WO1985001737A1 - Flexible uni-basecoat/two component clearcoat coating compositions - Google Patents

Flexible uni-basecoat/two component clearcoat coating compositions Download PDF

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Publication number
WO1985001737A1
WO1985001737A1 PCT/US1983/001604 US8301604W WO8501737A1 WO 1985001737 A1 WO1985001737 A1 WO 1985001737A1 US 8301604 W US8301604 W US 8301604W WO 8501737 A1 WO8501737 A1 WO 8501737A1
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WO
WIPO (PCT)
Prior art keywords
clearcoat
basecoat
crosslinking agent
composition
composition according
Prior art date
Application number
PCT/US1983/001604
Other languages
English (en)
French (fr)
Inventor
Panagiotis I. Kordomenos
Kenneth R. Kurple
Delores J. Alexander
Original Assignee
Ford Motor Company
Ford Motor Company Of Canada, Limited
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 Ford Motor Company, Ford Motor Company Of Canada, Limited filed Critical Ford Motor Company
Priority to US06/598,551 priority Critical patent/US4530976A/en
Priority to PCT/US1983/001604 priority patent/WO1985001737A1/en
Priority to JP58503627A priority patent/JPS61500121A/ja
Priority claimed from US06/558,399 external-priority patent/US4588787A/en
Priority claimed from US06/598,551 external-priority patent/US4530976A/en
Priority claimed from US06/553,322 external-priority patent/US4524192A/en
Priority to DE8484306970T priority patent/DE3471680D1/de
Publication of WO1985001737A1 publication Critical patent/WO1985001737A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
    • 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
    • C08G18/83—Chemically modified polymers
    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

