WO1997022646A1 - Compositions durcies ultra-durables de polyisocyanate pour revetements brillants - Google Patents

Compositions durcies ultra-durables de polyisocyanate pour revetements brillants Download PDF

Info

Publication number
WO1997022646A1
WO1997022646A1 PCT/US1996/017724 US9617724W WO9722646A1 WO 1997022646 A1 WO1997022646 A1 WO 1997022646A1 US 9617724 W US9617724 W US 9617724W WO 9722646 A1 WO9722646 A1 WO 9722646A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
solution polymer
hydroxy
hydroxyl
acrylic
Prior art date
Application number
PCT/US1996/017724
Other languages
English (en)
Inventor
Suryya K. Das
Soner Kilic
Andrew J. Lauer
Original Assignee
Ppg Industries, Inc.
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
Application filed by Ppg Industries, Inc. filed Critical Ppg Industries, Inc.
Publication of WO1997022646A1 publication Critical patent/WO1997022646A1/fr

Links

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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols

Definitions

  • the present invention relates to polyisocyanate-curable, film-forming compositions, and processes for preparing multi-layered coated articles comprising a pigmented or colored base coat and a clear topcoat.
  • Color-plus-clear coating systems have become conventional as original finishes for automobiles. These systems typically involve the application of a pigmented base coat to a substrate. This is followed by the application of a clear topcoat over the base coat. These color-plus-clear systems have outstanding gloss and distinctness of image, most of which is provided by the clear topcoat.
  • the clear topcoat in this color-plus-clear system In addition to having a high gloss, it is often desirable for the clear topcoat in this color-plus-clear system to be ultradurable and acid etch resistant.
  • ultradurable refers to the ability of the topcoat to retain a large percentage of its original gloss when exposed to environmental conditions such as rain, sun, heat, freezing temperatures, and the like.
  • Coating systems which are known to be durable are described in U.S. Patent 4,565,730. That Patent describes coating compositions which contain as binders a combination of two specific hydroxyl-containing acrylate resins and an aliphatic and/or cycloaliphatic polyisocyanate or a mixture of such polyisocyanates.
  • the hydroxyl number of the first ofthe two specific acrylic polymers ranges from between 80 to 180 and is present in an amount ranging from between 50 to 90 % by weight, based on total acrylic polymers.
  • the hydroxyl number of the second of the two specific acrylic polymers ranges from between 40 to 120 and is present in an amount ranging from between 10 to 50 % by weight, based on total acrylic polymers.
  • This PCT Application discloses processes which use a transparent covering lacquer containing a hydroxyl group-containing polyacrylate resin produced by polymerizing: (a) 10 to 51% by weight, preferably 25 to 41% by weight, of 4-hydroxy-n- butylacrylate or 4-hydroxy-n-butylmethacrylate, or a mixture thereof, and (b) 28 to 85 % by weight, preferably 40 to 70% by weight, of an aliphatic or cycloaliphatic ester of methacrylic acid with at least 4 carbon atoms in the alcohol radical which is different from (a), above.
  • the resulting polyacrylate resin has a hydroxyl number ranging fiom between 60 to 200, preferably, from between 100 to 160.
  • Commonly-owned U.S. Patent 5,445,850 is entitled "Aminoplast
  • That Patent discloses coating compositions and their use in color-plus-clear coating systems. These coating compositions include acrylic polymers prepared with high levels of cycloaliphatic or aromatic ester of acrylic and methacrylic acid and hydroxypropyl- or hydroxybutyl acrylates and methacrylates and aminoplast crosslinking agents.
  • Another object of this invention is to provide a color-plus-clear coating system which includes a novel clear, high gloss topcoat which is ultradurable and resists acid etching.
  • a curable film-forming composition which includes: (a) a hydroxyl-containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent.
  • the hydroxyl-containing acrylic solution polymer is present in an amount ranging from between about 60 to about 90 weight percent; and, the polyisocyanate crosslinking agent is present in an amount ranging from between about 10 to about 40 weight percent.
  • the acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of acrylic acid or methacrylic acid (hereinafter referred to as "(meth)acrylic acid") having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component.
  • the cycloaliphatic and/or aromatic ester component is typically employed in an amount ranging from between about 45 to about 95 weight percent.
  • the hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number ofthe resulting acrylic solution polymer is less than about 200.
