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WO1998005722A1 - Composition de revetement, procede de revetement a l'aide de cette composition et article enduit d'apres ce procede - Google Patents

Composition de revetement, procede de revetement a l'aide de cette composition et article enduit d'apres ce procede Download PDF

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Publication number
WO1998005722A1
WO1998005722A1 PCT/JP1997/002668 JP9702668W WO9805722A1 WO 1998005722 A1 WO1998005722 A1 WO 1998005722A1 JP 9702668 W JP9702668 W JP 9702668W WO 9805722 A1 WO9805722 A1 WO 9805722A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
coating composition
coating method
type
compound
Prior art date
Application number
PCT/JP1997/002668
Other languages
English (en)
Japanese (ja)
Inventor
Hironori Tamura
Yukio Kosono
Eiichi Yoshikawa
Shigeharu Fukuzawa
Kenji Shibutani
Toshihiro Masaki
Masayasu Watanabe
Original Assignee
Chugoku Marine Paints, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP8203924A external-priority patent/JPH1046105A/ja
Priority claimed from JP8203925A external-priority patent/JPH1043681A/ja
Priority claimed from JP8212867A external-priority patent/JPH1052668A/ja
Priority claimed from JP8212866A external-priority patent/JPH1053744A/ja
Priority claimed from JP25712696A external-priority patent/JPH10151413A/ja
Priority claimed from JP25712596A external-priority patent/JPH10151411A/ja
Application filed by Chugoku Marine Paints, Ltd. filed Critical Chugoku Marine Paints, Ltd.
Priority to AU37075/97A priority Critical patent/AU3707597A/en
Publication of WO1998005722A1 publication Critical patent/WO1998005722A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • Japanese Patent Application Laid-Open No. 3-163718 discloses a coating film curing method (coating 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • the paint viscosity inevitably increases, usually to a viscosity of more than 250 cps.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • the coating of plastic foams 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.”
  • 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.
  • RIM urethane rim
  • 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.
  • 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.
  • 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
  • a polymer capping compound (A) A polymer capping compound (A),
  • 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.
  • polyisocyanate (B) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenyl methane diisocyanate, etc. can be used in combination.
  • 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.
  • the second coating composition according to the present invention comprises: a polymercaptocarboxylic acid ester of an aliphatic polyhydric alcohol (D);
  • 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.
  • 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),
  • Coating composition (2) Polymercaptocarboxylate (D) of aliphatic polyhydric alcohol,
  • the coating composition (1) or (2) can be subjected to electrostatic coating in the presence of a vapor-phase amine catalyst.
  • the coating compositions (1) and (2) The degree is preferably less than 500 cPs.
  • 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.
  • the viscosity of the coating composition (3) is preferably 500 cPs or less.
  • 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.
  • the coating composition (3) 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.
  • carbodiimide-type polyisocyanate examples include carbodiimide-type difuninylmethanedithiocyanate, carbodiimid-type tolylenediisocitrate, carbodiimide-type dimethylbiphenyle-diisocyanate, A carposimid hexylene diisocyanate is preferred.
  • 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).
  • 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.
  • 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.
  • plastic foam coated product according to the present invention
  • a coating film comprising the coating composition (1), (2) or (3) is formed on the plastic foam.
  • plastic foam coated articles using the coating composition (3) are preferred.
  • 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)
  • 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
  • the coating composition according to the present invention, its coating method, and the coated product coated by the method will be specifically described.
  • 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).
  • the poly mercapto compound (A) is a compound having two or more mercapto groups (one SH group).
  • 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.
  • aliphatic polyol (a) examples 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.
  • 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.
  • 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.
  • 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, ⁇ '-dimethylcapto- ⁇ -xylol.
  • C ⁇ — groups.
  • Diphenyl methane diisocyanate, carbodiimide-type toluene diisocyanate, carbodiimide-type dimethylbiphenylene diisocyanate, carbodiimide-type hexamethylene diisocyanate is preferably used.
  • Societelets are preferably used.
  • diphenyl methane diisocyanate 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.
  • a polyol (C) may be blended into the coating composition.
  • 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
  • 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.
  • 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)
  • the components of the polymercapto compound (A), the carpoimide-type polyisocyanate (B), the poly (C) and the polyisocyanate (B-1) are ,
  • 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 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.
  • calposimid type polyisocyanate (B) 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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 such as sonorebit, mannite, galactitol, and arozurcit are included. Of these, greaserol, trimethylolpropane, and pentaerythritol are particularly preferred.
  • mercapto lower fatty acid (ii) examples 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.
  • a mercaptocarboxylic acid ester with an aliphatic monohydric alcohol can be used as a diluent or a plasticizer.
  • 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.
  • 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.