Definitions

  • Basecoat/clearcoat systems comprise a finish of a clear topcoat layer in film adherence to a basecoat that is in adherence to a substrate. More particularly, the invention relates to a basecoat/clearcoat coating composition wherein the basecoat and the clearcoat composition each comprise hydroxy-containing urethane modified polyesters, made from urethane modified diols reacted with polyol and diacid component, crosslinking agent and, optionally, a high molecular weight linear polyurethane.
  • the basecoat which additionally contains pigment, employs amine-aldehyde crosslinking agent while the clearcoat employs polyisocyanate crosslinking agent.
  • Patent 3,962,522 are exemplary of numerous patents which describe flexible coating compositions wherein the resin comprises polyurethane modified polyesters formed by reacting polyisocyanate with polyester polyols. These resins are cured with amine aldehyde crosslinkers. It is taught therein, that the presence of the urethane groups in the polymer significantly contributes to the flexibility as well as improved weathering properties, gloss, and abrasion resistance of the coating. However, while it is thus desirable to employ a substantial number of urethane groups in these resins, the amount which may be included in these types of resins is limited.
  • This invention is directed to a flexible basecoat/clearcoat coating composition which is suitable for use over various substrates, including rubbery, resilient materials as well as metal.
  • the basecoat/clearcoat coating composition of this invention is characterized in that the basecoat composition and the clearcoat composition each independently comprises: (A) hydroxy-containing urethane modified polyester (i) having a number average molecular weight (M n ) of between about 1000 and about 10,000, (ii) having a hydroxyl number of between about 30 and about 200, and (iii) containing between about 1 and about 10 urethane groups per molecule, and being made from reactants comprising:
  • urethane modified diol made by reacting:
  • acid component selected from dicarboxylic acids and anhydrides thereof
  • (C) 0-60 weight percent, based on the total weight of (A) and (B) of the composition, of a linear polyurethane having a number average molecular weight of between about 15,000 and about 40,000, preferably of between about 20,000 and about 30,000.
  • the basecoat composition additionally comprises pigment.
  • the crosslinking agent of the clearcoat composition of this invention is a polyisocyanate crosslinking agent.
  • the crosslinking agent of the basecoat composition of this invention is an amine-aldehyde crosslinking agent.
  • the flexible basecoat/clearcoat coating compositions of the invention of this application possess superior weathering properties as well as excellent adhesion to metal and plastic, thus making them well suited for use as coatings on various car components.
  • the urethane linkages are advantageously incorporated into the backbone of the modified polyester, since they are formed in an initial reaction of diisocyanate with the diol, rather than being incorporated into the polyester in a later reaction step as is done when forming prior art urethane polyester resins. It has now been found that the initial incorporation of the urethane linkage into the backbone of the modified polyester allows the formation of more flexible coatings with improved weathering properties, particularly suitable to form automotive basecoat/clearcoat coatings.
  • This invention is directed to flexible basecoat/clearcoat coating compositions, wherein the basecoat composition and the clearcoat composition comprise hydroxy-containing urethane modifying polyester and crosslinking agent.
  • the basecoat composition crosslinking agent is amine-aldehyde while the clearcoat composition crosslinking agent is polyisocyanate.
  • the basecoat composition additionally comprises pigment.
  • the basecoat composition and/or the clearcoat composition may include a high molecular weight linear polyurethane.
  • the novel hydroxy-containing urethane modified polyester is made from urethane modified diols reacted with polyol and diacid component. The various components of the compositions of this invention will be discussed in detail.
  • the hydroxy-containing urethane modified polyester of the basecoat/clearcoat coating composition of this invention has a number average molecular weight (M n ) of between about 1000 and about 10,000, preferably between about 2000 and about 4000.
  • M n number average molecular weight
  • This modified polyester has a hydroxyl number of between about 30 and about 200, preferably between about 50 and about 120. It also contains between about 1 and about 10 urethane groups per molecule.
  • One of the reactants used to form the hydroxy-containing urethane modified polyester is a urethane modified diol which is made by reacting diol and diisocyanate.
  • the diol and the diisocyanate are reacted in a molar ratio of from about 4:1 to about 4:3, preferably in a molar ratio of from about 2:1.8 to about 2:1.2, most preferably in about a 2:1 molar ratio.
  • the diols employed in making the urethane modified diol include, but are not limited to, alkylene glycols, such as butylene glycol, neopentyl glycol, 1,5,pentene glycol, 3-cyclohexene-1,1-dimethynol, and other glycols such as hydrogenated bisphenol A, caprolactone diol (i.e., the reaction product of caprolactone and ethylene glycol), hydroxy alkylated bisphenols, polyether glycols, e.g., poly(oxytetramethylene) glycol, polyester diols, e.g., 2,2-dimethyl-3-hydroxy ⁇ ro ⁇ yl-2,2-dimethyl-3-hydroxypropionate, and the like.
  • alkylene glycols such as butylene glycol, neopentyl glycol, 1,5,pentene glycol, 3-cyclohexene-1,1-dimethynol
  • other glycols such as
  • Preferred diols are neopentyl glycol and 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3hydroxypropionate, the latter material being commercially available as Esterdiol 204 (a trademark of and available from Union Carbide, New York, N.Y.). While a number of types of diols have been mentioned above as suitable for use as the diol component in making the urethane modified diol of this invention, their disclosure is not meant to be limiting. A great many diols are known in the art. Selection of other diols which would be suitable for use in forming the urethane modified diol would be well within the skill of those in the art. Mixtures of diols may also be employed to make the urethane modified diol.
  • the diisocyante employed in making the urethane modified diol may be essentially any diisocyanate. Many such organic diisocyanate are known in the art. Suitable diisocyanates include hydrocarbon diisocyanate or substituted hydrocarbon diisocyanate, such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, biphenyl diisocyanate, toluene diisocyanate, and 3,3-dimethyl-4,4-biphenylene diisocyanate.
  • hydrocarbon diisocyanate or substituted hydrocarbon diisocyanate such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, biphenyl diisocyanate, toluene diisocyanate, and 3,3-dimethyl-4,4-biphenylene diisocyanate.
  • the diisocyanate may be any of a number of aliphatic, cycloaliphatic, and aromatic diisocyanates, it is preferred that the diisocyanate be an aliphatic diisocyanate, such as 4,4-dicyclohexylmethanediisocyanate. As would be apparent to those skilled in the art, mixtures of various diisocyanates may also be employed at the diisocyanate component used in forming the urethane-modifying diol.
  • the polyol component used in forming the hydroxy-containing urethane modified polyester of the basecoat/clearcoat compositions comprise at least about 5 weight percent triol (based on the weight of the polyol component).
  • Preferred triols are conventional low molecular triols such as 1,2,6-hexene triol, 1,1,1-trimethylol propane, pentaerythritol, 3-(2-hydroxypropoxy)-1,2-pro ⁇ anediol and polycaprolactone triols, which are commercially available as, for example PCP-301 (trademark. Union Carbide Corp., New York, N.Y.).
  • This polyol component may also comprise, in addition to the triols other polyol materials such as diols or tetrols.
  • these other polyols when employed. consist of diols.