  • the hydroxy functional acrylic monomer component ofthe present invention does not contain a significant amount 4-hydroxy-n-butylacrylate or 4- hydroxy-n-butylmethacrylate or a mixture thereof. It has been discovered that the coating compositions made in accordance with the present invention are not only ultradurable, but also acid etch resistant.
  • This invention also provides a process for applying a composite coating onto a substrate. This process includes: (a) applying a film-forming base coat onto a substrate, (b) at least partially curing the base coat, and (c) applying a clear, film-forming top coat over the at least partially cured base coat.
  • the clear top coat being applied over the base coat includes the curable, film-forming composition described above.
  • the present invention pertains to the development of a novel, crosslinkable film-forming composition which has a high gloss, is ultradurable and resists acid etching.
  • This film-forming composition includes: (a) a hydroxyl- containing acrylic solution polymer, and (b) a polyisocyanate crosslinking agent.
  • a hydroxyl- containing acrylic solution polymer and (b) a polyisocyanate crosslinking agent.
  • acrylic solution polymer means that the acrylic polymer is prepared by solution polymerization techniques while in the presence of suitable initiators such as organic peroxides or azo compounds (e.g., benzoyl peroxide or 2,2'-azobis(2-methylbutanenitrile)). This polymerization can be carried out in an organic solvent in a conventional manner in which the monomers and polymers produced are soluble.
  • the acrylic solution polymer is typically present in the film-forming composition in an amount ranging from between about 60 to about 90 weight percent, and preferably, from between about 70 to about 85 weight percent. These weight percentages are based upon the total resin solids weight of a hydroxyl-containing acrylic solution polymer in the film-forming composition.
  • the polyisocyanate crosslinking agent is typically present in the film-forming composition in an amount ranging from between about. 10 to about 40 weight percent, and preferably, from between about 15 to about 30 weight percent. These weight percentages are based upon the total resin solids weight of an polyisocyanate crosslinking agent in the film-forming composition.
  • the acrylic solution polymer is the reaction product of: (a) a cycloaliphatic and/or aromatic ester of (meth)acrylic acid having at least 6 carbon atoms in the cycloaliphatic and/or aromatic group, and (b) a hydroxyl functional acrylic monomer component.
  • the hydroxyl functional acrylic monomer component is present in an amount such that the hydroxyl number ofthe resulting acrylic solution polymer is less than about 200.
  • the hydroxy functional acrylic monomer component ofthe present invention does not contain a significant concentration of 4-hydroxy-n-butylacrylate or 4-hydroxy-n-butylmethacrylate or a mixture thereof.
  • concentration of 4- hydroxy-n-butylacrylate or 4-hydroxy-n-butylmethacrylate or a mixture thereof in the hydroxy functional acrylic monomer component of the present invention is less than 10 weight percent.
  • concentration of 4-hydroxy-n-butylacrylate or 4- hydroxy-n-butylmethacrylate or a mixture thereof in the hydroxy functional acrylic monomer component is less than about 7 weight percent, preferably, less than about 5 weight percent, more preferably, less than about 3 weight percent, and even more preferably, less than about 1 weight percent.
  • hydroxy functional acrylic monomer component of the present invention contains substantially no 4-hydroxy-n-butylacrylate or 4- hydroxy-n-butylmethacrylate.
  • the cycloaliphatic or aromatic ester component is typically employed in an amount ranging from between about 45 to about 95 weight percent, and preferably, from between about 60 to about 90 weight percent. These weight percentages are based upon total weight of monomers used in preparing the acrylic solution polymer. Moreover, although the cycloaliphatic or aromatic ester component has at least 6 carbon atoms in the cycloaliphatic or aromatic group, typically, it has from between 6 to 12 carbon atoms. Examples of such compounds which can be used when practicing this invention include: benzyl methacrylate, phenyl methacrylate, t- butyl-cyclohexyl methacrylate and cyclohexyl methacrylate or mixtures thereof.
  • the hydroxyl functional acrylic monomer component is typically employed in an amount such that the hydroxyl number of the resulting acrylic solution polymer is less than about 200.
  • the amount of the hydroxyl functional acrylic monomer component employed is such that the acrylic solution polymer's hydroxyl number is in the range from between about 25 to about 150, and more preferably, from between about 30 to about 125.
  • Any suitable hydroxyl functional monomer, or combination thereof, can be used when practicing this invention.