  • the polyisocyanate compound (E) used in the present invention is N-(2-isocyanate compound (E)-N-(2-isocyanate compound (E) used in the present invention.
  • 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 such as sorbit, mannitol, galactitol, and aroznolesit. Above all, Tri-Mouth Pro-Ha. And Penyu Elithreur are particularly preferred.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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) 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) 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) 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) is a substantially solvent-free or solvent-free coating composition, and is composed of
  • 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. ⁇ ⁇ ⁇ ;
  • 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 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;
  • 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.
  • ethylene glycol propylene glycol, 1,6-hexanediol, glycerol, and trimethylolproha.
  • Pentaerythritol, polyester polyols, and acrylonitrile polyols are preferred.
  • the polymercapto compound (polythiol) (F2) used in the present invention is a compound having two or more mercapto groups (one SH group).
  • 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.
  • aliphatic polyol examples 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 such as sonorebit, mannite, galactitol, and aroznorecit. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferred.
  • glycidyl ethers such as bisphenol A glycidyl ether, hydrogenated bisphenol A glycidyl ether, bisphenol F glycidyl ether, and novolak epoxy can be used.
  • 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.
  • acetic acid mercaptopropionic acid
  • mercaptosalicylic acid menolecaptoglycolic acid
  • N- (2-hydroxyxethyl) thioglycolic acid mercaptoconoic acid
  • citric acid and mercaptolingoic acid mercaptolingoic acid.
  • mercaptoacetic acid HSCH 2 COOH
  • 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.
  • a thiol compound having one mercapto group can be used as a diluent or a plasticizer.
  • a polymercap compound (F 2) which does not require a solvent and has no or little odor.
  • polyisocyanate (G) used in the present invention specifically,
  • a null form or an adduct form derived from the above-described isocyanate can also be used.
  • polyisocyanate (G) other than the above include the following carposimid type polyisocyanate.
  • 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.
  • 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
  • Bis Isoocyanate Methyl
  • 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.
  • 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 such as sorbitol, mannite, galactitol, and arozurcit are mentioned. Among them, trimethyl alcohol and pentaerythritol are particularly preferred.
  • TDI tolylenedioxide
  • XDI xylylenedisulfide
  • MXDI mexylenedilysocyanate
  • HDI or HMDI hexamethylenedilysocyanate
  • IPDI isophorone diisocene
  • IPDI bis (isocene monomethyl) cyclohexane
  • hydroogenated XDI, H6XDI) ii
  • T DI tolylene glycol
  • XDI Xylylene Range Isolate
  • 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.
  • 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.
  • 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.
  • the above-mentioned carbodiimide-type polyisocyanate is used in combination with a polysociate other than the calposimid type as the polyisocyanate (G).
  • 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.
  • the above-mentioned coating composition (3) can form a clear coating film as a clear coating composition.
  • 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.
  • 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 M ⁇ .
  • the coating composition having such an electric resistance value is finely atomized by spraying.
  • 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.
  • the coating composition (3) 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.
  • the electrostatic coating method (c) is particularly preferable.
  • any of a fixed (automatic) coating device and a portable (handheld) coating device can be used.
  • a fixed coating device for example, a grid type coating device is used. , Rotating cup electrode type, and rotating disk type.
  • 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.
  • the cathode In a portable (hand-held) coating device, the cathode is set at the tip of the spray gun.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • various molded objects such as ships and fishing vessels (eg: ropes, fishing nets).
  • 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
  • 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.
  • 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.
  • plastic foam examples 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.
  • 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.
  • 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 ⁇ .
  • the second coating composition (coating composition (2)) 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.
  • 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.
  • 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.
  • 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.
  • the coating composition (1) 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the coating composition (3) is preferred.
  • 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.
  • 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.
  • the curing time of the paint is JISK540 (6.5 (5) (C) curing and drying) The measurement was performed according to the following.
  • 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.
  • 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.
  • 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.
  • Shotblasted mild steel 150 x 70 x 3.2
  • 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.
  • 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.
  • 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.
  • PVC Pigment volume offer Table 2 (3 ⁇ 4 « ⁇ fruits)
  • 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.
  • 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. .
  • 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.
  • the curing time of the paint was measured according to JIS K 5400 (6.5 (5) (b) semi-cured drying).
  • the hardness of the coating film is evaluated according to ISO 1522-1973 3.1. KKoenig penduium) did.