  • suitable diols which may be included in the polyol component are those which have been disclosed above as a component for forming the urethane modified diol.
  • the polyol component may comprise materials such as a diol in addition to the triol, the polyol component may consist essentially of triols.
  • diols By employing diols in the polyol component in addition to the triols the flexibility of the coating composition is generally increased.
  • selection of the polyol component to be used in forming the hydroxy-containing urethane modified polyester of the clearcoat will be dependent on the particular desired properties and application of the coating composition.
  • the polyol preferably comprises from about 10 to about 80 weight percent triols and from about 90 to about 20 weight percent diols.
  • the acid component which is used to form the modified polyester of the compositions of this invention comprises aliphatic, aromatic , cycloaliphalic dicarboxylic acid or anhydrides.
  • Preferred dicarboxylic acids are the C 6 - C 12 acids, which include adipic, azelaic, sebasic, or dodecane dicarboxylic acid, or cyclohexanedicarboxylic acid. More preferably, the dicarboxylic acids employed are aliphatic dicarboxylic acids, most preferably, additionally being linear. Mixtures of suitable acids and/or their anhydrides may also be used as the acid component in this invention.
  • the diol (a) and the diisocyanate (b) described above are combined and reacted, generally at an elevated temperature so as to form the urethane modified diol.
  • the ratio of the diol to diisocyanate i.e., a molar excess of diol
  • This urethane modified diol is then combined and reacted with the polyol and acid components, generally in the presence of a catalyst and at elevated temperatures, so as to effect formation of a hydroxy-containing urethane modified polyester.
  • Suitable catalysts for the carboxy/hydroxy condensation reaction include such catalysts as tetraisopropyl titanate, strong acids such as p-toluene phosphonic acid, phosporic acid sulfuric acid and materials such as zinc oxide, antimony oxide (Sb 2 O 3 ) and sodium acetate.
  • Other catalysts will be apparent to those skilled in the art.
  • the reactions, whereby the hydroxy-containing urethane modified polyesters of the basecoat or clearcoat are formed, are generally carried out in the presence of solvents commonly employed for coating formulations such as toluene, xylene, methyl amyl ketone, etc.
  • the hydroxy-containing urethane modified polyester of the basecoat coating composition and the clearcoat coating composition employed in the basecoat/clearcoat system may be similar or different embodiments of this polyester. Selection of the particular modified polyester to be employed in the coatings would be dependent on the particular properties and application of the coatings desired. Such selection will be well within the skill of one in the art.
  • the crosslinking agent of the clearcoat coating composition of the invention is a polyisocyanate crosslinking agent, i.e., a compound having 2 or more, preferably 3 or more, reactive isocyanate groups per molecule.
  • polyisocyanate crosslinking agent i.e., a compound having 2 or more, preferably 3 or more, reactive isocyanate groups per molecule.
  • These polyisocyanate materials function as a crosslinking agent in the composition of the invention by reaction with the hydroxyl functionality of the hydroxy containing urethane modified polyester (A) and by reaction with the hydroxyl functionality on the linear polyurethane if such linear polyurethane is included in the composition.
  • This polyisocyanate crosslinking agent is generally included in the clearcoat coating composition of the invention in an amount of between about 5 and about 60, more preferably between about 20 and about 40 weight percent based on the weight of the hydroxy-containing urethane modified polyester of the clearcoat composition. Selection of the optimal amount of polyisocyanate crosslinking agent to be employed in the coating composition is dependent on the desired properties (e.g., flexibility) as well as its intended use and selection of such amount would be within the skill of one in the art.
  • Polyisocyanates are well known in the art and numerous suitable organic isocyanates having 2 or more reactive isocyanate groups per molecule will be apparent to those skilled in the art.
  • suitable polyisocyanates are aliphatic, cycloaliphatic and aromatic isocyanate compounds.
  • isocyanates which may be employed are (1) aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyante, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2 propylene diisocyanate, 1,2 butylene diisocyanate, 2,3 butylene diisocyanate, 1,3 butylene diisocyanate, 1,3 butylene diisocyanate, ethylidene diisocyanate, butylidene diisocyanate, 4,4'bis( isocyanate hexyl) methane, bis(2-isocyanate-ethyl) fumarate, 2, 6-diisocyanate methyl caproate, 2,2,4(2,4,4)trimethylhexamethylene diisocyanate, and dimer acid diisocyanates; (2) cycloaliphatic diisocyanates such as 1,3 cyclopentane diisocyanate, 1,4
  • a polyisocyanate crosslinking agent for the clearcoat is a polyisocyanate having a biuret structure.
  • This type of polyisocyanate is well known as are methods for making the same.
  • One such polyisocyanate crosslinking agent is a high molecular weight biuret of 1,6 hexamethylene diisocyanate sold by Mobay Chemical Company under the tradename Desmodur N.
  • Exemplary of other biuret type polyisocyanates are those prepared in accordance with U.S. Patent 3,976,622 to Wagner et al.
  • the crosslinking agent of the basecoat coating composition of this invention is an amine-aldehyde crosslinking agent.
  • Amine-aldehyde crosslinking agents suitable for crosslinking hydroxy functional bearing materials are well known in the art. Typically, these crosslinking materials are product of reactions of melamine, or urea with formaldehyde and various alcohols containing up to and including 4 carbon atoms.
  • the amine-aldehyde crosslinking agents useful in this invention are amine-aldehyde resins such as condensation products of formaldehyde with melamine, substituted melamine, urea, benzoguanamine or substituted benzoguanamine.
  • Preferred members of this class are methylated melamine-formaldehyde resins such as hexamethoxymethylmelamine.
  • the particular preferred crosslinkers are the high solids melamine resins which has substantially 100 percent nonvolatile content as measured by the foil method at 45 °C for 45 minutes.
  • suitable amine-aldehyde crosslinking agents will be apparent to one skilled in the art.
  • the amine-aldehyde materials function as a crosslinking agent in the basecoat compositions of the invention by reacting with the hydroxy functionality of the hydroxy-containing urethane modified polyester (A) of the basecoat composition and by reaction with the hydroxy functionality on the linear polyurethane (C), if such materials are included in the basecoat compositions.
  • the amine aldehyde crosslinking agent is generally included in the basecoat composition in an amount of between about 5 and about 60, more preferably, between about 20 and about 40 weight percent based on the weight of the hydroxy-containing urethane modified polyester. Selection of the particular amount of amine-aldehyde crosslinking agent to be employed in the basecoat composition is dependent on the desired properties of the coating compositions as well as its intended use as would be apparent to one skilled in the art.
  • crosslinking agents are the amino crosslinking agents sold by American Cyanamid under the trademark "Cymel”.
  • Cymel 301, 303,325, 1130, 1156, which are alkalated melamine aldehyde resins are useful in the compositions of this invention.
  • the crosslinking reactions are catalytically accelerated by acids.
  • One such catalyst for example which may be so employed is p-toluene sulfonic acid which, when employed, is generally added to the composition in about .5% by weight based on the total weight of the amine-aldehyde crosslinker and hydroxy-containing modified polyester of the basecoat composition.
  • the amounts of crosslinking agent to be employed in the basecoat composition and in the clearcoat composition are selected individually, i.e., the weight percent amounts of crosslinker employed in the basecoat composition and in the clearcoat composition of a particular basecoat/clearcoat system may be different or be similar.
