition as described above, a coating film having practically necessary coating film properties, for example, particularly as a (heavy) anticorrosion coating film, has not been obtained.

However, in the coating method using the conventional coating composition as described above, the applicable range of the concentration of the vapor-form amine catalyst is usually 800 to 1200 ppm, which is extremely narrow. The range in which conditions can be set is very narrow. If the concentration of the vapor-form amine catalyst is out of the above range, the effect of promoting the curing of the coating film is not recognized, or the surface of the coating film cures too rapidly, so that the amine catalyst cannot be cured inside the coating film. This makes it difficult to obtain a uniform coating film. Since the range of application of the concentration of the vapor-form amine catalyst is extremely narrow as described above, the above-mentioned Japanese Patent Application Laid-Open Publication No. Hei. When implementing the coating method (coating film curing method) disclosed in the report, it was extremely difficult to set the coating conditions.

 Thus, the emergence of (heavy) fast-curing coating compositions suitable for anticorrosion and other applications that can cure to form uniform coatings in the presence of vaporous amine catalysts, and A wide range of application methods for spray catalysts, easy setting of spray coating conditions, and rapid curing of coating compositions to form uniform coatings are emerging. ing. By the way, large steel structures such as ships, land structures, bridges, etc. are usually coated with heavy anticorrosive paint or cathodic protection to prevent corrosion.

 In heavy-duty anti-corrosion coating, a coating film with a thickness of hundreds to thousands of micron is formed on the steel sheet surface to shield the steel sheet surface and prevent corrosion of the steel sheet by preventing ingress of oxygen, chlorine, water vapor, etc. are doing.

 Conventionally, tar-epoxy paints, tar-urethane paints, modified epoxy paints, epoxy paints, and the like have been used for such heavy duty anticorrosion coatings.

 Of these paints, tar-based paints have been pointed out as carcinogenic, and if scattered outside during painting, there is a risk of environmental pollution.In addition, since they are usually black, they are aesthetically pleasing. There is a problem that it cannot always meet the demands of the people.

When the above-mentioned tar-based and non-tar-based paints are used for heavy duty anticorrosion coatings, a single coating can produce a thick coating of several hundred micron or more. By selecting pigment particles, vehicle, etc. as appropriate, the thixotropy (when stirred under high shear, it becomes a sol and the fluidity and coatability increases, and it adheres to the substrate. After coating, it loses fluidity and becomes gel-like, and has the property of forming a thick coating film). In the case of ve coat ings), the paint viscosity inevitably increases, usually to a viscosity of more than 250 cps.

Also, when application of paints such a high viscosity thick, although even high Eyaresu (spray) coating is employed if, paint ejection discharge pressure at this time to 1 8 0 kg Z cm ² Reach.

 In the high-pressure air (spray) coating performed under such conditions, since the viscosity of the coating is set high as described above, the particle size of the coating when atomized is about 100 micron. Is larger, and belongs to a large class as the particle size of the sprayed paint.

 When applying high-pressure airless paint, which sprays such large-grained atomized paint at high speed, to objects to be coated such as hulls, underwater / water structures, etc., edges and narrow portions of steel plate edges, protrusions, holes, etc. It is difficult to form a coating film with a uniform film thickness in parts and the like. In addition, the edges of steel plates, edges such as holes, and narrow parts are apt to concentrate stress. But it's raw If high-pressure air spray coating is performed to avoid such problems, and manual brush-touching (correction coating) is also performed, work efficiency will be greatly reduced.

Therefore, the present inventors have conducted intensive research to solve the above problems, Based on the idea that if anti-corrosion coating is applied to an object (substrate) by electrostatic coating, a uniform coating film can be formed on the edge of the object to be coated, etc. We tried electrostatic coating for heavy corrosion protection with epoxy paint. In other words, when the existing heavy-duty anticorrosive paint was used, and the paint viscosity was set high to secure a film thickness of several hundred microns or more by one electrostatic coating, the paint with a large particle size Such paint particles need to be spray-coated at high pressure and high speed, and the speed of the paint particles is high. Therefore, even if the paint particles are charged by the electrostatic coating device, electrostatic attraction with the object to be coated is obtained. The effect of force (eg, uniformity of end face film thickness) was hardly obtained.

 Therefore, a heavy-duty anti-corrosion coating film with a uniform film thickness with excellent anti-corrosion properties can be easily obtained even on ships, on-water / under-water structures, especially on the edges of these steel plates, protrusions, holes, etc., and also on narrow parts. Therefore, the emergence of an electrostatic coating method for a heavy-duty anticorrosion coating composition that can reduce the number of man-hours if an automatic coating system such as robot coating is adopted is desired. On the other hand, plastic foams are widely used for applications such as trays used for food packaging of fish and vegetables, insulation materials used for appliances, insulation materials, and floating piers. I have.

Conventionally, plastic foam used as a heat insulating material and a cold insulator used in electrical appliances has been used by coating the foam surface with a film so that dew condensation may occur. If the plastic foam surface could be coated with paint instead of this film, the cost of the plastic foam surface treatment process could be significantly reduced. The floating pier is made of polystyrene foam, This polystyrene foam is used by covering the surface of the polystyrene foam with a film so that water does not penetrate inside. If the polystyrene foam surface can be coated with paint instead of this film, it can be processed so that water does not penetrate into the foam, and the foam It also helps prevent body collapse, greatly reduces the cost of the plastic foam surface treatment process, and also allows the application of antifouling lysate on the surface of the coating film .

 However, the coating of plastic foams, especially polystyrene (foam) surfaces, may be disintegrated or disintegrated by the foam soluble components in the coating film during the drying process of the coating film. It is very difficult to form a coating film on a plastic foam without impairing the shape of the foam, because the foam shrinks due to heating to cure the film. I got it. Due to these problems in the method of applying a plastic foam, the surface of the plastic foam was not actually painted in the past.

Japanese Patent Publication No. 3-67107 discloses an invention relating to a "method of strengthening a foamed protective body", and discloses "having a urethane film provided by a urethane elastomer spray method." There is a teaching of "a foamed polystyrene molded article characterized by the following." In the invention described in this publication, the urethane paint is spray-painted for the purpose of reinforcing the surface of the foamed styrene molded article, and is substantially painted by urethane rim (RIM) spray. It is difficult to obtain a uniform thin film of several hundred meters or less, and this urethane rim spray coating Workability was remarkably poor, and it was not economically advantageous.

 Therefore, it is possible to uniformly form a coating of several meters to several tens of meters on a plastic foam without changing the shape of the foam. It is desired to develop a method and a plastic foam coated article coated by the method, and to develop a coating method which is excellent in coating workability and is economically advantageous. The first object of the present invention is to solve the above problems associated with the prior art. The application range of the concentration of the vapor-form amine catalyst, ffl, is wide, and the coating conditions of the spray coating are large. An object of the present invention is to provide a coating composition which can be easily set, and which can be cured quickly to form a uniform coating film, in particular, a coating composition having excellent anticorrosion properties and a coating method thereof.

 Further, a second object of the present invention is to provide excellent anticorrosion properties easily on ships, on-water and underwater structures, particularly on edges of steel plates, edges such as protrusions and holes, and narrow spaces. An electrostatic coating method for a heavy-duty anticorrosion coating composition and a method that can reduce the number of work steps by employing an automatic coating system such as a robot coating method. It is to provide painted anticorrosion paint products.

Further, a third object of the present invention is to uniformly form a coating film of several hundred m to several hundred thousand m on a plastic foam without impairing the shape of the foam. An object of the present invention is to provide a method for coating a plastic foam which can be applied and a plastic foam coated article coated by the method. Disclosure of the invention

 [Coating composition]

 The first coating composition according to the present invention,

 A polymer capping compound (A),

 Calposimid-type poly-society (B) and

It is characterized by consisting of

 As the polymercapto compound (A), a mercapto lower fatty acid ester of an aliphatic polyol, in particular, a mercaptoacetate of pentaerythritol is preferable.

 Examples of the above-mentioned carbodiimide-type polyisocyanate (B) include a carbodiimide-type diphenylmethane silane, a carbodiimide-type tri-range thiocyanate, a carbodiimide-type dimethylbiphenyle-range thiocyanate, and a carbodiimide. A mid-type hexamethylene diisocyanate is preferred.

 In addition to the carposimid type polyisocyanate (B), diphenyl methane diisocyanate, tolylene diisocyanate, dimethyl biphenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and naphthalene diisocyanate Polyisocyanate (B-1) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenyl methane diisocyanate, etc. can be used in combination.

Further, the first coating composition according to the present invention contains a polyol (C) in addition to the above-mentioned polymercapto compound (A) and karposimid type polyisocyanate (B). Can be done. Further, the second coating composition according to the present invention comprises: a polymercaptocarboxylic acid ester of an aliphatic polyhydric alcohol (D);

 Adducts (El) of tri- or higher aliphatic polyhydric alcohols (i) with bis (isosinate methyl) cyclohexane (ii), and bis oen

 (Isocyanate methyl) The following formula [I] consisting of cyclohexane

ヽ

 0 = C C = 0

 \ /

 N

And at least one polyisocyanate compound (E) selected from the group consisting of an isocyanurate structure (nurate structure) (E 2) having a ring represented by It is special. Examples of the polymercaptocarboxylic acid ester (D) include a mercapto lower fatty acid ester of an aliphatic polyol, especially a pentaerythritol mercaptopropionate or a mercaptoacetate, or trimethylolpropane. Menolecaptopropionate or mercaptoacetate are preferred. [Painting method]

 The coating method according to the present invention,

 The coating composition (1) or (2;) is cured on a substrate in the presence of a vapor-form amine catalyst to form a uniform coating film.

 Coating composition (1): polymercapto compound (A),

 Carbodily-type poly-sodium

 (B) a coating composition comprising [the first coating composition according to the present invention Ij].

 Coating composition (2): Polymercaptocarboxylate (D) of aliphatic polyhydric alcohol,

 To the adduct (E 1) of bis (isomethine methyl) cyclohexane (ii) with an aliphatic polyhydric alcohol (i) having three or more valences, and to bis (isomethyl monomethyl) cyclo At least one member selected from the group consisting of isocyanurate structures (nurate structures) (E 2) consisting of xane and forming a ring represented by the above formula [I] A coating composition comprising the polyisocyanate compound (E) [the second coating composition according to the present invention].

In the coating method according to the present invention, the coating composition (1) or (2) can be subjected to electrostatic coating in the presence of a vapor-phase amine catalyst. In this electrostatic coating, the coating compositions (1) and (2) The degree is preferably less than 500 cPs.

 Further, the coating method of the anticorrosion coating composition according to the present invention is characterized in that a polyol (F 1) and / or a polymer cap compound (F 2) and It is characterized in that a coating composition (3) consisting of a single piece (G) is electrostatically coated.

 In this electrostatic coating, the viscosity of the coating composition (3) is preferably 500 cPs or less.

 Further, another coating method according to the present invention,

 The coating composition is characterized in that the coating composition (1), (2) or (3) is cured on a plastic foam in the presence of a vapor-phase amine catalyst to form a coating film. ing.

 In the method of applying the plastic foam, it is preferable to use the coating composition (3).

 The polymer cap compound (A) constituting the coating composition (1) used in the above coating method is a mercapto lower fatty acid ester of an aliphatic polyol, in particular, a mercapto acetate ester of Penyu erythritol Is preferred.

 Examples of the above-mentioned carbodiimide-type polyisocyanate (B) include carbodiimide-type difuninylmethanedithiocyanate, carbodiimid-type tolylenediisocitrate, carbodiimide-type dimethylbiphenyle-diisocyanate, A carposimid hexylene diisocyanate is preferred.

In addition to the calposimid-type polysocyanate (B), diphenylmethanthocyanate, tolylenediisocyanate, Methylbiphenylene diisocyanate, xylylene diene cyaneate, naphthylene diene cyaneate, hexamethylene diene cyaneate, isophorone diene cyaneate, hydrogenated xylylene diene cyaneate, hydrogenated diphenylene cyaneate And the like (B-1).

 In addition, the coating composition (1) contains a polyol (C) in addition to the polymer cap compound (A) and the rubodiimide-type polyisocyanate (B). be able to.

 The polymer captocarboxylate (D) constituting the coating composition (2) used in the above-mentioned coating method is a fatty acid polyol lower fatty acid ester, in particular, pentaerythritol. Preferred are mercaptopropionate or mercaptoacetate, or trimethylpropanolate or mercaptoacetate.

 Examples of the polyol (F1) constituting the coating composition (3) used in the above coating method include ethylene glycol, propylene glycol, 1,6-hexanediol, glycerol, and triglyceride. Methyl roll proha. Or erythritol, polyester, or acrylic polyol.