  • the adhesion of the coating film was measured and evaluated according to JIS K 5400 1.1.1.
  • the impedance of the coating film was measured according to JIS K 5400 8.15 (4.3), and evaluated by ta ⁇ a.
  • PETP manufactured by Yodo Chemical Co., Ltd.
  • Coronate HX manufactured by Japan Polyurethane Industry Co., Ltd.
  • D-190N manufactured by Takeda Pharmaceutical Co., Ltd.
  • Coronet L manufactured by Japan Polyurethane Industry Co., Ltd. Product name Coronate L
  • Barium sulfate manufactured by Sakai Chemical Industry Co., Ltd., trade name: Barium sulfate B A
  • Titanium white manufactured by SCM Chemical Co., Ltd.
  • Blistered mild steel plate 150 x 70 x 3.2 mm
  • 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.
  • 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.
  • the coating films were formed in a short curing time in each of the examples and the comparative examples.
  • 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.
  • 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.
  • the coating performance of the H6XDI TMP adduct-type isocyanate is excellent.
  • 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)
  • the coating films were formed in a short curing time in each of the examples and the comparative examples.
  • the H6XDI TMP adduct-type isocyanate has excellent coating performance among general nutrates.
  • 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 curing time of the paint was measured according to JIS K 5400 (6.5 (5) (b) semi-cured drying).
  • the film thickness of the coating film was measured with an electromagnetic film thickness meter (trade name: LE-210) manufactured by Kett Science Laboratory.
  • LE-210 electromagnetic film thickness meter manufactured by Kett Science Laboratory.
  • Raw materials used in Examples and Comparative Examples are as follows. Poly mercaptoethanol
  • Average particle size 6 ⁇ 8 ⁇ m
  • FIG. 1 (B) is a perspective view of the test piece (1)
  • FIG. 1 (A) is a side view thereof.
  • the numbers a to g indicate the positions where the paint adheres on the test pieces or the parts of the test pieces.
  • FIG. 2 is a perspective view of the test piece (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). .
  • the film thickness (micron) of each part of the test piece was measured.
  • the film thickness (micron) of each part of the test piece was measured.
  • 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.
  • Example 7 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.
  • tar epoxy paint Biscon HB-200 manufactured by China Paint Co., Ltd. was used.
  • the viscosity of the paint was 25 cPs.
  • the film thickness (micron) of each part of the test piece was measured.
  • Tables 8 and 9 show the results.
  • 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.
  • Example 9 Comparative example 15 Comparative example 16 Composition 1 Composition 2 Composition 3 Composition 4 Composition 1 Tar epoxy 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 Coating condition Good Good Good Good Good e part Dust e part dust Spray Spray ⁇ Thickness measurement result
  • 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.
  • the curing time of the coating was measured according to JIS K540 (6.5 (5) (b) semi-curing and drying).
  • 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.
  • the paint film applied to a foamed styrene test piece of size 150 x 70 x 20 mm was dried for ⁇ days, immersed in deionized water at 40 ° C for 7 days, Was observed for appearance and adhesion.
  • Coronate HX Produced by Polyurethane Industry Co., Ltd., Trade name: Coronate HXHDI series, NCO content 21.1%
  • Average particle size 6 ⁇ 8 ⁇ m
  • Aerosil 200 Specific surface area-200 mV g (BET method)
  • 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.].
  • 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 ⁇ m in a bit gauge.
  • 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.
  • 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.
  • 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)
  • Pikachu 1007 (Bisfuninol A-type epoxy resin), manufactured by Yuka Shell Epoxy Co., Ltd. Hydroxyl content 0.36 (0 ⁇ 1 in 100)
  • 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.
  • the amine used was dimethyl ether ethanol (a first-class reagent from Katayama Chemical Co., Ltd.).
  • 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.
  • 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.
  • Example 16 Lost lake 1 ⁇ lol iffiUU lH
  • Example 19 Formulation Hardener D-110N D-140N D-212L Corot L
  • Example 21 Example 22
  • Example 23 Example 24
  • 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.].
  • amine vapor concentration 300 to 600 ppm.
  • the amine vapor concentration was measured using a Kitagawa A-amine detector tube manufactured by Komei Rika Kogyo Co., Ltd.
  • the painting was performed so that the thickness of the crotch was 200 mm in a foot gauge.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne une composition de revêtement qui comprend les éléments suivants: un composé polymercapto tel qu'un ester polymercaptocarboxylique d'un alcool polyhydrique aliphatique, un composé polyisocyanate particulier d'un carbodiimide, un produit d'addition à base d'alcool polyhydrique aliphatique, un isocyanurate ou autre et, enfin, un éventuel polyol. Cette invention concerne également un procédé de revêtement faisant appel à cette composition, laquelle est capable de se solidifier rapidement, même à température ambiante, en présence d'un catalyseur amine gazeux. Cette composition permet d'obtenir un enduit régulier par revêtement isostatique ou analogue. L'enduit ainsi obtenu possède d'excellentes propriétés anticorrosion, est peu sujet au décollement à des températures très élevées ou très basses, et peut être utilisé pour des protections d'une grande résistance ainsi que dans d'autres applications. Cette invention concerne enfin un procédé de revêtement qui utilise du plastique en qualité de substrat, et qui permet d'obtenir des mousses enduites possédant une excellente résistance à l'eau ainsi que d'autres propriétés.
PCT/JP1997/002668 1996-08-01 1997-07-31 Composition de revetement, procede de revetement a l'aide de cette composition et article enduit d'apres ce procede WO1998005722A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37075/97A AU3707597A (en) 1996-08-01 1997-07-31 Coating composition, method for coating with the same, and article coated by said method