  • suitable monomers include: hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate or mixtures thereof.
  • the hydroxyl functional monomers most preferred for providing acid etch resistance are 2-hydroxybutyl acrylate and 2-hydroxypropyl acrylate.
  • the acrylic solution polymer may further include up to 45 weight percent of a monomer(s) such as vinyl aromatic compounds and alkyl acrylates and methacrylates which contain from 1 to 8 carbon atoms in the alkyl group. This weight percent is based upon total weight of monomers used in preparing the acrylic solution polymer.
  • Suitable vinyl aromatic compounds which can be used include: styrene and vinyl toluene. Styrene is preferred.
  • Suitable alkyl acrylates and methacrylates which can be used include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. A mixture of n-butyl acrylate and methyl methacrylate is preferred.
  • the acrylic solution polymer typically has a number average molecular weight ranging from between about 1 ,000 to about 30,000, and preferably, from between about 1,500 to 20,000. These molecular weights are determined by gel permeation chromatography using polystyrene as standard.
  • the crosslinking agent can be any one or more polyisocyanate(s) which can be used in organic solvents.
  • polyisocyanates which can be used when practicing this invention include: toluene diisocyanates, isocyanurates of toluene diisocyanate, diphenylmethane 4,4-'diisocyanate, isocyanurates of 4,4'- diisocyanate, 1 ,4-cyclohexane diisocyanate, p-phenylene diisocyanate, triphenylmethane 4,4',4"-triiocyanate, metaxylene diisocyanate and polyisocyanates, 1 ,6-hexarnethylene diisocyanate, isocyanurates of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, isocyanurates of isophorone diisocyanate, methylene bis- 4,4'-isocyanatocyclohexane, and
  • polyisocyanates preferred use is made of 1 ,6-hexamethylene diisocyanate and isophorone diisocyanate, isocyanurate- and/or biuret-containing polyisocyanates which are derived from the latter and which preferably contain more than 2 isocyanate groups in the molecule.
  • the polyisocyanates used when practicing this invention can be both in free and in blocked form. If the polyisocyanate being employed is in a blocked form, any blocking agent can be used, provided that the agent has a sufficiently low deblocking temperature.
  • Groups suitable for use as the blocker portion of a blocked isocyanate are also well-known in the art.
  • suitable groups include: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols and amines.
  • oximes e.g., acetone oxime, methyl ethyl ketoxime, methyl amyl ketoxime, diisobutyl ketoxime, formaldehyde oxime
  • oximes e.g., acetone oxime, methyl ethyl ketoxime, methyl amyl ketoxime, diisobutyl ketoxime, formaldehyde oxime
  • the film-forming composition contains a catalyst to accelerate the cure of the polyisocyanate and other crosslinkable groups.
  • a catalyst to accelerate the cure of the polyisocyanate and other crosslinkable groups.
  • useful catalysts include: metal acetonyl acetates, quaternary ammonium salts, zinc N-ethyl-N-phenyl dithiocarbamate, pentamethyl- diethylenetriamine benzoate, cyclohexylamine acetate, n,n-dimefhyl cyclohexylamine acetate, ketimines, N-methyl morpholine, tin octoate, stannic chloride, butyl tin trichloride, dibutyl tin diacetate, dibutyl tin dilaurate, bis(2-ethylhexyl) tin oxide, 1,3- diacetoxy tetrabutyl stannoxate, dibutyl dibutoxy
  • zirconium octoate tin, dibutyl tin maleate, stannous oxalate, stannous stearate, barium nitrate, zinc nitrate, dibutyltin dilauryl mercaptide, bismuth stearate, lead stearate, dimethyltin dichloride, stannous naphthate, dibutyltin bis-O-phenylphenate, dibutyltin S,S-dibutyldithio-carbonate, and triphenylantimony dichloride.
  • Organometallic catalysts having tin as the metal are preferred. Of these, dibutyltin dilaurate is most preferred.
  • the catalyst is usually present in an amount ranging from between about 0.1 to about 5 weight percent, and preferably, from between about 0.5 to about 2 weight percent. These weight percentages are based upon the total weight of the resin solids in the coating composition.
  • optional ingredients such as plasticizers, flow controllers, anti-oxidants, UV light absorbers and other similar additives known in the art, can also be included in the coating composition. If employed, the cumulative weight of these optional ingredients are typically present at up to about 25 weight percent. This weight percentage is based upon the total weight of the iresin solids in the coating composition.
  • the crosslinkable film-forming coating composition of the present invention can be used as the clear top coat layer in a "color-plus-clear" coating system.
  • the base coat in a color-plus-clear system encompassed by the present invention can be any of the compositions useful in coatings applications, particularly those in automotive and general industrial applications.