Examples of the polymercapto compound (F 2) include pentaerythritol and mercaptoacetic acid or mercaptopropionic acid, or trimethylolpropane and mercaptoacetic acid or mercaptopropionic acid. Esters having from 2 to 4 mercapto groups are particularly preferred. Examples of the polyisocyanate (G) include a carbodiimide-type diphenylmethane sorbate, a carbodiimide-type tri-range sorbate, a carbodiimide-type dimethyl biphenylerange silicate, and a carbodimidite. Hexamethylene diisocyanate is preferred.

[^ ¾ 00 J

 Heavy anticorrosion paint coated product according to the present invention,

 The above-mentioned electrostatic coating method for a heavy-duty anticorrosion coating composition according to the present invention is characterized in that a coating film is formed on a ship, an underwater / over-water structure.

 Further, the plastic foam coated product according to the present invention,

 According to the above-mentioned method for applying a plastic foam, a coating film comprising the coating composition (1), (2) or (3) is formed on the plastic foam.

 In particular, plastic foam coated articles using the coating composition (3) are preferred.

 BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 shows a T-shaped test piece (1) used in Examples and Comparative Examples. Fig. 1 (B) is a perspective view of the test piece (1), and Fig. 1 (A) is a side view thereof.

FIG. 2 shows a test piece (2) used in Examples and Comparative Examples. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the coating composition according to the present invention, its coating method, and the coated product coated by the method will be specifically described.

 First, the first coating composition according to the present invention (the coating composition (1) used in the mounting method according to the present invention) will be described.

 The first coating composition according to the present invention comprises a polymercap compound (A.), a sorbodimid-type polyisocyanate (B) as a crosslinking agent, and optionally a polyol. (C).

 Poly mercapto compound (A)

 The poly mercapto compound (A) is a compound having two or more mercapto groups (one SH group). Among them, the preferred polymer compound is an ester consisting of an aliphatic polyol (a) and a mercapto lower fatty acid (b), and has two mercapto groups (one SH group). It may have all of the above, and all of the hydroxyl groups may be esterified, or one or more hydroxyl groups may remain.

Specific examples of the aliphatic polyol (a) include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and neopentinoreguri. Kohl, trimethylen-llutan, trimethylolpropane, 1,6-hexanediol, glycerol, diglycerol, polyglycerol, sorbitol, polytetramethylethylene glycol, sicc Polyvalent hydroxy compounds such as rohexanedimethanol, polytetramethylethylene glycol, cyclohexanedimethanol, pentaerythritol and resorcinol are exemplified. Among them, pentaerythritol is preferred. It is also possible to use glycidyl ethers such as bisphenol A glycidyl ether, hydrogenated bisphenol A glycidinol ether, bisphenol glycidyl ether, and novalac type epoxy. it can.

Also, as the mercapto lower fatty acid (b), physically, mercaptoacetic acid, menolecaptopropionic acid, mercaptosalicylic acid, mercaptoglycolic acid, N- (2hydroxyxyl) thioglycolic acid And mercaptoconic acid, mercaptoric acid and the like. Among them, mercaptoacetic acid (HSCH ₂ COOH) is particularly preferred. The polymercapto compound (A) particularly preferably used in the present invention has two or more, preferably 2 to 4 mercapto groups composed of pentaerythritol and mercaptoacetic acid. It is an ester.

 The mercapto compound having one mercapto group can be used as a diluent or as a plasticizer.

 Examples of the polymenolecapto compound (A) other than the above mercapto lower fatty acid esters of aliphatic polyols include 1,4-butanedithiol, 2,3-dimethylcaptopropanol, and toluene 3 , 4-dithiol, hi, α'-dimethylcapto-ρ-xylol. In the present invention, it is desirable to use a polymercapto compound (Α) which does not require the use of a solvent and has no or little odor.

<A carbodiimide-type polyisocyanate (Β) and a calposimid-type polyisocyanate (Β) used in the present invention have one or more C = Ν— groups. Is the carposimi Diphenyl methane diisocyanate, carbodiimid triphenyl thiocyanate, carbodiimid dimethyl biphenylenediocyanate, carbodiimid xylendiphenyl thiocyanate, and carbodiimid naphthalene diisocitane To the calposimid type, to the hexamethylene diisocyanate, to the calposimid type, to the rosin radical, to the carposimid type, to the hydrogenated xylylenedisilane, and to the carposimid type. And so on. Above all, a carpoid medium? Diphenyl methane diisocyanate, carbodiimide-type toluene diisocyanate, carbodiimide-type dimethylbiphenylene diisocyanate, carbodiimide-type hexamethylene diisocyanate is preferably used. Societelets are preferably used.

 In addition, a carposimide-type polyisocyanate having one —N = C = N— group can be represented by the following formula.

(0 CN-R ')-N = C = N-(R ² -NC 0)

[In the formula (OCN- R '), (R 2 - NCO) is a port Li Lee Soshiane Bok. ]

In addition, together with the calposimid type polysocyanate (B), diphenyl methane diisocyanate, tolylene diisocyanate, dimethyl biphenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, naphthalene diisocyanate, Polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenyldiene dithiocyanate — G (B-1) can be used together.

 Polyol (C1

 In the present invention, a polyol (C) may be blended into the coating composition.

 As such polio (c), specifically,

 Diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, 1,5 Polyhydric hydroxy compounds such as pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, diglycerol, polyglycerol, cyclohexanedimethanol, polytramethylene glycol, etc. Polyglycol compounds having up to about 10 carbon atoms, and

 Polyester polyols or acrylonitrile polyols derived from phthalic anhydride, sebacic acid, fatty acids, epoxy resins, etc.

And the like.

 <Blending ratio>

 In the present invention, the respective components of the polymercapto compound (A) and the carbodiimide-type polyisocyanate (B) are equivalent to the isocarbonate group contained in the carbodiimide-type polyisocyanate (B). The ratio [NCO group ZSH group] of the thiol group contained in the polymercapto compound (A) to 0.2 to 4, preferably 0.5 to 3, and more preferably 1 to It is used in an amount falling within the range of 2.

In addition, the polymercap compound (A) and the carposimid type Polyisolate (B-) which can be used in combination with polyol (C) and carpo-midide-type polysocket (B), in addition to the isolate (B) When 1) is used, the components of the polymercapto compound (A), the carpoimide-type polyisocyanate (B), the poly (C) and the polyisocyanate (B-1) are , The equivalent amount of the isocyanate 含 ま contained in the carbodiimide-type polyisocyanate (B) and the total amount of the equivalents of the isocyanate-group contained in the polyisocyanate (B-1) The ratio [NCO group Z (SH group + 0H group)] of the equivalent of the thiol group contained in the polymercap compound (A) and the total amount of the hydroxyl group contained in the polyol (C) is 0. 2-4, preferably ◦ .5-3, more preferred It is used in an amount that falls within the range of 1-2.

 When the above-mentioned polyisocyanate (B-1) is used in combination with the carbohydrate-type isocyanate (B), the carbodimid-type isocyanate (B) is 5 parts by weight or more and less than 100 parts by weight, preferably 20 parts by weight or more 10 parts by weight, based on 100 parts by weight of the total amount of the sodium salt (B) and the polyisocyanate (B-1) Used in amounts less than 0 parts by weight.

 When the calposimid type polyisocyanate (B) is used in the amount described above, a coating composition which can be rapidly cured to form a uniform coating film can be obtained.

 <Material composition (1) ゝ

The first coating composition (coating composition (1)) according to the present invention is a clear coating composition capable of forming a clear coating film as a coating composition. Conventionally known paint additives such as color pigments, fire-resistant pigments, dispersants and the like can be blended within a range that does not impair the object of the present invention, and can be used as ordinary paint compositions.

 The glue composition (1) containing the above-described polymercap compound (A) and the carbodiimide-type polyisocyanate (B) has a long pot life and is easy to handle. . The coating composition (1) can be cured at room temperature. Next, the second coating composition according to the present invention (the coating composition (2) used in the coating method according to the present invention) will be described.

 The second coating composition according to the present invention contains a polymercaptocarboxylic acid ester (D) and a polyisocyanate compound (E) as a crosslinking agent.

 Polymercaptocarboxylic acid ester (D),

The polymercaptocarboxylate (D) used in the present invention is a polymercaptocarboxylate of an aliphatic polyhydric alcohol, and is a compound having two or more mercapto groups (one SH group). Among these, the polymercap ester (D) which is preferably used is an ester composed of an aliphatic polyhydric alcohol (i) and a mercapto lower fatty acid (ii), and has a mercapto group (one sH group). And at least one hydroxyl group may be esterified, or one or more hydroxyl groups may remain. The polymer carboxylic acid ester (D) used in the present invention is a complete ester or a partial ester. As the aliphatic polyhydric alcohol (i), a dihydric or higher aliphatic alcohol is used. Specifically,

 Dihydric alcohols such as ethylene glycol, propanediol, butanediol, 1,6 hexanediol, alkanediol, cyclohexanedimethanol;

Glycerol, trimethylolprono, ⁰ (TMP), 1,2,6 hexane, trimethylol, 2,4 dihydroxy-3-hydroxymethylpentane, 1,1 , 1-tris (bishydroxymethyltinole) propane, 2,2 bis (hydroxymethyl) butanenor 3 etc.

 Pentahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabit, ribitol, and xylitol (pentitic);

 Hexahydric alcohols (hexites) such as sonorebit, mannite, galactitol, and arozurcit are included. Of these, greaserol, trimethylolpropane, and pentaerythritol are particularly preferred.

Specific examples of the mercapto lower fatty acid (ii) include mercaptoacetic acid, mercaptopropionic acid, mercaptosalicylic acid, mercaptoglycolic acid, N- (2-hydroxyxethyl) thioglycolic acid, Mercaptosuccinic acid, mercaptolingic acid and the like can be mentioned. Among them, mercaptoacetic acid and mercaptopropionic acid are preferred. Polymeric carboxylic acid ester (D) which is particularly preferably used in the present invention is composed of pentyl erythritol and mercaptoacetic acid or mercaptoacetic acid. Captopropionic acid or trimethylolproha. It is an ester having 2 to 4 mercapto groups consisting of methacrylate and mercaptoacetic acid or mercaptopropionic acid.

 In addition, a mercaptocarboxylic acid ester with an aliphatic monohydric alcohol can be used as a diluent or a plasticizer. In the present invention, it is desirable to use a polymercaptoacetate (D) which does not require the use of a solvent and which may or may not be used.

 The polymercaptocarboxylate (D) is obtained by the ratio of the equivalent of the isocyanate group contained in the polyisocyanate compound (E) to the equivalent of the thiol group contained in the polymercaptocarboxylate (D). [NCO group / SH group] The amount used is in the range of 0.2 to 4, preferably 0.5 to 3, and more preferably 0.7 to 2.

 When the polymercaptocarboxylic acid ester (D) is used in the above amount, the applicable range of the concentration of the vapor-form amine catalyst can be expanded to 200 to 400 ppm, and the spray coating can be used for spray coating. It is possible to obtain a coating composition which can easily set the coating conditions and can rapidly cure to form a uniform coating film.

 Polysocyanate compound (E)>

 The polyisocyanate compound (E) used in the present invention is

 An adduct (E 1) of a tri- or higher aliphatic polyhydric alcohol (i) with bis (isosinate methyl) cyclohexane (ii), and Z or

Bis (isosinate methyl) cyclohexane, the above formula It is an isocyanurate structure having a ring represented by [I] (a null structure) (E 2).

 Specific examples of the tri- or higher-valent aliphatic polyhydric alcohol (i) used as a component of the L-product (E 1) include:

 Glycerol, trimethylone mouth (D-MP), 1,2,6 hexane triol, trimethyloylethane, 2,4 dihydroxy-3-hydroxymethylpentane, 1,1 , 1 tris (bishydroxymethyltinol) propane and 2,2-bis (hydroxymethylbutanol 3)

 Pentahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols (pentit) such as arabit, ribitol, xylitol;

 Hexahydric alcohols (hexites) such as sorbit, mannitol, galactitol, and aroznolesit. Above all, Tri-Mouth Pro-Ha. And Penyu Elithreur are particularly preferred.

 In addition, bis (isocynatemethyl) cyclohexane (hydrogenated XDI, H6XDI) (ii) used as a component of the above-mentioned adduct (E1) includes 1,3-bis (i 1,4-bis (isomethyl) cyclohexane, 1,4-bis (isomethyl) cyclohexane, and 1,3 -Bis (isomethyl) cyclohexane is preferred.

The adduct (E 1) used in the present invention comprises the above-mentioned trihydric or higher aliphatic polyhydric alcohol (i) and bis (isosocyanate methyl) cysteine. It can be obtained by addition polymerization of chlorohexane (ii).