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP8203924A JPH1046105A (ja) 1996-08-01 1996-08-01 塗料組成物
JP8203925A JPH1043681A (ja) 1996-08-01 1996-08-01 塗装方法
JP8/203925 1996-08-01
JP8/203924 1996-08-01
JP8212867A JPH1052668A (ja) 1996-08-12 1996-08-12 塗装方法
JP8/212866 1996-08-12
JP8212866A JPH1053744A (ja) 1996-08-12 1996-08-12 塗料組成物
JP8/212867 1996-08-12
JP8/257126 1996-09-27
JP8/257125 1996-09-27
JP25712696A JPH10151413A (ja) 1996-09-25 1996-09-27 重防食用塗料組成物の塗装方法およびこの方法により塗装された塗装品
JP25712596A JPH10151411A (ja) 1996-09-25 1996-09-27 プラスチック発泡体の塗装方法およびその方法により塗装されたプラスチック発泡体塗装品

Publications (1)

Publication Number Publication Date
WO1998005722A1 true WO1998005722A1 (fr) 1998-02-12

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AU (1) AU3707597A (fr)
WO (1) WO1998005722A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51101918A (fr) * 1975-02-01 1976-09-08 Bayer Ag
JPS5227703A (en) * 1975-08-23 1977-03-02 Bayer Ag Method of partial dicarbodiimidation of isocyanate group of organic isocyanate
JPS5265221A (en) * 1975-11-21 1977-05-30 Bayer Ag Polyisocyanate containing carbodiimide group stable when preserved
JPS61283669A (ja) * 1985-05-31 1986-12-13 アシユランド・オイル・インコ−ポレ−テツド 塗料
JPS63317560A (ja) * 1987-06-19 1988-12-26 Mitsui Toatsu Chem Inc 含硫ウレタン塗料
JPH0393873A (ja) * 1989-09-06 1991-04-18 Mitsui Toatsu Chem Inc 塗料用樹脂組成物及び塗装方法
JPH03100083A (ja) * 1989-09-13 1991-04-25 Mitsui Toatsu Chem Inc 塗料用樹脂組成物及び塗装方法
JPH03100084A (ja) * 1989-09-13 1991-04-25 Mitsui Toatsu Chem Inc 塗料用樹脂組成物及び塗装方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51101918A (fr) * 1975-02-01 1976-09-08 Bayer Ag
JPS5227703A (en) * 1975-08-23 1977-03-02 Bayer Ag Method of partial dicarbodiimidation of isocyanate group of organic isocyanate
JPS5265221A (en) * 1975-11-21 1977-05-30 Bayer Ag Polyisocyanate containing carbodiimide group stable when preserved
JPS61283669A (ja) * 1985-05-31 1986-12-13 アシユランド・オイル・インコ−ポレ−テツド 塗料
JPS63317560A (ja) * 1987-06-19 1988-12-26 Mitsui Toatsu Chem Inc 含硫ウレタン塗料
JPH0393873A (ja) * 1989-09-06 1991-04-18 Mitsui Toatsu Chem Inc 塗料用樹脂組成物及び塗装方法
JPH03100083A (ja) * 1989-09-13 1991-04-25 Mitsui Toatsu Chem Inc 塗料用樹脂組成物及び塗装方法
JPH03100084A (ja) * 1989-09-13 1991-04-25 Mitsui Toatsu Chem Inc 塗料用樹脂組成物及び塗装方法

Also Published As

Publication number Publication date
AU3707597A (en) 1998-02-25

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