  • the basecoat coating composition of the invention also include pigments, as noted above.
  • pigments are available and known for use in coating compositions by those skilled in the art. Selection of the optimal amount of pigment to be included in the basecoat composition would be dependent on, e.g., desired color, hiding requirements of the coating, etc., and would be within the skill of those in the art.
  • Additional materials which may be employed in the coating compositions of this invention include a high molecular weight linear polyurethane which has a number average molecular weight of between about 15,000 and about 40,000, preferably between about 20,000 and about 30,000. It may be made by reacting one of the above mentioned diisocyanates and diols, such as oligoester diol, polycaprolactone diol, polyoxypropylene diol, polyether diols, etc. Suitable high molecular weight linear polyurethane materials are commercially available, for example, as Spenlite L06-30S, (available from and a trademark of Spencer-Kellogg, Buffalo, N.Y.).
  • the high molecular weight polyurethane may be employed in the composition in amounts up to about 60 weight percent based on the total weight of the hydroxy-containing urethane modified polyester and crosslinking agent. When employed, it is preferred that they be included in the composition in amounts of between about 10%-60%, more preferably 30%-50% by weight as described. It has been found that by incorporating this polyurethane in the basecoat of basecoat/clearcoat systems, the depth of color and metallic glamour of the basecoat/clearcoat system is improved. While this linear polyurethane, when employed, is generally preferably only included in the basecoat composition, it may be employed in either or both coats and the amounts are independently selected.
  • solvents used in the coating composition of this invention are those which are commonly used, e.g., to facilitate spray application and high solids content and include toluene, xylene, methylethyl ketone, acetone, 2-ethoxy-1-ethanol, diacetone alcohol, tetrahydrofuran, ethyl acetate, dimethylsuccinate, dimethylglutarate, dimethyladipate or mixtures thereof.
  • the solvent in which the hydroxy-containing urethane modified polyester is prepared may be employed as a solvent for the composition thus eliminating the need for drying the resin after preparation, if such is desired.
  • Typical of the ultraviolet stabilizers that are useful in this invention are benzophenones such as dodecyl oxibenzophenone, 2,4-dihydroxybenzophenone,hydroxybenzophenones containing sulfonic groups, 2-4-dihydroxy-3'5'-ditertiary butyl benzophenone, 2,2',4',trihydroxy benzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic mono esters of 2,2',4-trihydroxy-4' alkoxybenzophenone; 2-hydroxy-4-methoxy-2-carboxybenzo ⁇ henone; triazoles such as 2-phenyl-4-(2'4'-dihydroxybenzoyl) - triazoles substituted benzotriazoles such as hydroxy-phenyltriazoles such as 2-(2'hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-phenyl) benzotriazole, 2-(2'
  • These stabilizers contain the sterically hindered polyalkylpiperidine radical and at least two primary hydroxyl groups available for reacting with the crosslinking agent, e.g., amine-aldehyde or polyisocyanate, of the coating composition.
  • the basecoat would preferably contain a benzotriazole U.V. stabilizer such as Tinuvin 328 (a trademark of and commercially available from Ciba-Geigy, Ardsley, N.Y.), and the clearcoat would contain a benzotriazole U.V. stabilizer, e.g., Tinuvin 328, the polymeric hindered amine light stabilizer of the aforementioned concurrently filed application to Kordomenos et al, and an antioxidant, e.g., Irganox-1010. (available from and a trademark of Ciba-Geigy). While preferred combinations of stabilizer and antioxidant have been described, these teachings are not meant to be limiting.
  • a benzotriazole U.V. stabilizer such as Tinuvin 328 (a trademark of and commercially available from Ciba-Geigy, Ardsley, N.Y.)
  • Tinuvin 328 a trademark of and commercially available from Ciba-Geigy, Ardsley, N.
  • surface modifiers or wetting agents are common additives for liquid paint compositions. Exact mode of operation of these surface modifiers is not known but it is thought that their presence contributes to better adhesion of coating compositions to the surface being coated and helps formation of thin coatings, particularly on metal surfaces.
  • the choice of surface modifiers or wetting agents is dependent upon the type of surface to be coated. Selection of appropriate surface modifiers will be well within the skill of the artesian. Typical of these surface modifiers are polybutyl acrylate and a wide variety of silicon wetting agents which are commercially available.
  • NAD's such as described by Porter (S. Porter, Jr., and B.N. McBane, U.S. Patent 4,025,474, May 24, 1977). These particle dispersions may be included generally in amount up to 15% by weight of the total composition.
  • Other types of NAD's such as described by D.L. Maker and S.C. Peng (U.S. Patent 3,814,721, June 4, 1974) or by S.K. Horvath (U.S. application Serial No. 292,853, filed August 14, 1981) also may be included in the coating compositions.
  • the coating composition can be applied by conventional methods known to those in the art. These methods include roll coating, spray coating, dipping or brushing and of course the particular application technique chosen with the particular substrate to be coating and the environment in which coating operation takes place.
  • Particular preferred techniques for applying these coating compositions is spray coating through the nozzle of the spray gun.
  • the basecoat can be applied as a single component by means of a single component spray gun.
  • spray applying the clearcoat composition the hydroxy1-containing urethane modified polyester and the optional linear polyurethane along with other additives such as pigments, U.V. absorbers, antioxidants and other nonreactive materials are admixed with a solvent. These materials are fed as one component of a two component system into a spray gun which combines the materials as they are sprayed onto the automotive substrate.
  • the other material is the polyisocyanate crosslinking agent, which may or may not be cut with a suitable nonreactive solvent.
  • PCP-0301 polycaprolactone triol, trademark of Union Carbide, New York, N.Y.
  • 263 gms of adipic acid, 3 gms of dibutyl tin oxide, and 215 gms of xylene were added.
  • the mixture was heated up to 204°C and water was distilled off until the acid number dropped below 10.
  • the batch was then thinned with 480 parts of methyl amyl ketone.
  • the final product had Z3 viscosity at 70.8% NV and acid number 1.2.
  • PCP-0301 polycaprolactone triol, trademark of Union Carbide, New York, N.Y.
  • 263 gms of adipic acid, 3 gms of dibutyl tin oxide, and 215 gms of xylene were added.
  • the mixture was heated up to 204°C and water was distilled off until the acid number dropped below 10.
  • the batch was then thinned with 480 parts of methyl amyl ketone.
  • the final product had Y viscosity at 72% NV and acid number 7.9.
  • PCP-0301 polycaprolactone triol, trademark of Union Carbide
  • 263 gms of adipic acid 402 gms of dodecanoic acid, 4 gms of dibutyl tin oxide, and 200 gms of xylene were added.
  • the mixture was heated up to 204°C and water and xylene was distilled off until the acid number dropped below 10.
  • the batch was thinned with 480 parts of methyl amyl ketone.
  • the mixture was kept at this temperature until no NCO pick was observed in an IR spectrum.
  • the batch was thinned with 860 gms of toluene and 1,260 gms isopropanol.
  • the final product had a weight viscosity at 33.1% NV.
  • PCP-0301 polycaprolactone triol, trademark of Union Carbide, New York, N.Y.
  • 131 gms of adipic acid and 133 gms of phthalic anhydride, 3 gms of dibutyl tin oxide, and 215 gms of xylene were added.
  • the mixture was heated up to 204°C and water was distilled off until the acid number dropped below 10.
  • the batch was then thinned with 480 parts of methyl amyl ketone.
  • the final product had Z5 viscosity at 70.1% NV and acid number 3.