 The adduct (E 1) preferably used in the present invention includes, for example, compounds represented by the following formula.

 (1) The product of TMP and hydrogenated XDI

CH ₂ 0-C0-NH-CH ₂ -R-CH ₂ -NC0

CH.CH2-C- CH20- C0- H- CH2-R-CH ₂ -NC0

CH ₂ 0-C0-NH- CH2-R-CH ₂ -NC0

 [R in the formula: 1,3 cyclohexylene group]

 (2) Adduct between pentaerythritol and hydrogenated XDI

C [-CH ₂ —CO— NH— CH ₂ — R— CH ₂ — NC〇] R [R in the formula: 1,3 cyclohexylene group]

 The isocyanurate structure (nurate structure) (E 2) used as the polyisocyanate compound (E) in the present invention is represented by the above-mentioned formula [I] in the molecule. It has one or more rings.

 The isocyanurate structure (E 2) used in the present invention may be, for example, a trimerization reaction of bis (isosinetomethyl) cyclohexane (hydrogenated XDI, H6 XDI) described above. It can be obtained by performing a mersification reaction and a heptamersation reaction.

 In the present invention, the polyisocyanate compound (E) is obtained by converting the equivalent of the isocyanate group contained in the polyisonate compound (E) to the thiol group contained in the polymercaptocarboxylic acid ester (D). It is used in such an amount that the ratio [NCO group ZSH group] to the equivalent is in the range of 0.2 to 4, preferably 0.5 to 3, and more preferably 0.7 to 2.

When the polyisocyanate compound (E) is used in the above amount, The concentration application range of the vapor-form alumina catalyst can be expanded to 200 to 400 ppm, the setting of spray coating conditions is easy, and the force is quickly cured and uniform. Thus, a coating composition capable of forming a coating film can be obtained.

 Paint composition (2),

 In the second coating composition (coating composition (2)) according to the present invention, conventionally known coating additives such as coloring pigments, anti-pigmenting pigments, and dispersants are impaired for the purpose of the present invention. It can be blended in a range that does not exist.

 The premix composition (2) comprising the above-mentioned polymercaptocarboxylic acid ester (D) and the polyisocyanate compound (E) has a long pot life (pot life). I want to handle it. The composition (2) can be cured at room temperature. Next, the coating method according to the present invention will be described.

 The coating method according to the present invention comprises a method of curing the above-mentioned coating composition (1) or coating composition (2) on a substrate in the presence of a vapor-form amine catalyst to form a uniform coating film. For example, there are the following aspects.

(1) A coating method in which a coating composition is sprayed onto a substrate with a spray gun and rapidly cured in the presence of a vapor-form amine catalyst to form a uniform coating film.

 (2) The coating composition is sprayed onto a substrate with a spray gun to form an uncured coating film, and then the uncured coating film is brought into contact with a vapor-form amide catalyst to rapidly cure the coating film. Method to form a uniform coating film.

(3) At the same time that the coating composition is sprayed onto the substrate with a spray gun, the amine catalyst is sprayed onto the substrate with another spray gun to obtain a uniform cured coating. A coating method for forming a film.

 In the present invention, the coating method (3) is particularly preferable.

 The amine catalyst used in the present invention is: tertiary amine. Specifically, trimethylamine, dimethylethylamine, triethylamine, triethylamine, tributylamine and dimethylamine are used. Tilbenzilamin, dimethylaminocyclohexylamine, dimethylethylanoreamine, getyluenoramine, triethanolamine, pyridin, 4-phenylpropylpyridin, 2 , 4,6-collidine, quinoline, isoquinoline, ethylmorpholine, triethylenediamine and the like. Even in the case of burb, dimethyl noramine and triethylamine are preferably used.

 The above amine catalyst is used in the form of a vapor with a spray gun. When the above-mentioned coating composition (〗) or (2) is used as the coating composition, the concentration of the vapor-form amide catalyst in spray coating is set in a wide range of 20 to 400 ppm. be able to. Preferred concentrations of the vaporous amine catalyst are between 500 and 2000 ppm.

 When the coating composition (1) or (2) is atomized with a spray gun and sprayed onto a substrate in the presence of a vapor-form amine catalyst having a concentration of 200 to 400 ppm, it takes less than several minutes. And a uniform coating film is obtained.

 In addition, after the coating composition (1) or (2) is spray-coated on a substrate to form an uncured coating film, the coating composition is exposed to a vapor-form amine catalyst having a concentration of 200 to 400 ppm. The composition forming an uncured coating film rapidly cures, and a uniform coating film can be obtained within a few minutes.

Immediately before using the coating composition (1) or (2), an amide catalyst is added to the coating composition (1) or (2) and spun on the substrate. It is also possible to obtain a coating film that is lay-painted and cured uniformly. In this method, the coating composition to which the amide catalyst is added rapidly cures, and therefore needs to be used in a short time.

 Specific examples of the substrate (object to be coated) used in the present invention include iron, steel, copper, aluminum, zinc-coated steel, and gold such as lead !; wood materials, organic fiberboards, and resins. Materials (plastic foam, non-plastic foam); paper and the like.

 The coating method according to the present invention includes not only the coating methods of the above aspects (1) to (3), but also the electrostatic coating method described below. Next, an electrostatic coating method of the heavy duty anticorrosion paint composition according to the present invention and a heavy anticorrosion paint coated product obtained by the electrostatic coating method will be described. The electrostatic coating method for a heavy duty anticorrosion coating composition according to the present invention comprises the steps of: preparing a polymer (F 1) and Z or a polymercapto compound (F 2) in the presence of a vapor-form amine catalyst; This is a method of electrostatically applying a coating composition (3) comprising a polyisocyanate (G).

 The vapor-phase amine catalyst used here is the same as the above-mentioned vapor-phase catalyst.

 The coating composition (3) is a substantially solvent-free or solvent-free coating composition, and is composed of a polyol (F1) and a phenolic or polymercap compound (F2) and a crosslinking agent. Polysocyanate (G).

Polyol (F 1)-The polyol (F 1) used in the present invention includes, specifically, Ethylene glycol, Diethylene glycol, Triethylene glycol, Polyethylene glycol, Propylene glycol, Dipropylene glycol, Tripropylene glycol, Polypropylene glycol, Butylene glycol, Dibutylene glycol, Triethylene glycol Divalent alcohols such as butylene glycol, polybutylene glycol, 1,5-pentenediol, neopentyl glycol, 1,6-hexanediol, 1,10 decanediol, alkanediol, cyclohexanedimethanol, etc.ー ノ レ ；

 Glycerol, trimethylolprono ,. (TMP), 1,2,6-hexantriol, trimethylolethane, 2,4 dihydroxy-3hydroxymethylpentane, 1,1, tritris (bishydroxymethyl) propane, 2, 2-bis (hydroxymethyl) butanol 3 etc.

 Tetravalent alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabit, ribitol and xylitol;

 Hexahydric alcohols (hexites) such as sonorebit, mannite, galactitol, and arroshcit;

 Polyglycol compounds having up to about 10 carbon atoms, such as polyvalent hydroxy compounds such as polyglycerol and polytetramethylene glycol; and

Polyester polyols derived from phthalic anhydride, sebacic acid, fatty acids, epoxy resins, etc., epoxy polyols (epoxy-modified epoxy resin), polyether polyols or acrylic polyols Riol and the like.

 Among them, ethylene glycol, propylene glycol, 1,6-hexanediol, glycerol, and trimethylolproha. Pentaerythritol, polyester polyols, and acrylonitrile polyols are preferred.

 Polymeric compound (F 2),

 The polymercapto compound (polythiol) (F2) used in the present invention is a compound having two or more mercapto groups (one SH group). Examples of polymercapto compounds (F 2):-Physically, 1,3 propanedithiol, 1,4-butanedithiol, 1,6 hexanedithiol, 2,3-dimethylcaptopropanol, toluene 3 , 4 dithiol, hi, α'-dimethylcapto-p-xylol, dimercaptoethane, diethylenglycol dimenolecaptan, triethyleneglycone resinmercaptan, dithiocatechol, 3-chlorothiocatechol, dithioresonoresin, dimenolecaptotol Noren, xylylene dimenolecaptan, 1,3,5-trimercaptobenzene, dimercaptonaphthalene, didodecandithiol, dithiophenol, 4,4'-dithiophenol, 2,2'-dimethyl-4 , 4'-Ciodiphenol, Zimercap Tovenzothiazole, Dicheoeri Thritol and the like.

 Specific examples of the polymer capto compound (F 2) other than those described above include a complete ester or a partial ester composed of an aliphatic polyol and a mercapto lower fatty acid.

 Specific examples of the aliphatic polyol include:

Ethylene glycol, diethylene glycol, triethylene glycol Cole, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, polybutylene glycol 2 filli alcohols, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,10 decanediol, alkanediol, cyclohexanedimethanol;

 Glycerol, trimethylolpropane (TMP), 1,2,6 hexyltriol, trimethylolethane, 2,4 dihydroxy-3-hydroxymethylpentane, 1,1,1 tris (bishydrin) Trivalent phenols such as droxymethyl) prononone and 2,2bis (hydroxymethyl) butanol-3;

 Tetravalent alcohols such as pentaerythritol and diglycerol; pentahydric alcohols (pentit) such as arabit, ribitol, and xylitol;

 Hexahydric alcohols (hexitic) such as sonorebit, mannite, galactitol, and aroznorecit. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferred.

 Also, glycidyl ethers such as bisphenol A glycidyl ether, hydrogenated bisphenol A glycidyl ether, bisphenol F glycidyl ether, and novolak epoxy can be used.

In addition, specific examples of the above mercapto lower fatty acids include: And acetic acid, mercaptopropionic acid, mercaptosalicylic acid, menolecaptoglycolic acid, N- (2-hydroxyxethyl) thioglycolic acid, mercaptoconoic acid, citric acid and mercaptolingoic acid. Of these, mercaptoacetic acid (HSCH ₂ COOH) and mercaptopropionic acid are preferred.

 Polymercapto compounds (F 2) which are particularly preferably used in the present invention are pentaerythritol and mercaptoacetic acid or mercaptopropionic acid, or trimethylolprono, and methylolcaptoacetic acid. Or an ester having 2 to 4 mercapto groups consisting of menolecaptopropionic acid.

 Note that a thiol compound having one mercapto group can be used as a diluent or a plasticizer.

 In the present invention, it is desirable to use a polymercap compound (F 2) which does not require a solvent and has no or little odor.

 <Polysociate (G)

 As the polyisocyanate (G) used in the present invention, specifically,

Hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), 1,3-bis (isocyanatomethyl) cyclohexane (hydrogenated XDI, H6XDI), tri-range isocyanate (HDDI) TDI), diphenyl methane diisocyanate (MDI), 4,4-bis (isocyanatocyclohexyl) methane (hydrogenated MDI), naphthylene diisocyanate (NDI), isoforo Njiy Sociane (IPDI), mexylylene diisocyanate (MXDI), lysine diisocyanate (2,6-diisocyanate methylcaproate) (LDI), methylcyclohexane -2,4 (or2,6) digi Societane (hydrogenated TDI or HTDI), trimethylhexamethylene diisocyanate (MDI), dimer monoacid diisocyanate (DDI), trizindiisocyanate (T〇D)), p-phene Diisocyanates, such as nirange isocyanate, transcyclohexane-1,4 diisocyanate, tetramethylxylene diisocyanate (TMXDI);

 Triphenyl methane trisocyanate, tris (iso cyanone triphenyl) thiophosphonate, lysine ester triisocyanate, 1,6,11-indecantry isocyanate, Triisocitanes such as 1,8-diisocitrate-4_isothiate methyloctane, 1,3,6-hexamethylenetriisolate, and bicycloheptantriisolate No.

 A null form or an adduct form derived from the above-described isocyanate can also be used.

Further, specific examples of the polyisocyanate (G) other than the above include the following carposimid type polyisocyanate. This carposimid-type polyisocyanate has at least one —N = C = N— group. Specifically, the carposimid-type diphenylmethane diiso- nate and the carposimid-type tolylenedisilane Carbodimid dimethyl biphenylene diisocyanate, carbodimid xylen diisocyanate, and carbodiimide naphthalene range Isocene, carposimid hexamethylene diisocyanate, carposimid isosophorone succinate, carbodimid hydrogenated xylylene diisocyanate, carbodimid hydride hydrogenated diphenylmethane Social networks.

 The polyisocyanate (G) preferably used in the present invention includes a carbodiimide-type diphenylmetanediocyanate, a carbodiimide-type trirangedisilane, and a carbodimid-type dimethyltilbif Idirangediisomethane. It is a carposimid type hexamethylene diisocyanate. In particular, carbodimid-type diphenylmethanediisosinate is preferably used.