  • the film-forming composition of the base coat typically includes a resinous binder and a pigment. Examples of particularly useful resinous binders include acrylic polymers, polyesters (including alkyds) and polyurethanes.
  • the base coat compositions may be solvent-borne or water-borne.
  • water-borne base coats in a color-plus-clear system encompassed by the present invention are disclosed in U. S. Patent 4,403,003.
  • water-borne polyurethanes such as those disclosed in U. S. Patent 4,147,679, can also be used as the resinous binder in the base coat to prepare a coating-plus-clear system which is encompassed by the present invention.
  • water-borne coatings such as those described in U. S. Patent 5,071,904, can also be used as a base coat.
  • Base coats also often contain pigments in order to give them the desired color.
  • base coat compositions containing metallic flake pigmentation are often used in the production of so-called "glamour metallic" finishes. These types of finishes are mainly used in the automotive industry. Examples of metallic flakes which can be used in a base coat of a color-plus-clear system encompassed by this invention include: aluminum flake, copper bronze flake and metal oxide coated mica.
  • the base coat compositions may also contain non-metallic color pigments conventionally used in surface coatings.
  • pigments examples include: inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green.
  • inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, and carbon black
  • organic pigments such as phthalocyanine blue and phthalocyanine green.
  • non-metallic pigments are typically incorporated into the base coat composition in an amount ranging from between about 1 to about 80 percent by weight based on the total weight of coating solids.
  • metallic pigments are typically employed in an amount ranging from between about 0.5 to 25 percent by weight based on the total weight of coating solids.
  • the base coat composition may contain additional materials well known in the art of formulated surface coatings.
  • additional materials include: surfactants, flow control agents, thixotropic agents, fillers, anti- gassing agents, organic co-solvents, catalysts, and other customary auxiliaries. If employed, the cumulative weight of these materials can constitute up to 40 percent by weight of the total weight of the coating composition.
  • the base coat compositions of a color-plus-clear system encompassed by the present invention can be applied to various substrates such as metals, plastics, wood, glass, woven fibers, non-woven fibers, foams, or a combination thereof. They are, however, particularly useful when applied over metals and elastomeric substrates that are found on motor vehicles.
  • the base coat compositions can be applied over such substrates by conventional means including brushing, dipping, flow coating, spraying and the like. Most often, the base coat composition is applied by spraying. Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used.
  • the base coat thickness ranges from between about 0.01 to about 10 mils, and preferably, from between about 0.05 to about 5 mils, and even more preferably, from between about 0.1 to about 2 mils.
  • a film is formed on the surface of the substrate by driving solvent out of the base coat by heating or by an air drying period.
  • the drying period is only for that time which is sufficient to ensure that the clear top coat can be applied over the base coat without the top coat dissolving the base coat. Suitable drying conditions will depend, in part, upon the particular base coat composition, the ambient humidity, and the like.
  • a drying time of from about 1 to about 5 minutes, at a temperature of about 68-250°F (20-121 °C), will be adequate to ensure that mixing or "soak-in" of the two coats is minimized.
  • the base coat film is adequately wetted by the clear top coat composition so that satisfactory intercoat adhesion is obtained.
  • More than one base coat and/or top coat may be applied to develop the optimum appearance of a color-plus-clear system encompassed by the present invention.
  • the previously applied coat is flashed (i.e., exposed to ambient conditions for about 1 to 20 minutes) between coats .
  • the clear top coat composition can be applied over the base coat film by any conventional coating technique. Examples of such conventional techniques include: brushing, dipping, flow coating, spraying and the like. Mos1 often, the top coat is applied by spraying. Conventional spray techniques and equipment for air spraying and electrostatic spraying and either manual or automatic methods can be used. After application ofthe top coat over the base coat, the coated substrate is heated to cure the coating layers.