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  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
PCT/US1983/001604 1983-10-13 1983-10-13 Flexible uni-basecoat/two component clearcoat coating compositions WO1985001737A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US06/598,551 US4530976A (en) 1983-10-13 1983-10-13 Flexible uni-basecoat/two component clearcoat coating compositions
PCT/US1983/001604 WO1985001737A1 (en) 1983-10-13 1983-10-13 Flexible uni-basecoat/two component clearcoat coating compositions
JP58503627A JPS61500121A (ja) 1983-10-13 1983-10-13 可撓性コ−テイング組成物
DE8484306970T DE3471680D1 (en) 1983-10-13 1984-10-12 Flexible coating compositions

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US06/558,399 US4588787A (en) 1983-10-13 1983-10-13 Flexible two component urethane coating compositions
US06/598,551 US4530976A (en) 1983-10-13 1983-10-13 Flexible uni-basecoat/two component clearcoat coating compositions
PCT/US1983/001604 WO1985001737A1 (en) 1983-10-13 1983-10-13 Flexible uni-basecoat/two component clearcoat coating compositions
US06/553,322 US4524192A (en) 1983-10-13 1983-10-13 Flexible coating compositions
PCT/US1983/001596 WO1985001694A1 (en) 1983-10-13 1983-10-13 Flexible coating compositions

Publications (1)

Publication Number Publication Date
WO1985001737A1 true WO1985001737A1 (en) 1985-04-25

Family

ID=27536319

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1983/001604 WO1985001737A1 (en) 1983-10-13 1983-10-13 Flexible uni-basecoat/two component clearcoat coating compositions

Country Status (3)

Country Link
JP (1) JPS61500121A (cs)
DE (1) DE3471680D1 (cs)
WO (1) WO1985001737A1 (cs)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882189A (en) * 1971-05-20 1975-05-06 Ashland Oil Inc Polyester resins prepared from organic polyisocyanates and blends with other resins or monomers
US3962522A (en) * 1973-04-02 1976-06-08 Ppg Industries, Inc. Poly(esterurethane) coating cured with an aminoplast on a solid substrate
US4021505A (en) * 1975-03-20 1977-05-03 American Cyanamid Company Mar-resistant coating composition of reaction product of hydroxy-terminated urethane and melamine resin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882189A (en) * 1971-05-20 1975-05-06 Ashland Oil Inc Polyester resins prepared from organic polyisocyanates and blends with other resins or monomers
US3962522A (en) * 1973-04-02 1976-06-08 Ppg Industries, Inc. Poly(esterurethane) coating cured with an aminoplast on a solid substrate
US4021505A (en) * 1975-03-20 1977-05-03 American Cyanamid Company Mar-resistant coating composition of reaction product of hydroxy-terminated urethane and melamine resin

Also Published As

Publication number Publication date
JPS61500121A (ja) 1986-01-23
JPH0449876B2 (cs) 1992-08-12
DE3471680D1 (en) 1988-07-07

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