 In addition, a carposimid type polyisocyanate having one —N = C = N— group can be represented by the following formula.

(OCN-R ')-N = C = N-(R ² -NC 0)

[(OCN—R ¹ ) and (R ² -NC 0) in the formula are polyisocyanates. ]

 Further, as specific examples of the polyisocyanate (G) other than the above polyisocyanate,

 (1) Trihydric or higher aliphatic polyhydric alcohol (i), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), mexylylene diisocyanate (MXDI), hexame Adducts with Chillen Isocene (HDI or HMDI), Isophorone Disocinate (IPDI), or Bis (Isoocyanate Methyl) Cyclic Hexane (ii), and

(2) Hexamethylene diisocyanate (HDI or HMD I) An isocyanurate structure (nurate structure) having a ring represented by the above formula [I], which is composed of sophoronediisocyanate (IPDI) or bis (isosinate methyl) cyclohexane. be able to.

 As the trihydric or higher aliphatic polyhydric alcohol (i) used as a component of the above-mentioned adduct, specifically,

Glycerol, trimethylolprono, ⁰ (TMP), 1,2,6-hexantriol, trimethylolethane, 2,4 dihydroxy-3-hydroxymethylpentane, 1,1,1 -Trivalent alcohol such as tris (bishydroxymethyltinole) propane and 2,2-bis (hydroxymethyl) butanol-3;

 Pentahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabit, ribitol and xylitol (pentitic);

 Hexahydric alcohols (hexitic) such as sorbitol, mannite, galactitol, and arozurcit are mentioned. Among them, trimethyl alcohol and pentaerythritol are particularly preferred.

In addition, a tolylenedioxide (TDI), a xylylenedisulfide (XDI), a mexylenedilysocyanate (MXDI), a hexamethylenedilysocyanate (HDI or HMDI), isophorone diisocene (IPDI), bis (isocene monomethyl) cyclohexane (hydrogenated XDI, H6XDI) (ii), 1,3 bis (isomethine methyl) Cyclohexane, tolylene glycol (T DI) and Xylylene Range Isolate (XDI) are preferred.

 The above-mentioned adduct (1) used in the present invention may be, for example, an aliphatic polyhydric alcohol (i) having 3 or more valences as described in (1) and bis (isomethine-methyl) cyclohexane, etc. (ii) Can be obtained by addition polymerization of Preferred examples of the adduct used in the present invention include a compound represented by the following formula.

 (1) The product of DMP and hydrogenated XDI

CH ₂ 0-C0-NH- CH2-R-CH ₂ -NC0

CH, CH ₂ -C-CH2O-CO-NH-CH ₂ -R-CH ₂ -NCO

CH ₂ 0-C0-NH- CH2- -CH ₂ -NC0

 [R in the formula: 1,3-cyclohexylene group]

 (2) Adduct of Penyu-erythritol with hydrogenated XDI

_{C [-CH 2 0 - CO -} NH - CH 2 - R - CH 2 - NCO] "[R in the formula: 1, 3 xylene group to consequent b]

 The isocyanurate structure (nurate structure) used as the polyisocyanate (G) in the present invention has one or two rings represented by the formula [I] in the molecule. Have more than one.

 The isocyanurate structure used in the present invention includes, for example, a trimerization reaction, a pentamerization reaction of bis (isosinate methyl) cyclohexane (hydrogenated XDI, H6 XDI) described above. It is obtained by performing a heptamerization reaction.

 Mix ratio

In the present invention, each of the components of the polyol (F 1) and the polymer or the compound (F 2) and the polyisocyanate (G) is The total equivalent of the isocyanate group contained in the polyisocyanate (G), the equivalent of the hydroxyl group contained in the polyol (F1), and the equivalent of the thiol group contained in the polymercapto compound (F2) The ratio to the amount [NC 0 group (0 H group + SH group)] is usually 0. To 5, preferably 0.2 to 4, more preferably 0.5 to 3, and particularly preferably 0.7 to 2.

 In addition, the above-mentioned carbodiimide-type polyisocyanate is used in combination with a polysociate other than the calposimid type as the polyisocyanate (G). In this case, the calposimid type isocyanate is usually used in an amount of at least 1 part by weight and less than 200 parts by weight, preferably at least 5 parts by weight, based on 100 parts by weight of the total amount of these polyisocyanates. It is used in an amount of less than 150 parts by weight, more preferably from 20 parts by weight to less than 100 parts by weight.

 When the carbodimid-type polysocyanate is used in the amount described above, a coating composition capable of rapidly curing to form a coating film is obtained.

 <Coating composition (3),

 The above-mentioned coating composition (3) can form a clear coating film as a clear coating composition. However, a conventionally known coating additive such as a coloring pigment or a dispersant is added to the coating composition of the present invention. It can be used as an ordinary coating composition by blending it within a range that does not impair the purpose.

 The coating composition comprising the above-mentioned polyol (F 1) and Z or the polymer cap compound (F 2) and the polyisocyanate (G) has a long pot life and is easy to handle.

The alumina catalyst used here is the same as the alumina catalyst described above. It is used as a vapor with a spray gun. When the above-mentioned paint composition (3) is used, the concentration of the vapor-form amine catalyst in spray coating can be set in a wide range of 20 to 400 ppm. The preferred concentration of the vaporous amine catalyst is between 500 and 2000 ppm.

 The viscosity of the coating composition (3) used in the electrostatic coating method for the heavy duty anticorrosion coating composition according to the present invention may be any viscosity as long as it allows electrostatic coating, and is generally 500 c. It is at most Ps, preferably at most 300 cPs, particularly preferably at most 100 cPs (measured with a B-type viscometer). Such a low-viscosity coating composition (3) tends to be finely atomized into fine particles, and is suitable for low-pressure, low-flying-speed electrostatic spray coating. Efficiency can be improved.

 The electric resistance value of the coating composition (3) used in the present invention is usually about 30 to 100 MΩ. The coating composition having such an electric resistance value is finely atomized by spraying.

 In electrostatic coating, a grounded object is used as an anode (+) and a paint sprayer is used as a cathode (1) to apply a high voltage to form an electrostatic field between the two electrodes and scatter the paint in the static field. This is a method of forming a coating film on the surface of the object to be coated by applying a negative charge to the substrate (object to be coated) and sucking the substrate.

When the above coating composition (3) is electrostatically coated as a heavy-duty anticorrosion coating composition, the coating composition is sufficiently and evenly applied to the edges of steel plates of steel structures such as ships, edges such as holes, and narrow portions. A coating film having an appropriate thickness can be formed. Therefore, according to this electrostatic coating method, an edge portion and a narrow portion, which are required by a simple wireless spray coating using a conventional tar-based heavy-duty anticorrosion coating, are required. Brush painting of the bottleneck eliminates the need for additional painting by hand, reducing man-hours.

 The above-described electrostatic coating method for heavy-duty anticorrosion coating has the following aspects.

 (a) A coating method in which a low-viscosity coating composition (coating composition) is applied to an object to be coated by an electrostatic coating method and rapidly cured in the presence of a vapor-form amine catalyst to form a coat. .

 (b) After the coating composition is applied to the object to be coated by the electrostatic coating method to form an uncured coating film, the uncured coating film is brought into contact with a vapor-form amine catalyst to form the coating film. A method of rapidly curing and forming a coating film.

 (c) At the same time as spraying the paint composition from one paint spraying device (eg, spray gun) on the electrostatic spraying method and attaching it to the object to be coated, spraying the amine catalyst from the other spraying device. A coating method in which a cured coating film is formed by spraying on the object.

 Among these electrostatic coating methods, the electrostatic coating method (c) is particularly preferable.

 The electrostatic coating equipment used for these electrostatic coatings and the coating conditions will be described in more detail.

 In the case of such electrostatic coating, any of a fixed (automatic) coating device and a portable (handheld) coating device can be used. As a fixed coating device, for example, a grid type coating device is used. , Rotating cup electrode type, and rotating disk type.

Of these, a portable coating device using a spray gun is preferably used when painting vessels (objects to be coated) such as tankers, fishing boats, cruise ships, etc. because of its excellent workability in a narrow environment. The distance between the object to be coated and the cathode during such electrostatic coating, the applied DC high voltage value, the paint feed pressure, the paint spray air pressure, etc. depend on the type of paint used, its viscosity, and the required film. It can be appropriately set according to the thickness, the moving speed of the coating apparatus, and the like, and is not particularly limited.

In a portable (hand-held) coating device, the cathode is set at the tip of the spray gun. When the trigger is triggered, a negative charge is applied to the sprayed paint particles, and the coating is separated by several to several tens of centimeters. It is possible to apply electrostatic coating of painted objects. The power supply voltage is low, and the spray gun is easy to carry, so it is suitable for on-site painting of hulls, for example. The spray gun includes, for example, an air atomizing type, an airless atomizing type, an electrostatic atomizing type (rotating cup type), and the like, and any type may be employed. In the grid coating, a DC high voltage of 30 to 200 kV (preferably 65 to 110 kV) is applied, and the object to be coated and the grid (cathode grid frame) are applied. Keep the distance between 10 and 100 cm (preferably about 30 to 50 cm), and when spraying, spray air pressure 0.5 to 5 _kg / cm ² (preferably 1.5 to ^2.5 kg / cm ² ) and paint feed pressure 0.2 to 2 kg Z cm ² , secondary pressure (air pressure) 50 SOO kg Z cm ^{2 for} air spray, travel speed 20 to 200 cmZ Seconds (preferably 40 to 90 c seconds) should be set.

In the case of a rotating cup, the rotating speed is kept within the range of 300 to 300 rpm / min (preferably 750 to 180 rpm). The paint can be fed in and electrostatically applied to the object with an applied voltage of about 50 to 70 kV. The grid and spray gun as in the above-mentioned grid type are unnecessary, and handling is easy. In any case, it is preferable that the surrounding wind speed at the time of coating is as small as possible from the viewpoint of paint loss and skin, and it is desirable that the wind speed is 0.3 m / sec or less.

 When an electrostatic coating of an object to be coated is performed by such a method, adopting an automatic coating system such as a robot coating is particularly effective in reducing the number of work steps.

 The anticorrosion paint-coated product according to the present invention is obtained by forming a film on a substrate (substrate) by using the above-described coating composition (3) and the above-mentioned electrostatic coating method. .

 The object to be coated is not particularly limited as long as electrostatic coating with the heavy-duty anticorrosive paint comprising the above-mentioned coating composition (3) can be performed. However, it is preferable that the article to be coated by such a method be used. , Underwater and overwater structures (eg: Gulf roads, submarine tunnels, harbor facilities, canals, waterways, etc., for the construction of various types of marine civil engineering equipment, such as membranes for preventing sludge diffusion, rafts, floating docks, and water pipes for power plants , Oil and gas drilling); onshore structures such as bridges; and various molded objects such as ships and fishing vessels (eg: ropes, fishing nets).

These coated products coated by the above-mentioned electrostatic coating method are excellent in anticorrosion properties, are not easily destroyed in structure, and are excellent in durability. Next, a method for coating a plastic foam according to the present invention and a plastic foam coated article obtained by the coating method will be described. The method for coating a plastic foam according to the present invention comprises the step of coating the above-mentioned coating composition (1), (2) or (3), preferably the coating composition (3), in the presence of a vapor-phase catalyst. Cured on a plastic foam This is a method for forming a coating film. That is, the coating method of the plastic foam is the same as the coating method according to the present invention described above, except that the coating composition is a coating composition other than the coating compositions (1) and (2). (3) can be used.

 The amine catalyst used here is the same as the above-mentioned amine catalyst, and is used in the form of vapor with a spray gun or the like. By using the above composition (3), the concentration of the vapor-form amine catalyst in spray coating can be determined over a wide range of 20 to 400 ppm. Preferred concentrations of the vaporous amine catalyst are between 500 and 2000 ppm.

 Specific examples of the plastic foam include polystyrene, polyurethane, ABS resin, AS resin, polyvinyl chloride, polyethylene, polypropylene, phenol resin, urea resin, epoxy resin, and gay resin. , Polyphenylene oxide, polyimide resin, polycarbonate, unsaturated polyester, polyethylene terephthalate, polybutylene terephthalate, NBR rubber, urethane rubber, etc. Foams made of resin are exemplified.

 The plastic foam coated article according to the present invention can be prepared by the above-described coating method according to the present invention, for example, the following coating method.

 (1) A coating method in which a paint composition is sprayed onto a plastic foam with a spray gun and rapidly cured in the presence of a vapor-form amine catalyst to form a coating film.

(2) Spray the coating composition onto the plastic foam with a spray gun Forming an uncured coating film by contacting the uncured coating film with a vaporized amine catalyst to rapidly cure the coating film to form a coating film.