  • the heating or curing operation is usually carried out at a temperature of about 160- 350°F (71-177°C). If needed, however, lower or higher temperatures may be used as necessary to activate crosslinking mechanisms.
  • the thickness ofthe clear coat layer usually ranges from between about 0.1 to about 10 mils, preferably, from between about 0.5 to about 7 mils, and even more preferably, from between about 1 to about 5 mils.
  • the free radical addition polymers containing various amount of cyclohexyl methacrylate and hydroxyl functional monomers were prepared similar to Example 1 and their composition, solvent, solids content, Gardner-Holdt viscosity and number average molecular weight are tabulated in Table I.
  • a hydroxy functional polymer was prepared in accordance with Example II.1 of U.S. Patent 4,565,730. That polymer was prepared as follows:
  • Aromatic hydrocarbon blend available from Exxon Chemical Company.
  • the initial charge was heated in a reaction vessel with agitation to reflux temperature (163°C). At reflux, Feeds A and B were initiated simultaneously and continued in a substantially continuous manner.
  • the monomer mixture (Feed A) was added over a period of 4 hours and the initiator solution (Feed B) was added over 4.5 hours while maintaining the reaction mixture at reflux temperature.
  • the reaction mixture was held for 1 hour at reflux temperature to complete the polymerization.
  • the reaction mixture was cooled and filtered.
  • the resultant acrylic resin had a total solids content of 61.9 percent determined at 1 10°C. for one hour and number average molecular weight of 2092 as determined by gel permeation chromatography using polystyrene as a standard.
  • the resin had a Gardner- Holdt viscosity measured at 25°C of I-.
  • a hydroxy functional polymer was prepared in accordance with Example III.1 of U.S. Patent 4,565,730. That polymer was prepared as follows:
  • the initial charge was heated in a reaction vessel with agitation to reflux temperature (131°C). At reflux, Feeds A and B were initiated simultaneously and continued in a substantially continuous manner.
  • the monomer mixture (Feed A) was added over a period of 4 hours and the initiator solution (Feed B) was added over 4.5 hours while maintaining the reaction mixture at reflux temperature.
  • the reaction mixture was held for 1 hour at reflux temperature to complete the polymerization.
  • the reaction mixture was cooled and filtered.
  • the resultant acrylic resin had a total solids content of 60.8 percent determined at 110°C. for one hour and number average molecular weight of 12787 as determined by gel permeation chromatography using polystyrene as a standard.
  • the resin had a Gardner- Holdt viscosity measured at 25°C of Z7-.
  • a pigmented black base coating composition was used v/hich is a high- solids polyester base coating composition available from PPG Industries, Inc. as POLYCRON ® III base coat.
  • a clear film forming composition was formulated from the following ingredients:
  • Bis(l ,2,2,6,6-pentamethyl-4-piperidinyl) sebacate hindered amine stabilizer available from Ciba Geigy Corp. (dissolved in isobutanol after neutralization with dodecylbenzene sulfonic acid).
  • the base coating composition prepared according to Example 15 was air-atomized spray applied to pretreated aluminum panels at room temperature to attain a dry film thickness of 0.8 to 1.2 mils. After a 10 minute flash, the panels were then baked for 10 minutes at 350°F (177°C). The panels were allowed to cool room temperature and the prepared clear coating compositions were applied to the base coating.
  • the clear coatings of Examples 16 to 27 and Comparative Examples 28 to 32 were applied in four successive coats at room temperature with film ranges from 1.8 to 2.2 mils. Each panel was given a 10 minute flash at room temperature, 10 minute "force" flash at 150°F (66 °C), and then baked for 30 minutes at 285°F (141 °C). The films were then evaluated for durability and acid etch resistance.
  • the durability tests were done using Xenon arc Weather-Ometer with quartz/borosilicate filter combination from 340 nm. The cycle was: 40 minutes light; 20 minutes light with specimen spray; 60 minutes light; 60 minutes dark cycle with both specimen and rack spray. The results after 2000 hours exposure are tabulated in Table IV.
  • the acid etch resistance ofthe films were evaluated via a 3-cycle sulfurous acid spray test
  • the acid solution with pH of 2 was prepared by adding 12 grams of H 2 SO ⁇ to 350 grams of deionized water.
  • the test consists of misting 3"x5" panel sections with the acid solution to completely cover the panels densely with droplets and then placing the panels in a 120°F (49 °C) oven for 20 minutes. This constitutes one cycle. The procedure is then repeated two times. The panels are then washed with soap and water and towel dried for evaluation.
  • the acid etch results are reported in Table IV.