 (3) A coating method in which a paint composition is sprayed on a plastic foam with a spray gun and, at the same time, an amine catalyst is sprayed on the plastic foam with another spray gun to form a cured coating film.

 In the present invention, the coating method (3) is particularly preferable. The invention's effect

 The first coating composition (coating composition (1)) according to the present invention comprises a polymercapto compound (A) and a carbodiimide-type polyisocyanate (B). In the presence of an amine catalyst, it cures rapidly to form a uniform coating.

The coating film formed with the first coating composition according to the present invention has excellent anticorrosion properties (adhesive strength, saltwater-peeling resistance, and cathodic-peeling resistance), and does not easily peel off even under severe cold and hot conditions. Suitable for heavy-duty corrosion protection and other applications, as it can reduce the generation of metal 锖. Further, the second coating composition (coating composition (2)) according to the present invention comprises a polymercaptocarboxylic acid ester of an aliphatic polyhydric alcohol (D), a trihydric or higher aliphatic polyhydric alcohol and bis (Isocyanate methyl) At least one selected from an adduct with cyclohexane (E1) and an isocyanurate structure (E2) composed of bis (isosine-tomethyl) cyclohexane. Since it contains one kind of polysocyanate compound (E), the application range of the concentration of the vapor-form amine catalyst is wide, It is easy to set the coating conditions for play coating, and it can be cured rapidly to form a uniform coating within a few minutes.

 The coating film formed with the second coating composition according to the present invention has excellent anticorrosion properties (adhesive strength, saltwater-peeling resistance, and cathodic-peeling resistance), and does not peel off even under severe cold chopstick conditions. It can reduce the occurrence of metal coatings, making it suitable for heavy duty corrosion protection and other uses.

 Further, the first and second coating compositions according to the present invention have a long pot life, can be used for indoor and outdoor spraying, and can be sprayed regardless of summer and winter. .

 The first and second coating compositions according to the present invention having the above-mentioned effects are required to have anticorrosive properties (corrosion resistance) for woodworking, automotive and industrial spray applications, particularly for steel plates and pipelines. It is suitable for spray coating for various applications.

 According to the coating method of the present invention using the coating composition (1), the coating composition (1) is cured on a substrate in the presence of a vapor-form amine catalyst. 1) can rapidly cure to form a uniform coat.

 By such a coating method, the coating film formed of the coating composition (1) has excellent anti-corrosion properties (adhesive strength, salt-water-peeling resistance, and cathodic-peeling-resistance), and does not peel off even in severe cold and hot conditions. In addition, it is possible to prevent the sale of the metal to be coated from occurring.

By using the coating composition (1) as described above, the applicable range of the concentration of the vaporous amine catalyst can be expanded to 20 to 400 ppm, and the coating conditions for spray coating can be increased. Is easy to set. Further, according to the coating method of the present invention using the coating composition (2), the coating composition (2) is cured on a substrate in the presence of a vapor-form amine catalyst. (2) quickly cures and can form a uniform coating within a few minutes.

 With such a coating method, the coating formed with the coating composition (2) has excellent anticorrosion properties (adhesive strength, saltwater-peeling resistance, and cathodic-peeling resistance), and does not easily peel off even under severe cold and hot conditions. In addition, it is possible to prevent the generation of the color of the metal to be coated.

 By using the coating composition (2) as described above, the applicable range of the concentration of the vaporous amine catalyst can be expanded to 200 to 400 ppm, and the spray coating can be applied. Setting conditions ^ Easy.

 The coating method according to the present invention can be performed indoors and outdoors irrespective of summer and winter by using the coating compositions (1) and (2).

The coating method according to the present invention using the coating compositions (1) and (2) is spray coating for woodworking, automobile, and industrial use, particularly for anticorrosion applications such as steel plates and pipelines. Suitable as a coating method. According to the method for electrostatically coating a heavy duty anticorrosion coating composition according to the present invention, a polymercapto compound or a polyisocyanate which is rapidly cured by a vapor-form amine catalyst. Since the low-viscosity coating composition (3) containing urethane resin is electrostatically coated on the object to be coated, the surface of the steel plate such as the hull is shielded from seawater, outside air, etc., and oxygen, chlorine, water Necessary to prevent the penetration of steam, etc. to prevent corrosion of steel plates. ・ A worker can easily and quickly form a coating film with a sufficient thickness on the surface of the object to be coated. High environmental safety.

 According to this electrostatic coating method for heavy-duty corrosion protection, the coating composition (3) can be rapidly cured without heating to form a crotch on the object to be coated. Therefore, even when applied to a vertical wall surface of a ship or the like, it is possible to form a thick coat having a thickness of several hundreds of micrometer without causing paint dripping and slippage.

 This electrostatic coating method for heavy duty anticorrosion coating can be applied indoors and outdoors regardless of summer and winter. According to the method for coating a plastic foam according to the present invention, the coating composition (1), (2) or (3) is rapidly cured on the plastic foam without heating, and It is possible to form a coating film of several meters to several hundred thousand m uniformly without changing the shape of the body. In this coating method, the coating composition (3) is preferred.

This method for coating a plastic foam has excellent coating workability and is economically advantageous. Moreover, it can be performed indoors and outdoors regardless of summer and winter. The anticorrosion paint coated product according to the present invention is a coated product for ships, underwater / water structures, and the like. Since these coated products are prepared by the electrostatic coating method for heavy anticorrosion coating as described above, It has excellent corrosion protection, is resistant to structural damage, and has excellent durability. In addition, the plastic foam coated article according to the present invention is obtained by curing the coating composition (1), (2 or (3)) on a plastic foam without heating by the above-mentioned coating method, to form a coating film. Therefore, even if the coating film contains a few thousand plastic foam dissolved components, the plastic foam does not shrink or collapse, and the water resistance is high. Particularly preferred is a plastic foam coated product using the coating composition (3).

 This plastic foam-coated product is used for food packaging such as fish and vegetables; insulation materials used for electrical appliances; cooling materials; components used for piers; floats used for farms. Building insulation and interior materials, automotive interior materials, cold insulation materials, pipe covers, dew proof materials, fish boxes, packaging materials, shoe soles, cushion flooring materials, mattresses, sports It can be used for applications such as protection technology, oil reef, surfboards, and life jackets.

 Examples etc.

 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

 [1] Example and Comparative Example of First Paint Composition (Paint Composition (1)) According to the Present Invention and Its Coating Method

 The method of measuring the curing time of the paint and the methods of the cathodic peeling test, the salt spray test and the accelerating liquid test performed in Examples and Comparative Examples in [1] are as follows.

 (1) Method of measuring paint curing time

The curing time of the paint is JISK540 (6.5 (5) (C) curing and drying) The measurement was performed according to the following.

 (2) Cathodic peel test

 The cathodic peel test was performed in the following manner according to ASTM G8-90 (Method B).

 The center part of the coating applied to a 150 mm long and 70 mm wide test piece was cut into a 7 mm diameter circle using a drill to expose the steel plate base, and then the test pieces were removed. Immerse in purified water containing 1% by weight of anhydrous sodium chloride, anhydrous sodium sulfate and anhydrous sodium carbonate, and use the copper-copper sulfate electrode as a reference electrode. A voltage was applied to the film, and after 700 hours, the film was pulled up, and the coating film in the area where adhesion was reduced was peeled off with a cutter knife toward the outside of the circle, and the diameter (mm) of the peeled portion was measured. 7 mm was subtracted from the diameter of the peeled portion, and the value 2 was evaluated as the peel width.

 (3) Salt spray test

 After making a linear scratch of 4 cm in length with a force cutter knife on the coating film and performing a salt spray test for 700 hours in accordance with JISK540 (9.1), the appearance of the coating film is visually observed. Observation and evaluation were performed, and the adhesion of the coating film by an adhesion test (ISO 4624 7.3.2) and the width of the creep from scratches were measured.

 The width of the stripped area was measured by measuring the width (mm) of the area where the adhesion was reduced by using a cutter knife in one direction toward the outside of the scratch area. The peel width was defined as the creep width.

 (4) Accelerated liquid test

In the accelerated solution test, the coating film was immersed in a 3% acetic acid aqueous solution at 60 ° C for 3 weeks, The appearance of the paint film after immersion was visually observed and evaluated.Furthermore, the adhesion of the paint film by the adhesion test (ISO 4624 7.3.2) and the JISK 504.15 (4.3) The specified impedance (taηδ) was measured. Raw materials used in Examples and Comparative Examples are as follows. Poly mercapto compound

 (1) Ρ Ε Τ Ρ

 Pentaerythritol thoraxtipropionate manufactured by Yodo Chemical Co., Ltd.

 S H group equivalent = 1 3 6

 (2) 〇 T G

 Octyl thioglycolate, manufactured by Yodo Chemical Co., Ltd.

 S Η group equivalent = 2 0 4

 (3) Necils Ε Ρ X— L

 A 'Shichi' i Japan Co., Ltd.

 Product name Nesilus Ε Ρ X— L

Carbodimid-type poly isocyanate

 (4) M T L

 Made by Nippon Polyurethane Industry Co., Ltd., trade name MILIONET MTL Carbodimid-type diphenylmethanediocyanate

 N C 0 content-2 8.9%

Lee Seo Nu Rate

(5) 1 7 0 Η Ν Takeda Pharmaceutical Co., Ltd., Trade name D170 HNHDI-based isocyanurate, NC〇 content = 21.0%

(6) Coronet H X

 Said Polyurethane Industry Co., Ltd., trade name: Colony HXHDI-based isocyanurate, NC content = 21.1%

(7) DC 2 7 9 7

 According to Polyurethane Co., Ltd.

 Product name Coronet D C 2 7 9 7

 HDI-based bifunctional isocyanurate,

 N C 0 content = 2 2.1%

 Materials

 (8) Talc

 Product name, Talc NKK, manufactured by Fuji Talc Kogyo Co., Ltd.

 Average particle size = 6-8 / m

 (9) Barium sulfate

 Made by Sakai Chemical Industry Co., Ltd., product name

 (10) Titanium white

 Product name T R— 9 2

 (11) Polyamide Wax

 Made by Ito Oil Co., Ltd., trade name A S A-T 350 F

 (12) Colloidal silica

Nippon Aerosil Co., Ltd. Product name Aerosil 200 Specific surface area = 200 m ² Z g (BET method) Examples〗 to 3 and Comparative Examples 1 to 3

 Shotblasted mild steel (150 x 70 x 3.2) and inorganic zinc shop primer [China Paint Co., Ltd., trade name Cerabond] The surface of the coated mild steel is shown in Table 1. The coating composition was sprayed in the presence of an amine vapor catalyst to form a coating.

 In this test, the coating was carried out at an alumina vapor concentration of 1000 to 2000 ppm. The amine vapor concentration was measured with a Kitagawa type amine detector tube manufactured by Komei Rikagaku Kogyo. The coating was performed such that the thickness of the coating film became 200 m in a weight gauge.

 Then, the coated test piece obtained as described above was left at room temperature for 7 days after coating, and the above-mentioned cathodic peel test, salt spray test and accelerating liquid test were performed.

 The curing time of the paint was measured according to the method described above.

Table 2 shows the results.

Table 1 (Distribution ^ ¾)

PVC: Pigment volume offer Table 2 (¾ «^ fruits)

 33 ：: ife3 blasted fcife steel plate

I ZP: Zinc Shop Primer ^^ As is clear from Table 2, the coating films were formed in a short curing time in each of the examples and the comparative examples.

 In Example 1 in which the carbodimid-type polysocyanate was used alone, and in Examples 2 and 3 in which the calposimid-type polysocyanate was used in combination with the HDI-based polysocyanate, the accelerated solution test was performed. Very good results were obtained in the cathode peel test and the salt spray test.

 On the other hand, in Comparative Examples 1, 2, and 3, which did not use the carbodimid-type polysociate, the resistance was inferior in the accelerating solution test and the cathodic peeling test, and they did not exhibit sufficient anticorrosion performance. .

[2] Examples and comparative examples of the second coating composition (coating composition (2)) according to the present invention and its coating method

 The method for measuring the curing time and the pot life of the paint and the methods such as the cathodic peel test, the salt spray test and the accelerating solution test performed in the examples and comparative examples in [2] are as follows.

 (1) Method of measuring paint curing time

 The curing time of the paint was measured according to JIS K 5400 (6.5 (5) (b) semi-cured drying).

 (2) Method for measuring paint pot life

 The paints (base agent, curing agent) were mixed and adjusted, and the viscosity was measured with a B-type viscometer two hours later. When the paint viscosity was 25 poise or less, it was judged that there was no practical problem, and it was judged that the pot life was secured for 2 hours or more. (3) Vibration force hardness

The hardness of the coating film is evaluated according to ISO 1522-1973 3.1. KKoenig penduium) did.