Abstract

La présente invention concerne une composition durcissable, formant un film, qui comprend: (a) un polymère en solution acrylique, contenant un hydroxyle, et (b) un agent de réticulation de polyisocyanate. Le polymère en solution acrylique, contenant un hydroxyle, a une concentration d'environ 60 à environ 90 % en poids, et la concentration de l'agent de réticulation est d'environ 10 à environ 40 % en poids. Le polymère en solution acrylique est le produit de réaction de: (a) un ester cycloaliphatique ou aromatique, ou les deux, d'acide (méth)acrylique, ayant au moins 6 atomes de carbone dans le groupe cycloaliphatique ou aromatique, ou les deux, et (b) un constituant monomère acrylique fonctionnel hydroxyle, qui ne comporte pas une concentration importante de 4-hydroxy-n-butylacrylate ou de 4-hydroxy-n-butylméthacrylate ou d'un mélange des deux. De plus, le constituant monomère acrylique fonctionnel hydroxyle a une concentration telle que l'indice d'hydroxyle du polymère en solution acrylique qui est obtenu est inférieur à environ 200. La présente invention concerne aussi un système de revêtement à couche colorée plus une couche transparente. Ce système comprend: (a) l'application, sur un support, d'un revêtement de base formant un film et (b) l'application, sur la couche de base, d'une couche finale transparente formant un film. Cette dernière comprend la composition durcissable, formant un film, qui est décrite plus haut.
PCT/US1996/017724 1995-12-19 1996-11-05 Compositions durcies ultra-durables de polyisocyanate pour revetements brillants WO1997022646A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57488295A 1995-12-19 1995-12-19
US08/574,882 1995-12-19

Publications (1)

Publication Number Publication Date
WO1997022646A1 true WO1997022646A1 (fr) 1997-06-26

Family

ID=24298043

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/017724 WO1997022646A1 (fr) 1995-12-19 1996-11-05 Compositions durcies ultra-durables de polyisocyanate pour revetements brillants

Country Status (1)

Country Link
WO (1) WO1997022646A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999043721A1 (fr) * 1998-02-24 1999-09-02 Ppg Industries Ohio, Inc. Compositions filmogenes a base aqueuse durcissables a temperature ambiante
WO2003000434A1 (fr) * 2001-06-21 2003-01-03 Basf Corporation Composition d'appret renfermant un liant a base de poly(meth)acrylate
WO2003027198A1 (fr) * 2001-09-27 2003-04-03 Basf Corporation Composition de rénovation d'un enduit lustré acryl
WO2005030891A1 (fr) * 2003-09-22 2005-04-07 E.I. Dupont De Nemours And Company Procede de realisation d'une adhesion par recouvrement sur une couche de finition fluoree
US10934449B2 (en) 2016-07-29 2021-03-02 Behr Process Corporation Water based sealer with superior durability