 (4 Adhesive strength

 The adhesion of the coating film was measured and evaluated according to JIS K 5400 1.1.1.

 (5) Impedance

 The impedance of the coating film was measured according to JIS K 5400 8.15 (4.3), and evaluated by taη a.

 (6) Salt spray test

 Same as the salt spray test described above.

 (7) Cathodic peel test

 Same as the cathode peel test described above.

 (8) Accelerated liquid test

 In the test of the accelerating solution, the coating film was applied to a 3% aqueous acetic acid solution. C was washed for 3 weeks, and the appearance of the coating film, the adhesion by an adhesion test, and the impedance were measured and evaluated. Raw materials used in Examples and Comparative Examples are as follows. Polymeric carboxylate

 (1) PETP: manufactured by Yodo Chemical Co., Ltd.

 (Pentaerythritol tetrachischiprobione-to, SH equivalent-1 36)

 (2) 0TG: Yodo Chemical Co., Ltd. (Octyl thioglycolate,

 S H equivalent = 2 0 4)

Polyisocyanate compound

(1) D—121 N: manufactured by Takeda Pharmaceutical Co., Ltd. Product name Takenate D— 1 2 1 N

 (H6XD I Nurate,

 N C〇 content = 14.0%)

 (2) D-127 N: manufactured by Takeshi Pharmaceutical Co., Ltd.

 Product name Takenet D- 1 2 7 N

 (H6XDI nucleate, trimer of H6XDI, NCO content = 13.5%)

 (3) D-170N: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product name Take D- 1 7 0 N

 (HDI Nutrient, NCO content = 21.0%)

(4) D-170HN: Takeda Pharmaceutical Co., Ltd.

 Product name Takenate D—1 7 0 H N

 (HDI Nurate,

 N C 0 content = 22.7%)

 (5) D-177 N: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product name Takenate D—1 7 7 N

 (HDI nurate, NCO content = 20.0%)

(6) Coronate HX: manufactured by Japan Polyurethane Industry Co., Ltd.

 Product name Coronate H X

 (HDI Nutrition,

 NCO content = 21.1%)

 (7) DC2797: Nippon Polyurethane Industry Co., Ltd.

 Product name D C 2 7 9 7

(NDI content, NCO content = 22.1%) (8) D-190N: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product Name Evening D- 1 9 0 N

 (HDI nutrate, 1 ^ 00 content © = 202)

(9) MR—200: manufactured by Japan Polyurethane Industry Co., Ltd.

 Product name Millionate M R—2 0 0

 (Polymetric MDI,

 NCO content = 31.1%)

 (10) D-12ON: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product name Takenate D— 1 2 0 N

 (The product of H6XDI and TMP,

 N C〇 content = 11.0%)

(1DD-11 ON: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product name Takenate D—1 1 0 N

 (The product of XDI and TMP,

 N C〇 content = 1 1.8%)

 (12) D—140N: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product name Takenato D—1 4 0 N

 (The product of IPDI and TMP,

 N C 0 content = 1 0.5%)

 (13) D-212 L: manufactured by Takeda Pharmaceutical Co., Ltd.

 Product name Takenate D—2 1 2 L

 (Adduct of TDI and TMP,

 (NCO content = 7.5%)

(14) Coronet L: manufactured by Japan Polyurethane Industry Co., Ltd. Product name Coronate L

 (Adduct of TDI and TMP,

 (NC 0 content = 13.2%)

Pigments, etc.

 (1) Talc: Fuji Talc Kogyo Co., Ltd., Trade name Talc NKK

 (Average particle size = 6 to 8 micron)

 (2) Barium sulfate: manufactured by Sakai Chemical Industry Co., Ltd., trade name: Barium sulfate B A

(3) Titanium white: manufactured by SCM Chemical Co., Ltd.

 Product name R C L — 5 7 5

 (4) Polyamide Wax: manufactured by Ito Oil Co., Ltd.

 Trade name A S A—T 350 F Example 4 and comparative examples 4 to 7

 Blistered mild steel plate (150 x 70 x 3.2 mm) and inorganic zinc shop primer "Cerabond, manufactured by China Paint Co., Ltd." The composition was sprayed under a dimethylethanolamine vapor catalyst to obtain a coating film. In this test, the coating was performed in the range of 800 to 100 ppm of vapor concentration. Amin vapor concentration was measured with a kitagawa type amin detector tube manufactured by Komei Rika Kogyo Co., Ltd.

 The above coating was performed so that the thickness of the coating film was 200 micron with a d gauge.

Next, the coated test piece obtained as described above was left at room temperature for 7 days after coating, and the physical properties of the coated film were evaluated. The coating composition in Table 3, Table 4 shows the results ₍

Table 3 (Distribution ^ ¾)

PVC: pigment Table 4

*: Unable to form coating film

As is clear from Table 4, the coating films were formed in a short curing time in each of the examples and the comparative examples.

H 6 XDI of Bok Li methylotrophic one Rupurono, ⁰ Adaku preparative I Soshiane is one preparative D-1 2 0 N of emissions (TMP) in突施Example 4 was used alone, prompting Susumueki test, cathodic disbondment In the test and salt spray test, good knotting force was obtained.

 On the other hand, in Comparative Example 4 in which D—110N, which is an XDI TMP adduct type isocyanate, was used alone, the peeling width in the cathode peeling was large.

 In Comparative Example 5 in which D-14ON, which is an XDI TMP adduct-type isocyanate, was used alone, the state of the coating film was inferior in the accelerating solution test, the cathode peeling test, and the salt spray test.

 In Comparative Example 6, in which D2 L was used alone, which is a TMP TMP adduct type isolate of TDI, the pot life was short and not practical, and a smooth coating film could not be obtained. Similarly, in Comparative Example 7, in which Coronet L, which is a TDI TMP adduct type isotope, was used alone, the state of the coating film after spraying with salt water was poor, and the peeling width after cathode peeling was large.

 As described above, among the general TMP adduct-type isocyanates, the coating performance of the H6XDI TMP adduct-type isocyanate is excellent.

Examples 5 and 6 and Comparative Examples 8 to: 14

 Coating was performed in the same manner as in Example 4, and after the coating was allowed to stand at room temperature for 7 days, physical properties of the coating were evaluated.

Table 5 shows the paint composition and Table 6 shows the results. Table 5 (Recipe table)

PVC: Pigment volume concentration

Table 6

Damage

As is clear from Table 6, the coating films were formed in a short curing time in each of the examples and the comparative examples.

 In Examples 5 and 6, where the H6 XDI isocyanurates D-121N and D-127N were used alone, extremely high levels were obtained in the accelerating solution test, the polar peel test, and the salt spray test. The result was good.

 In Comparative Example 8 using D—17 ON, which is an HDI isocyanate, the pot life is short, less than one hour, and is not practical.

 In Comparative Example 9 using D-170 HN, which is an HDI's isocyanurate, the peeling width in the cathodic peeling test was large, and the film state after the accelerating solution test was poor, and the value of tan (was large.

 In Comparative Examples 10, 11, and 12 using D-177N, Coronate HX and DC-277, which are HDI's isocyanates, the peeling width in the cathode peeling test was large. Further, the state of the coating film after the accelerating liquid test was poor, and occurrence of blisters was observed.

 In Comparative Example 13 using D-190N, which is an oxaziazine trione (ODT) derivative of HDI, the pot life was extremely short and no practical use was recognized as a paint.

 In Comparative Example 14 using MR-20, which is a polymeric MDI, the pot life is as short as one hour or less, which is not practical. In addition, the peeling width in the salt spray test exceeded 10 mm, and the value of tan S after the accelerating solution test was large.

As described above, the H6XDI TMP adduct-type isocyanate has excellent coating performance among general nutrates. [3] Coating composition (3) Examples of lysing method using [Coating composition for heavy-duty corrosion prevention] and coated articles coated by the method! Examples and comparative examples Examples and comparison in this [3] The methods for measuring the coating I during the curing of the paint I: and the test methods for the appearance and water resistance of the coating film are as follows.

 (1) Method of measuring paint curing time

 The curing time of the paint was measured according to JIS K 5400 (6.5 (5) (b) semi-cured drying).

 (2) ^ Appearance of membrane

 In accordance with JISK 540 0 7.1, we observed glares, unevenness, dents, dents, and pits.

 (3) Film thickness

 The film thickness of the coating film was measured with an electromagnetic film thickness meter (trade name: LE-210) manufactured by Kett Science Laboratory. Raw materials used in Examples and Comparative Examples are as follows. Poly mercap

 (1) P E T P

 Yodo Chemical Co., Ltd., Penyu Erythritol Tetracchiopropionate, equivalent of SH group = 1 36

 (2) 0 T G

 Yodo Chemical Co., Ltd., octyl thioglycolate,

 S H group equivalent = 2 0 4

Polio (1) XU-K 1 3 5

 Takeda X U—Κ135, manufactured by Takeda Pharmaceutical Co., Ltd., Castor oil polyol, hydroxyl equivalent = 198

Plasticizer

 (1) Necils Ε Ρ X— L

 Ai Shii 'manufactured by IJAPAN

 Product name Nesilus Ε Ρ X— L

 (2) D Β Ρ

 Dibutyl phthalate manufactured by Dainippon Ink & Chemicals, Inc.

Policy

 (1) M T L

 Made by Japan Polyurethane Industry Co., Ltd.

 Product name Mi Lionate M T L

 (Carbodimid-type diphenylmethane diisocyanate,

 (NCO content = 28.9%)

 (2) D-1 2 7 Ν

 Takeda Pharmaceutical Co., Ltd., trade name Takenate D-127 Ν (H6XDI-based nucleate, H6XDI trimer,

 (NC 0 content = 13.5%)

 (3) D-1 7 0 Η Ν

 Takeda Pharmaceutical Co., Ltd., trade name Takenate D-170 Η H (HDI-based nurate, NCO content = 22.7%)

 (4) Coronet H X

Product name: Coronate HX, manufactured by Japan Polyurethane Industry Co., Ltd. (HDI series, NC〇 content = 21.1%)

 Pigments

 (1) Talc

 Product name, Talc NKK, manufactured by Fuji Talc Kogyo Co., Ltd.

 Average particle size = 6 ~ 8 〃 m

 (2) Barium sulfate

 Made by Sakai Chemical Industry Co., Ltd., product name

 (3) Titanium white

 Made by Ishihara Sangyo Co., Ltd. Product name Titanium white C R— 9 3

 (4) Polyamide Wax

 Ito Oil Co., Ltd., trade name A S A-T 350 F Examples 7 and 8

 Specimen>

 As shown in Fig. 1, a steel plate with dimensions of 450 x 450 x 20 mm (SS-400) and a steel plate with dimensions of 450 x 100 x 20 mm (SS-4 0) was welded to produce a T-shaped test piece (1) (FIG. 1). FIG. 1 (B) is a perspective view of the test piece (1), and FIG. 1 (A) is a side view thereof. In FIG. 1 (A), the numbers a to g indicate the positions where the paint adheres on the test pieces or the parts of the test pieces.

As shown in Fig. 2, a semi-circular notch k with a radius of 30 mm was formed in a steel plate (SS-400) test piece (450 x 100 mm). The test piece (2) was prepared by welding a steel sheet with a plate and another steel sheet (450 x 450 x 2 O mm) (Fig. 2). FIG. 2 is a perspective view of the test piece (2). In FIG. 2, reference numbers 1 to k indicate the position of the adhesive on the test piece or the site of the test piece (k: notch). .

 'Painting,

Kuchimoto Wagner's spray composition (GM200 EAC) manufactured by Spraytech Co., Ltd. was used, and the coating composition shown in Table 7 was used (Example 7: Composition 1, Example 8: composition 2) a spray灼度5 0 (degrees), the discharge amount 5 7 0 m 1 Bruno min, the applied voltage 8 0 k V, Eyako one WINCH for 'pressure 0. 2 kg /' cm ^2, and the object to be coated Painted at a distance of 30 cm. The coating was performed by spraying in the presence of an alumina vapor catalyst. In this test, the coating was performed at an aminium vapor concentration of 1000 to 2000 ppm.

 The film thickness (micron) of each part of the test piece was measured.

 Tables 8 and 9 show the results.

 Paint each test piece with the gun pointing in the upward (ΐ) direction indicated by the arrow “2” and in the horizontal direction indicated by the arrow “1” as shown in Figure 1 (A), and dried for one day. Thereafter, the thickness of the coating film was measured with an electromagnetic film thickness meter. The measurement points are shown in the figure.

 In the case of “1” where the gun was painted sideways, with the electrostatic coating, a nearly satisfactory film thickness could be secured even in the area e parallel to the flight of the paint spray, which usually has poor paint application efficiency.

In the electrostatic coating of the present invention, in the case of “2” with the gun facing upward, the surface parallel to the flight direction of the paint spray is similar (the paint application efficiency is poor in the conventional ordinary method). Almost satisfactory film thickness was secured in the, b, c, d, and f sections. Similarly, in the method of the present invention (electrostatic coating), the method of flying the paint spray and:, | ' Almost satisfactory film thickness was obtained even with 2) k).

 Example 9, 10

 ,Painting,

Said Wagner. Using a paint techno (GM2000 EAC) manufactured by Spraytech Co., Ltd., and having the composition shown in Table 7 (Example 9: Composition 3, Example 1). 0: Spray composition 4): if] degree 50 (degrees), discharge amount 570 ml Z min, applied voltage 80 kv, air for air conditioning f: 0.2 kg / cm ² , coating It was painted at a distance of 30 cm from the painted material. The coating was performed by spraying in the presence of an alumina vapor catalyst. In this test, the coating was carried out at an amine vapor concentration of 300 to 600 ppm.

 The film thickness (micron) of each part of the test piece was measured.

 Tables 8 and 9 show the results.

 Paint each test piece with the gun pointing in the upward (t) direction indicated by the arrow “2” and in the horizontal (1) direction indicated by the arrow “1” as shown in Fig. 1 (A). After drying on a day, the thickness of the coating film was measured with an electromagnetic film thickness meter. The measurement points are shown in the figure.

 Similarly, in the method of the present invention (electrostatic coating), the notch (k in FIG. 2) parallel to the paint spray flight direction, where the coating efficiency of the paint is inferior with the conventional method, is low. Almost satisfactory film thickness could be secured.

Comparative Example 15

The coating was performed in the same manner as in Example 7 except that the applied voltage for electrostatic coating was not applied. Tables 8 and 9 show the results.

 In this test example, in the case of “1” with the gun mounted sideways, it was difficult to secure the desired film thickness in the “e part” which is a plane parallel to the flight direction of the artificial spray.

 Similarly, in the case of `` 2 '' with the gun painted upward, it is also difficult to secure the crotch at the `` a, b, c, d, f sections '' parallel to the paint spray flight direction. Was.

 Similarly, it was difficult to secure a desired film thickness even in the notch “k” (Fig. 2) parallel to the paint spray flight direction.

Comparative Example 16

 The coating was performed in the same manner as in Example 7 except that the coating was performed under the same conditions as in Example 7, except that the tar epoxy coating was used and the coating was performed under the conditions.

 As the tar epoxy paint, Biscon HB-200 manufactured by China Paint Co., Ltd. was used. The viscosity of the paint was 25 cPs.

<Coating conditions>

Using jet techno (GM200 EAC) manufactured by Nippon Wagner Spray Tech Co., Ltd., spray the tar epoxy paint at a spray angle of 40 (degrees), discharge amount of 1140 m1Z, applied voltage 8 0 kv, Eyako - pneumatic 0. 2 kg Bruno cm ² for Bok and painting at a distance 3 0 cm between the object to be coated. The painting was performed by spraying without using an alumina vapor catalyst.

 The film thickness (micron) of each part of the test piece was measured.

Tables 8 and 9 show the results. In this test example, in the case of “1” where the gun was painted sideways, the desired film thickness was secured in the “e part”, which is parallel to the paint spray flight direction, despite the static painting. Was difficult.

 Similarly, in the case of “2” with the gun painted upward, it is also difficult to secure the film thickness on the “a, b, c, d, and f sections” parallel to the flight direction of the paint spray. Was.

Similarly, it was difficult to secure the desired film thickness even at the “k portion” (FIG. 2) of the cutout surface parallel to the paint spray flight direction.

Table 7 (Recipe table)

PVC: pigment concentration, MIBK: methyl isobutyl ketone Table 8 (Film translation setting example 7 Example 8 Comparative example 1 5 Comparative example 1 6 Composition 1 Electrostatic coating Composition 2 Electrostatic coating composition 1 Jarestal epoxy Shizusagi Curing Κ (20) 2 minutes 10 minutes 3 6 hours 1 7 hours Painting direction * _L | ^M JO 1 port 1 port 0 igt ^

 L '丄 I j 塗 Coating condition Good Good Good Good Good e part dust dust spe part dust dust spray Lay Spray Lay Measurement kneading

a 2 7 2 1 6 8 2 3 4 1 8 7 2 3 2 5 5 1 9 1 4 4 b 2 4 5 1 4 3 2 3 9 1 7 6 2 1 0 7 5 1 1 8 6 2 c 2 3 8 1 8 6 2 5 5 2 2 0 2 5 3 8 4 2 1 6 3 6 d 2 5 4 2 1 8 2 7 6 2 5 4 2 2 7 1 4 6 2 2 3 3 9 e 1 8 6 2 9 5 1 7 6 3 0 5 7 5 2 6 5 6 4 3 4 2 f 2 7 5 2 8 0 2 3 5 2 7 4 2 5 0 5 6 2 4 3 2 4 g 2 6 8 3 5 2 5 1 5 0 2 1 5 5 1 7 0 0 Average film thickness 2 4 8 1 8 9 2 3 8 2 0 9 2 0 9 9 8 1 7 5 7 8

Table 9 (Film thickness measurement results) Example 7 Example 8 Example 9 Example 10 0 Comparative example 15 Comparative example 16 Composition 1 Composition 2 Composition 3 Composition 4 Composition 1 Tar epoxy Electrostatic coating Electrostatic coating Electrostatic Coating Electrostatic coating Wireless coating Electrostatic coating Curing time (20 V) 2 minutes 10 minutes 20 minutes 15 minutes 36 hours 17 hours Painting direction Sideways Sideways Sideways Sideways Sideways Sideways Sideways Sideways Sideways Sideways Coating condition Good Good Good Good e part Dust e part dust Spray Spray 状 Thickness measurement result

 h 2 9 4 2 1 6 2 1 8 2 7 2 2 3 2 2 3 0

•

 1 2 4 8 2 4 3 2 6 5 2 3 3 2 1 0 2 6 8

•

J 2 6 5 2 5 9 2 5 0 2 2 5 2 5 3 2 4 3 k 2 0 3 1 8 6 2 0 3 2 7 8 1 0 4 5 2 Average film thickness 2 5 3 2 2 6 2 3 4 2 5 2 2 0 0 1 9 8

[4] Examples and comparative examples of a method for coating a plastic foam using the coating composition (3) and a plastic foam coated article coated by the method

 The method of measuring the curing time of the materials and the method of testing the appearance and water resistance of the coating film performed in the examples and comparative examples in [4] are as follows.

 (1) Method of measuring paint curing time

 The curing time of the coating was measured according to JIS K540 (6.5 (5) (b) semi-curing and drying).

 (2) Method of measuring paint pot life

 The paints (base agent, curing agent) were mixed and adjusted, and two hours later, the viscosity was measured with a B-type viscometer. If the paint viscosity was 25 poise or less, it was judged that there was no problem in practical use, and it was judged that pot life was secured for 2 hours or more. (3) Appearance of coating film

 In accordance with JISK 540 0 7.1, we observed glares, unevenness, dents, dents, and pits.

 (4) Water resistance test

 According to JISK 540.19.19, the paint film applied to a foamed styrene test piece of size 150 x 70 x 20 mm was dried for 日間 days, immersed in deionized water at 40 ° C for 7 days, Was observed for appearance and adhesion.

 (5) Adhesiveness

According to the JISK 540 8.5.3 x-cut tape method. Raw materials used in Examples and Comparative Examples are as follows. Poly mercapto compound

 (1) P E T P

 Yuri Kagaku Co., Ltd., Penyu Eri Sri Thorte Traquisciopropionate

 S H group equivalent = 1 3 6

 (2) 0 T G

 Octyl thioglycolate, manufactured by Yodo Chemical Co., Ltd.

 S H group equivalent = 2 0 4

Polyol

(1) X U-K 1 3 5

 Takeda X X—K 135, manufactured by Takeda Pharmaceutical Co., Ltd.

 Castor oil polyol, hydroxyl equivalent = 1 98

Polytechnical Society

 (1) MT L

 Made by Japan Polyurethane Industry Co., Ltd.

 Product name Millionate M T L

 Carbodimid-type diphenylene diisocyanate

 NCO content = 28.9%

 (2) D-1 2 1 N

 Takeda Pharmaceutical Co., Ltd., trade name Takenate D-121 NH6XDI Nurate, NCO content = 14.0%

 (3) D-1 2 7 N

Takeda Pharmaceutical Co., Ltd., trade name Takenate D-127 NH 6 XDI-based nurate, H 6 XDI trimer NC 0 content = 1 3.5%

 (4) D-170 H N

 Manufactured by Takeda Pharmaceutical Co., Ltd., Trade name: D-170 HN HDI Nurate, NCO content = 22.7%

 (5) M R-200

 Nippon Polyurethane Industry Co., Ltd.

 Product name Millionet M R— 2 0 0

 Polymeric MDI, NC0 content = 31.1%

 (6) D-120 N

 Made by Takeshi Pharmaceutical Co., Ltd. Product name D-120N NH 6 XDI and TMP, NCO content = 11.0%

(7) D-1 1 0 N

 Taketake Pharmaceutical Co., Ltd., trade name Takenate D—11 Adduct of ONXDI and TMP, NC〇 content = 11.8%

(8) D-140 N

 Takeda Pharmaceutical Co., Ltd., product name Takenet D-140 NIP DAD and TMP N-Cc content = 10.5%

(9) D-2 1 2 L

 Takeda Pharmaceutical Co., Ltd., product name Takenate D—21 L Lactic acid and TMP, NCO content = 7.5%

 (10) Coronate L

 Nippon Polyurethane Industry Co., Ltd. Product name Coronate LTDI and TMP adduct, NC〇 content = 13.2%

(11) Coronate HX Produced by Polyurethane Industry Co., Ltd., Trade name: Coronate HXHDI series, NCO content = 21.1%

(12) DC 2 7 9 7

 Nippon Polyurethane Industry Co., Ltd., trade name DC2797HDI bifunctional nurate, containing NC◦ iS = 22.1% pigments

 (1) Talc

 Product name, Talc NKK, manufactured by Fuji Talc Kogyo Co., Ltd.

 Average particle size = 6 ~ 8 〃 m

 (2) Barium sulfate

 Made by Sakai Chemical Industry Co., Ltd., product name

 (3) Titanium white

 Made by Yu-Kyxide, Inc., product name T R— 9 2

 (4) Polyamide wax

 Made by Ito Oil Co., Ltd., trade name A S A-T 350 F

 (5) Colloidal series force

 Nippon Aerosil Co., Ltd. Product name Aerosil 200 Specific surface area-200 mV g (BET method)

Plastic

 (1) Necilus E P X—L

 I-Shichi, manufactured by I Japan,

Product name Necilus EPX-L Example 1 1 to 1 A The coating composition shown in Table 10 was sprayed onto the surface of the polystyrene foam (150 × 70 × 20) in the presence of an amide vapor catalyst to form a coating film. The amine used was dimethyl ethyl ethanol [first grade reagent, manufactured by Katayama Chemical Industry Co., Ltd.].

 In this test, the coating was carried out at an alumina vapor concentration of 1000 to 2000 ppm. The amine vapor concentration was measured using a Kitagawa-type amine detector manufactured by Komei Rikagaku Kogyo. The coating was performed so that the thickness of the coating film became 200 μm in a bit gauge.

 Then, the coated test piece obtained as described above was allowed to stand at room temperature for 7 days after coating, and the appearance and water resistance test of the coating film were performed.

 The curing time of the paint was measured according to the above method.

 Table 13 shows the results.

Comparative Example 1 7

 A coating composition using an epoxy resin shown in Table 11 was applied to the surface of a polystyrene foam (150 x 70 x 20 mm) by air spray. Coating was carried out so that the thickness of the coating film became 200 m in a pet gauge. Within a few minutes after coating, the foamed styrene was dissolved by the solvent in the paint, and no film could be formed.

Comparative Examples 18 and 1 9

The coating composition shown in Table 12 was applied to the surface of a polystyrene foam (150 x 70 x 20 mm) by air spray. Coating was carried out so that the thickness of the coating film became 200 m in a jet gauge. Within a few minutes after coating, the foamed styrene was dissolved by the solvent in the paint, and a coating could not be formed. Table 10 (Blending Table)

 Ρ V C: pigment concentration

Replacement form (Rule 26) Table 1 1 (Recipe table)

 * 1 Toto Kasei Co., Ltd., trade name Epototo YD-011X-70 * 2 Maruzan Kureie Works, trade name Siri Rikisue M-C0 * 3 Harima Kasei Co., Ltd., trade name Newmide 2013

Replacement form (Rule 26) Table 12 (Recipe table)

 * 1: Pikachu 1007 (Bisfuninol A-type epoxy resin), manufactured by Yuka Shell Epoxy Co., Ltd. Hydroxyl content 0.36 (0 ^ 1 in 100)

* 2: Made by Dainippon Ink and Chemicals, Inc.

 Product name Parnock DE-140- 70

 * 3: Dibutyltin dilaurate, manufactured by Sankyoki Gosei Co., Ltd.

Table 13 (Test results)

Replacement form (Rule 26) Example 16 to 25

 The paint composition shown in Tables 14 and 16 was sprayed onto a polystyrene foam (150 X 70 X 20 mm) in the presence of an amine vapor catalyst to form a coating film. Was formed. The amine used was dimethyl ether ethanol (a first-class reagent from Katayama Chemical Co., Ltd.).

 In this test, the coating was carried out at an alumina vapor concentration of 1000 to 2000 ppm. The amine vapor concentration was measured with a Kitagawa-type amine detector tube manufactured by Kokonori Chemical 1: Industry Co., Ltd. Further, the coating was performed such that the thickness of the break-out was 200 m in a light gauge.

 Next, the coated test piece obtained as described above was allowed to stand at room temperature for 7 days after coating, and the appearance and water resistance test of the coated film were performed.

 In addition, the curing time and the pot life of the paint were measured according to the above method.

The results are shown in Tables 15 and 17.

Table 14 (Recipe table)

PVC: volume Table 15

 Example 16 Lost lake 1 ί lol iffiUU lH Example 19 Example 20 Formulation Hardener D-110N D-140N D-212L Corot L

 ΥΠΤ TUP t f if n

 lrul lMr IDI TMP TDI TMP ク ト τ 夕 'ク ト 塗装 塗装 Painting conditions Amin concentration (ppm) 1000 1000 1000 1000 1000

Coating pressure (kgf / cm ² ) 2 2 2 2 2

«Ί 化 化 問題 （分） 5 5 1 1 5 Potfif Initial 32 4 10 15 3

(Viscosity / poise) After 2 hours 21 13 20 68 2 SI property of plastic foam coated bag

 Good appearance Good Good Good Good

W aqueous good good good good good good

Table 16 (composition table)

PVC: pigment volume

Table 1 Ί

 Example 21 Example 22 Example 23 Example 24 Example 25 Formulation Curing agent D-121N D-127N Π-1710Η piece p Χ1Λ Λ Κ χ)

H6XDI N / A H6XDI N / A Hearing rate D-170HN Coating conditions Min. Concentration (PPD1) 1000 1000 1000 1000 1000 In-situ pressure (kgf / cni ² ) 2 2 2 2 2 Curing time ( Minutes) 20 15 10 5 1 Potfif Initial 3 1 4 14 9

(Viscosity / poise) After 2 hours 4 3 13 71 103 5J property of plastic foam coated product

 Good appearance Good Good Good Good Good

W aqueous good good good good good good

荬 Example 2 6, 2 7

 A polystyrene foam (150.times.70.times.20 mm) was sprayed with a coating composition as indicated by ^ 18 in the presence of an alumina vapor catalyst to form a coat. The amine used was dimethyl ethyl ethanol [first grade reagent, manufactured by Katayama Chemical Industry Co., Ltd.].

 In this test, coating was performed at an amine vapor concentration of 300 to 600 ppm. The amine vapor concentration was measured using a Kitagawa A-amine detector tube manufactured by Komei Rika Kogyo Co., Ltd. In addition, the painting was performed so that the thickness of the crotch was 200 mm in a foot gauge.

 Next, the coated test piece obtained as described above was allowed to stand at room temperature for 7 days after coating, and the appearance and water resistance test of the coating film were performed.

 In addition, the curing time and pot life of the paint were measured according to the methods described above.

The results are shown in Table 19.

Table 18 (Recipe table)

PVC: pigment volume ffiH

Table 1 9 Example 26

Combination

 Polyol

 Curing agent D-170H coating ^:

Amin [ppm] 5000 5000 Paint pressure [kgf / cm ² ] 4 4 Curing time [min] 10 5 Physical properties of plastic foam coating

 Thigh appearance Good Good Water resistance Good Good

Claims

Claims. A coating composition comprising a polymer compound (A) and a carbodiimide-type polyisocyanate (B). 2. The coating composition according to claim 1, wherein the polymercapto compound (A) is a lower fatty acid ester of an aliphatic polyol. 3. The coating composition according to claim 2, wherein the polymer cap compound (A) is a mercaptoacetate ester of Pencil Ethrystritol. The above-mentioned calposimid type polyisocyanate (B) force, calposimid type diphenylmethane diisocyanate, carposimid type tolylene diisocyanate, carposimid type dimethyl biphenyle range isocyanate, or calposimid. 2. The coating composition according to claim 1, wherein the coating composition is a mid-type hexamethylene diisocyanate. 2. The method according to claim 1, wherein a polyol (C) is contained in addition to the polymercapto compound (A) and the carposimid type polyisocyanate (B). Paint composition. -Polymeric carboxylic acid esters of aliphatic polyhydric alcohols (D), and triad or higher polyhydric alcohols (i) and bis (isosocyanate methyl) cyclohexane (ii) adducts (ii) E 1) and bis (isosinate methyl) cyclohexane, an isocyanurate structure having a ring represented by the following formula [I] \ ZN NC I] = CC = 0N (nurate A coating composition characterized by comprising at least one kind of polyisocyanate compound (E) selected from the group consisting of (structure) (E 2). 7. The coating composition according to claim 6, wherein the polymer carboxylic acid ester (D) is a mercapto lower fatty acid ester of an aliphatic polyol. The above polymercaptocarboxylate (D) power, ', mercaptopropionate or mercaptoacetate of pentaerythritol, or mercaptopropionate or mercaptoacetate of trimethylolpropane 8. The coating composition according to claim 7, which is an ester. A coating method characterized by curing the following coating composition (1) or (2) on a substrate in the presence of a vapor-form amine catalyst to form a uniform coating film; 1) a coating composition comprising a polymercapto compound (A) and a carbodiimide-type polyisocyanate (B); a coating composition (2) a polymercapto carboxylic acid ester of an aliphatic polyhydric alcohol (D), an adduct (El) of a trihydric or higher aliphatic polyhydric alcohol (i) with bis (i-N-socyanatomethyl) cyclohexane (ii), and bis (isosinetomethyl) ) At least one member selected from the group consisting of an isocyanurate structure (nurate structure) (E 2) having a ring represented by the following formula [I] [I] consisting of cyclohexane: Species of Polysocyanate Compound (E) That the coating composition. 0. The ninth aspect of the present invention, wherein the coating composition is sprayed onto the substrate with a spray gun, and at the same time, an amine catalyst is sprayed onto the substrate with another spray gun to form a uniform cured coating film. Coating method described in section.

 10. The coating method according to claim 9 or 10, wherein the coating composition (1) or (2) is electrostatically coated in the presence of a vapor-state amine catalyst. .

2. The coating method according to claim 11, wherein the viscosity of the coating compositions (1) and (2) is not more than 500 cPs. 3. The coating according to any one of claims 1 to 9, wherein the polymer compound (A) is a lower fatty acid ester of an aliphatic polyol. Method.

4. The coating method according to claim 13, wherein the polymercapto compound (A) is a mercaptoacetate ester of Pencil erythritol.

5. The above-mentioned carbodiimide-type polyisocyanate (B) force carbodiimide-type diphenylmethane diisocyanate, carbodiimide-type tri-diethylene silicate, carbodiimide-type dimethyl biphenyl nitrate silicate, or carbodiimide The coating method according to any one of claims 9 to 14, wherein the coating method is a mold hexamethylene diisocyanate.

6. The coating composition (1) contains a polyol (C) in addition to the polymercap compound (A) and the carbodiimide-type polyisocyanate (B). Claims 9 to characterized by the following The coating method according to any one of Items 15 to 15.

 7. The coating method according to any one of claims 9 to 12, wherein the polymercaptocarboxylic acid ester (D) is a mercapto lower fatty acid ester of an aliphatic polyol. . 8. Polyol (F 1) and z or polymercap compound (F 2) in the presence of vapor amine catalyst and polyisocyanate

(G) An electrostatic coating method for a heavy-duty anticorrosion coating composition, characterized by electrostatically applying the coating composition (3).

 9. The electrostatic coating method according to claim 18, wherein the viscosity of the coating composition (3) is 500 cPs or less.

 0. Polyol (F1) vigorously, ethylene glycol, propylene glycol, 1,6-hexanediol, glycerol, trimethylolpropane, pen-erythritol, polyester polyol or polyester polyol The electrostatic coating method according to claim 18 or 19, wherein the electrostatic coating method is an acrylic polyol.

 1. The above polymercapto compound (F 2), pentamer erythritol and mercaptoacetic acid or mercaptopropionic acid, or trimethylolproha. 20. An ester having from 2 to 4 mercapto groups, which is composed of a compound and mercaptoacetic acid or mercaptopropionic acid, according to any one of claims 18 to 20, Electrostatic coating method.

2. The above polyisocyanate (G) calposimid type diphenyl methane succinate, carposimid type tolylene diisocitane, and karposimid type dimethyl biphenylene diisocyanate The electrostatic coating method according to any one of claims 18 to 21, characterized in that the electrostatic coating method is a net or carbodimid hexamethylene diisocyanate.

3. A coating film is formed by curing the following coating composition (1), (2) or (3) on a plastic foam in the presence of a vapor-phase amine catalyst. Painting method;

 Coating composition (1): Polymercapto compound (A)

 A coating composition comprising a carbodimid-type polysocyanate (B),

 Coating composition (2): Polymercapto carboxylic acid ester of aliphatic polyhydric alcohol (D),

 Adducts (E 1) of tri- or higher aliphatic polyhydric alcohols (i) with bis (iso- cyanomethyl) cyclohexane (ii), and bis (iso-cyanate-methyl) cyclohexane The following formula [I] consisting of

 o = c c = o

H And at least one polyisocyanate compound (E) selected from the group consisting of isocyanurate peach structures (nurate structures) ('E 2) having a ring represented by

 A coating composition comprising

 Coating composition (3): Polyol (F1) and / or polymercapto compound (F2),

 Polysociate (G) and

 A coating composition comprising:

 4. The coating method according to any one of [ffl] to [23], wherein the polymercap compound (A) is a lower fatty acid ester of an aliphatic polyol.

 5. The coating method according to claim 24, wherein said polymercapto compound (A) is a mercaptoacetate of Penno Erythritol.

 6. The carbodiimide-type polyisocyanate (B) is a carbodiimid-type diphenylmethane succinate, a carbodiimide-type toluenediisocyanate, a carbodiimide-type dimethylbiphenyl nitrendiisocitane, or a carbodiimide. The coating method according to any one of claims 23 to 25, wherein the coating method is a mold hexamethylene range succinate.

7. The coating composition (1) contains a polyol (C) in addition to the polymercapto compound (A) and the carpoimide-type polyisocyanate (B). Claim 23 to claim 26. The coating method according to any one of items 26 to 26.

 8. The coating method according to claim 23, wherein said polymer carboxylic acid ester (D) is a mercapto lower fatty acid ester of an aliphatic polyol.

9. Polyol (F 1) force, ethylene glycol, propylene glycol, 1,6-hexanediol, glycerol, trimethylone-l-prono, ⁰ , pentaerythritol, 24. The coating method according to claim 23, wherein the coating method is a polyester polyol or an acrylic polyol.

0. The polymercap compound (F 2) pentaerythritol and mercaptoacetic acid or mercaptopropionic acid, or trimethylolproha. 24. The coating method according to claim 23, wherein the ester is an ester having 2 to 4 mercapto groups, comprising an ester and mercaptoacetic acid or mercaptopropionic acid.

 1. The above polyisocyanate (G) force, force, divinylmethandiate, carbodiimid, tolylenediamine, carbodiimide, dimethylbiphenylene dithiocyanate or carbodimine 24. The coating method according to claim 23, wherein the coating method is a hexamethylene diisocyanate. 2. The coating method according to claim 23, wherein the coating composition (3) is used.

3. A heavy-duty anticorrosive paint characterized in that a coating film is formed on a ship, an underwater / above-water structure by the electrostatic coating method according to any one of claims 18 to 22. Painted.

4. The method for coating a plastic foam according to any one of claims 23 to 31 is characterized in that a crotch is formed on the plastic foam. Plastic foam coated products.

5. The plastic foam-coated product according to claim 34, wherein the coating composition (3) is used.