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817174A (ja) * 1981-07-23 1983-02-01 Dainippon Ink & Chem Inc 塗料用樹脂組成物
JPS63142009A (ja) * 1986-12-05 1988-06-14 Nippon Shokubai Kagaku Kogyo Co Ltd 二液ウレタン樹脂塗料用組成物
EP0337744A2 (fr) * 1988-04-12 1989-10-18 Nippon Shokubai Co., Ltd. Copolymère stable aux rayons ultraviolets, son procédé de préparation et composition de revêtement le contenant
US5279862A (en) * 1991-10-21 1994-01-18 E. I. Du Pont De Nemours And Company Process for refinishing clear coat/color coat finish
DE4407415A1 (de) * 1994-03-05 1995-09-07 Basf Lacke & Farben Beschichtungsmittel auf Basis eines hydroxylgruppenhaltigen Polyacrylatharzes und seine Verwendung in Verfahren zur Herstellung einer Mehrschichtlackierung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817174A (ja) * 1981-07-23 1983-02-01 Dainippon Ink & Chem Inc 塗料用樹脂組成物
JPS63142009A (ja) * 1986-12-05 1988-06-14 Nippon Shokubai Kagaku Kogyo Co Ltd 二液ウレタン樹脂塗料用組成物
EP0337744A2 (fr) * 1988-04-12 1989-10-18 Nippon Shokubai Co., Ltd. Copolymère stable aux rayons ultraviolets, son procédé de préparation et composition de revêtement le contenant
US5279862A (en) * 1991-10-21 1994-01-18 E. I. Du Pont De Nemours And Company Process for refinishing clear coat/color coat finish
DE4407415A1 (de) * 1994-03-05 1995-09-07 Basf Lacke & Farben Beschichtungsmittel auf Basis eines hydroxylgruppenhaltigen Polyacrylatharzes und seine Verwendung in Verfahren zur Herstellung einer Mehrschichtlackierung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 12, no. 398 (C - 538) 21 October 1988 (1988-10-21) *
PATENT ABSTRACTS OF JAPAN vol. 7, no. 86 (C - 161) 9 April 1983 (1983-04-09) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999043721A1 (fr) * 1998-02-24 1999-09-02 Ppg Industries Ohio, Inc. Compositions filmogenes a base aqueuse durcissables a temperature ambiante
WO2003000434A1 (fr) * 2001-06-21 2003-01-03 Basf Corporation Composition d'appret renfermant un liant a base de poly(meth)acrylate
US6794442B2 (en) 2001-06-21 2004-09-21 Basf Corporation Fast drying basecoat refinish composition
WO2003027198A1 (fr) * 2001-09-27 2003-04-03 Basf Corporation Composition de rénovation d'un enduit lustré acryl
US7446149B2 (en) 2001-09-27 2008-11-04 Basf Corporation Fast drying clearcoat refinish composition
WO2005030891A1 (fr) * 2003-09-22 2005-04-07 E.I. Dupont De Nemours And Company Procede de realisation d'une adhesion par recouvrement sur une couche de finition fluoree
US7348389B2 (en) 2003-09-22 2008-03-25 E. I. Du Pont De Nemours And Company Method for achieving recoat adhesion over a fluorinated topcoat
US10934449B2 (en) 2016-07-29 2021-03-02 Behr Process Corporation Water based sealer with superior durability
US11572487B2 (en) 2016-07-29 2023-02-07 Behr Process Corporation Water based sealer with superior durability

Similar Documents

Publication Publication Date Title
US5663233A (en) Coating agents and the use thereof in processes for the production of multi-layer coatings
US6458885B1 (en) Fast drying clear coat composition
JP2001501986A (ja) ヒドロキシ官能価アクリル樹脂によるハイソリッドおよび粉末塗料
WO1995026384A1 (fr) Agent de revetement multicomposant aqueux, a base de polyurethanne, son procede de fabrication et son utilisation dans des procedes de fabrication d'un vernis multicouche
US5849835A (en) Polyisocyanate cured ultradurable glossy coating compositions
EP1201690B1 (fr) Compositions de copolymères de (meth)acrylate hydroxy-fonctionalisés ainsi que des compositions de revêtement
CA2146479C (fr) Polymere
JPH09509691A (ja) ポリ（メタ）アクリル樹脂を基礎とするイソシアネート架橋可能な被覆剤
US6001947A (en) Coating agent based on a hydroxyl group-containing polyacrylate resin and its use in processes for producing a multicoat paint system
CA1093238A (fr) Enduits a proprietes de liants, comprenant des polymeres acryliques contenant des hydroxyles reactifs
JPH0319271B2 (fr)
JPH11506477A (ja) 耐引掻性コーティング組成物
US7091278B2 (en) Aqueous two-component coating compositions
WO1997022646A1 (fr) Compositions durcies ultra-durables de polyisocyanate pour revetements brillants
WO1995016004A1 (fr) Procede de preparation de liants de peintures laques diluables dans l'eau et leur utilisation
US5612415A (en) Process for coating a substrate with coatings including high Tg acrylic polymers and coated article obtained thereby
US20040214942A1 (en) Two-component coating compositions
EP1211267B1 (fr) Compositions de revêtement à base de copolymères (meth)acrylique à fonction hydroxide
CA2648672C (fr) Compositions promotrices d'adhesion et procedes permettant d'ameliorer l'adhesion entre un revetement et un substrat
JP4296178B2 (ja) 塗料組成物及びそれを塗工してなる塗装物
CA2234377C (fr) Composition aqueuse de revetement
CN112888566B (zh) 汽车用部件
JP3416925B2 (ja) 一液低温硬化型着色エナメル塗料
US5658988A (en) Resinous composition for coating
JP3163443B2 (ja) 塗料用樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CZ EE FI HU LT MX NO PL RO RU SK TR UA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase