WO1987000851A1 - Compositions de revetement a base de carbamate - Google Patents

Compositions de revetement a base de carbamate Download PDF

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Publication number
WO1987000851A1
WO1987000851A1 PCT/US1986/001611 US8601611W WO8700851A1 WO 1987000851 A1 WO1987000851 A1 WO 1987000851A1 US 8601611 W US8601611 W US 8601611W WO 8700851 A1 WO8700851 A1 WO 8700851A1
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WIPO (PCT)
Prior art keywords
hydrogen
hydroxyethyl
propyl
groups
crosslinking agent
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PCT/US1986/001611
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English (en)
Inventor
Kenneth Look Hoy
Forrest Alden Richey, Jr.
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Union Carbide Corporation
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Publication date
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Publication of WO1987000851A1 publication Critical patent/WO1987000851A1/fr

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    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • High solids coatiftgs for the purpose of the present invention shall mean organic coating compositions in which the organic volatile solvents of the coating are minimized by the substitution of a reactive diluent and/or a reactive solvent for all or a part of the volatile solvent or diluent usually employed to make useful coating compositions from a particular film forming polymer.
  • the coating composition may be of two types: (1) stable dispersions of an organic polymer in an organic diluent (so called NAD or organosol), (2) solutions of organic polymers in organic solvents. It is the intent of this invention to disclose the preparation of high solids coating compositions which utilize at least one organic, non-volatile substituted, reactive carbamate which is also a solvent or dispersant for a film forming polymer to replace a part or all of the thinner required to reduce the coatings formulation to the required applications viscosity.
  • Reactive solvents and reactive diluents as used herein are nearly non-volatile organic materials which have as an integral part of their structure a plurality of functional groups which are co-reactive with the base film forming polymer and/or required crosslinking agents, and can replace a part or all of the volatile organic solvent and/or diluent required to reduce the formulation to a reasonable application viscosity. They may be liquids or solids providing, those which are solids are soluble, fusible, and compatible with the film forming components either before or after application and subsequent cure.
  • Adoption of this definition imposes some requirements on materials which can be considered as reactive solvents and reactive diluents. They must be: (1) essentially non-volatile under the conditions required for cure of the coating, (2) good solvents for the film forming polymers or in the case of the dispersions, be temporary plasticizers for the base polymer during film formation, (3) latently co-reactive with the film forming polymer and/or the cross-linking agents under conditions required for polymer conversion, and finally (4) be able to provide final film properties required for the intended application.
  • the properties of the coating are related not only to the properties of the film forming polymer but also to the properties attained from the reactive solvent or reactive diluent upon chemical incorporation into the composition. Often it is necessary to adjust the structure of the film forming polymer to compliment the structure of the reactive diluent.
  • Such polymers are designed for this intended use, and are preferable to polymers used in much of the prior art.
  • polymers of the prior art can be formulated, using reactive diluents and/or solvents, into coating compositions with lower emissions than the corresponding formulation of these identical polymers using only volatile non-reactive solvents and/or diluents.
  • FIG. 1 is a simplified phase diagram of a hypothetical dispersion high solids coatings system, representing the volatile diluent as A, the reactive diluent as C, and the film forming polymer including the cross-linking agent as B.
  • the area of a single phase, 2 is separated from the area of two phases, 4, by the curved line A-A'-B.
  • the point E represents the application composition of the high solids dispersion coating.
  • the straight line E-D represents the changing compositions during film formation; the dashed line E-B is the film forming pathway that the high solids coating of the prior art would take, in the later case the diluent C' is the fugitive plasticizer required for particle coalescence and must be removed from the film by vaporization otherwise performance properties would be degraded. In the former the reactive diluent remains an internal part of the film and is incorporated into the polymeric film by reacting with the polymer through the reactive functionalities provided.
  • the reactive diluent is compatible with (soluble in) the base film forming polymer; (ii) the reactive diluent serves as a transient plasticizer to allow film coalescence; (iii) the reactive diluent need not be totally soluble in the volatile diluent, but rather is initially distributed between the organic liquid phase and the polymer phase and during evaporation of the volatile diluent is translocated totally to the polymer phase; (iv) because the reactive diluent is essentially non-volatile and becomes a part of the final coating, the total non-volatiles (total solids) of the coating is equal to the sum of the polymer including the cross-linker and the reactive diluent thus allowing lower volatile organic emissions.
  • Figure 2 is a simplified compositional phase diagram of a hypothetical high solids solution coating composition representing A, as the volatile organic solvent, the reactive solvent as C, and the film forming polymer including any required cross-linking agent as B.
  • A the volatile organic solvent
  • C the reactive solvent
  • B the film forming polymer including any required cross-linking agent
  • the point E represents the applications composition of the high solids solution coating.
  • the straight line E-D represents the changing compositions during the film forming process.
  • the dashed line E-B represents the film forming pathway of a corresponding solution coating when C is a volatile organic solvent.
  • the notable features of Figure 2 are: (i) The reactive solvent is generally miscible with the volatile organic solvent; the line A-C is in the one phase region in its entirety. (ii) The coatings polymer is soluble in the reactive solvent; the line C-B is in the one phase region in its entirety. (iii) The reactive solvent is essentially non-volatile and becomes a part of the final coating and consequently, the total solids (non-volatiles) in the film, point D, is equal to the sum of the polymer including any required cross-linker and the reactive solvent.
  • reaction product of polymer, reactive diluent and/or reactive solvent and the cross-linking agent must have suitable properties such as toughness, adhesion, impact resistance, abrasion resistance, scratch resistance, resistance to solvents, chemicals, acids, and bases. It must have good color, gloss, and stability as is required according to the end use application. All of the above is well understood by those skilled in the art.
  • the coatings technologist adapted materials which were readily available for use as reactive solvents and reactive diluents. Many of these materials have limited utility because of excessive volatility, limited reactivity, poor compatibility with the base film forming system, and in general degradation of overall coatings performance.
  • Typical of the early reactive solvents and diluents are higher boiling polyols e.g., glycerol, monoglycerides of unsaturated fatty acids, 1,2,6-hexanetriol and its mono ester derivatives, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,4-butanediol, and the like.
  • polyether diols derived from bisphenol A and ethylene or propylene oxide. Still later, hydroxy terminated polyesters were introduced. These materials are low molecular weight polyesters of M.W. 300 to 3000 derived from caprolactone, cyclic diols, e.g., cyclohexane dimethanol and dibasic acids such as phthalic, isophthalic, maleic, succinic and the like. Often small quantities of triols or tetrols were used to create polyfunctionality in the polyester. These materials are in effect very low molecular weight oil less alkyds. They are characterized by a broad compatibility, good co-reactivity, and low volatility. These materials represent an improvement over the polyether diols, however they provide neither the viscosity reduction for many applications methods including spray and electrostatic spray nor performance required for the more demanding end uses.
  • the substituted carbamates of the present invention have as an integral part of their structure a plurality of reactive -OH and/or -NHCO- groups which are capable, through the application of heat and/or in the presence of catalytic agents when required, of reacting with the base film forming polymers and cross-linking agents.
  • High solids coating compositions meeting the objects above can be prepared by blending;
  • R' - -O-R'' wherein each of R' and R'' is a monovalent radical selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbons, hydroxyalkyl groups having 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolyalkyleneoxy groups and R''' is the same as R' or R'' except that it cannot be hydrogen, with the provisos that: said hydroxyalkyl, hydroxyalkyleneoxy and hydroxypolyalkyleneoxy groups contain at least 1 OH group; said R' and R'' or R' and R''' groups can unite to form a carbon ring structure; and said carbamate derivatives contain either at least one -NH and one -OH group or at least two OH groups;
  • the monovalent radicals may be substituted with ether, halogen, quaternary ammonium, sulfonium, phosphonium and like substituents.
  • Suitable organic polymers for use in the present invention include polymers which contain a plurality of reactive -OH and/or -NHCOO -groups.
  • Preferred crosslinkable organic polymers for use in this invention having as an integral part of their structure a plurality of reactive -OH and/or -NH groups include:
  • Hydroxyl containing vinyl interpolymers such as styrene/acrylic copolymers.
  • the ratio of the amounts of solvent and reactive diluent or cosolvent used to prepare the coating compositions is dictated by the type of coating desired.
  • the amount of reactive diluent is usually determined by the film properties desired. Usually these can be attained by ratios of reactive diluent/solvent in the range of about 5/95 to about 30/70.
  • the ratio of reactive cosolvent to solvent is limited by the solubility characteristics of the polymer. Thus a more soluble polymer would require less reactive cosolvent while a less soluble polymer would require more.
  • polymers of these types are soluble in a blend of reactive cosolvent/solvent of about 20/80 to about 60/40.
  • the base coating may be formulated at rather high ratios of reactive cosolvent/solvent i.e., about 60/40 to about 90/10 and then let down with solvent to attain application viscosities.
  • One skilled in the art can easily establish the optimum ratios for a particular coating composition with a minimum of experimentation.
  • the amount of organic polymer used in these compositions is not narrowly critical. However, a practical range for the solution type is about 15 to about 45% by weight of polymer with the amount of reactive solvent being about 10 to about 20% by weight, the amount of crosslinker being about 10 to about 30% by weight and the amount of solvent being about 60 to about 5% by weight.
  • a practical range of organic polymer used for the dispersion type of coating composition is about 35 to about 50% by weight, with the amount of reactive diluent being about 5 to about 20% by weight, the amount of crosslinker being about 5 to about 20% by weight and the amount of solvent beingabout 55 to about 10% by weight.
  • the reactive carbamate derivatives in the coating composition claimed herein can be designated as either reactive cosolvents or reactive diluents depending on the type of coatings formed.
  • the carbamates function as reactive diluents
  • the carbamates function as reactive cosolvents.
  • the term reactive is used herein to mean that the carbamate derivatives can be incorporated into the finished coating by crosslinking agents which cure through NH and/or OH groups.
  • the reactive carbamates used in this invention may be represented by the following: butyl 6-hydroxyhexylcarbamate 2-ethylhexyl 4-hydroxybutylcarbamate butyl 2-hydroxyethylcarbamate 2-ethylhexyl 2,3-dihydroxy-1-propylcarbamate butyl 2,3-dihydroxy-1-propylcarbamate hexyl bis-(2-hydroxyethyl)carbamate 2-(2-hydroxyethoxy) ethyl carbamate 4-hydroxybutyl carbamate 2-hydroxy-1-propyl carbamate 1-hydroxy-2-propyl carbamate 2-hydroxyethyl carbamate 1,3-dihydroxy-2-propyl carbamate 2,3-dihydroxy-1-propyl carbamate 2-hydroxydecyl carbamate 1-(hydroxymethyl)nonyl carbamate 2-hydroxyethyl ( 2-hydroxyethy1)-(ethyl)carbamate
  • Suitable crosslinking agents for the high solids coating compositions described herein are methylol phenols, such as 2,4,6-trimethylolphenol, polyepoxides, such as the glycidyl epoxides or cycloaliphatic epoxides (Araldite* 297, Epon* 582, etc.) and the aminoplasts such as the reaction product of an aldehyde (e.g. formaldehyde, acetaldehyde, paraformaldehyde, trioxane, etc.) with urea, thiourea, melamine, benzoguanamine, acetoguanamine, dicyandiamine and the like.
  • aldehyde e.g. formaldehyde, acetaldehyde, paraformaldehyde, trioxane, etc.
  • the aminoplasts may be etherified with a lower alcohol such as methyl, ethyl, butyl, isobutyl, propyl or isopropyl alcohol.
  • Aminoplasts which are of particular value in high soli.ds coating compositions are the methylated urea-formaldehyde resins, the alkylated benzoguanamines and methylated melamine-formaldehyde resins with the latter being the most desirable.
  • crosslinking agent is not an aminoplast unless there are two or more or no OH groups on the R''' moiety or unless R' and R'' are each hydrogen or neither R' nor R'' is hydrogen.
  • an acidic catalyst is preferred.
  • alkylsulfonic acids such as methane sulfonic acid, ethane sulfonic acid and the like
  • arylsulfonic acids such as p-toluene sulfonic acid
  • alkylaryl sulfonic acids such as a C 10 to C 18 alkylbenzene sulfonic acid
  • dialkyl hydrogen phosphates such as diamyl hydrogen phosphate
  • aryl hydrogen phosphates such as diphenyl hydrogen phosphate and phosphoric acid itself.
  • a blocked isocyanate is an isocyanate adduct which is stable at ambient conditions but dissociates to regenerate isocyanate functionality under the influence of heat. Temperatures of 120 to about 250°C are necessary to release the blocking groups which are usually volatilized from the coating.
  • the dissociation temperature of blocked isocyanates based on commercially utilized blocking agents decrease in the order: epsilon-caprolactam, phenols, methyl ethyl ketoxime, and active methylene compounds.
  • the amount of catalyst required to promote the reaction is dependent upon the curing conditions required in the coating process. Those skilled in the art may readily determine the catalyst level with a minimum of experimentation. In practice if a catalyst is desired it is usually in the level of .02 to about 1% based on the weight of the organic polymer.
  • Example 1 PREPARATION OF 2-HYDROXYETHYL DIMETHYLCARBAMATE
  • ethylene carbonate is treated as in U.S. 4,520,167 with an equimolar amount of dimethylamine, a mixture containing 2-hydroxyethyl dimethylcarbamate is obtained.
  • Example 1 with an equimolar amount of N-ethyl ethanolamine, a mixture containing 2-hydroxyethyl
  • glycerine When glycerine is treated with dimethylcarbonate, a mixture is obtained which contains cyclic carbonates of glycerine (4-hydroxymethyl-1,3-dioxol-2-one and 5-hydroxy-1,3-dioxan-2-one). When the mixture containing these cyclic carbonates is treated with ammonia, another mixture is obtained which contains 1,3-dihydroxy-2-propyl carbamate and 2,3-dihydroxy-1-propyl carbamate.
  • Example 6 When Example 6 is followed except that the ammonia is replaced by pyrrolidine, a mixture is obtained which contains 1,3-dihydroxy-2-propyl tetramethylene carbamate and 2,3-dihydroxy-1-propyl tetramethylenecarbamate.
  • CARGILL-7451 resin, CYMEL-303 crosslinker and p-toluenesulfonic acid catalyst is thermally cured to give a hard, tough glossy coating.
  • Example 9 PREPARATION OF HYDROXYETHYL BUTYLCARBAMATE 274.8 Grams of ethylene carbonate (3.12 moles) were placed in a round bottom flask equipped with stirrer, thermometer, addition funnel and reflux condenser. 228.2 Grams (3.12 mole) of butylamine were charged to the addition funnel and added to the stirred contents of the flask at a rate sufficient to maintain them at 50-80oC. Crude product purity by gas chromatography was 90.6 area % after the mixture had been allowed to stand overnight.
  • Hydroxyethyl butylcarbamate is a good solvent for a polyester resin (Cargill #7451).
  • Example 10 PREPARATION OF 2-HYDROXYETHYL METHYLCARBAMATE 44 Grams (.5 mole) of ethylene carbonate were placed in a 250-ml round bottom flask equipped with stirrer, addition funnel, and thermometer. 38.75 Grams of 40% aqueous methylamine (15.5 g., .5 mole contained methylamine) were charged to the addition funnel and added to the flask with stirring over 1.25 hr. and with the flask contents at 38 to 52°C. The resulting mixture was subjected to vacuum distillation giving 42.54 g. (35.7%) of clear, colorless liquid product boiling at 140°C at 8 mm Hg. The infrared spectrum of this material was consistent with the proposed structure. Purity by gas chromatography was 97.8 area %. The product had a melting point of approximately -36°C and was miscible with water.
  • Example 11 PREPARATION OF HYDROXYPROPYL BUTYLCARBAMATES 290.96 grams (2.85 moles) of propylene carbonate were charged to a 2-1, round bottom flask equipped with stirrer, heater, thermometer, addition funnel and reflux condenser. 211.3 Grams (2.85 moles) of butylamine were charged to the addition funnel and slowly added to the flask contents. The maximum temperature of the reaction was 98°C. The material was allowed to stand and a sample submitted for infrared analysis. The infrared spectrum was consistent with the proposed structures (i.e. an isomeric mixture of 2-hydroxy-1 and 1-hydroxy -2-propyl 1-butylcarbamates). The proposed structures given above were confirmed by Proton NMR analysis.
  • Cargill*-7451 Resin, CELLOSOLVE* Acetate and a blocked aromatic isocyanate prepolymer based on toluene diisocyanate (as taught in U.S. 4,518,522 assigned to Mobay) is thermally cured to a hard, tough glossy coating.
  • EPON*-828 and an amine catalyst is thermally cured to afford a hard, tough, glossy coating.
  • Example 14 PREPARATION OF HYDROXYPROPYL PROPYLCARBAMATES 722 Grams (7.0 moles @ 99% purity) of propylene carbonate was charged to a 2 1 round-bottom flask equipped with stirrer, heating mantle thermometer, feed tank and distillation head. The flask and contents were heated with stirring under nitrogen to 50°C. At this point addition of 436 grams (7 moles @ 98% purity) of n-propylamine was begun and continued for a total of 3.25 hrs. during which time the temperature was maintained between 50 and 62°C without external heat. The temperature was then raised to 72°C and held at this value for an additional 3 hrs. then the flask and contents were allowed to cool and stand overnight. Lights were removed by heating to a maximum temperature of 105°C under 2 mm Hg pressure during 1 hr. with stirring.
  • Example 9 When Example 9 is followed except that a chemically equivalent amount of 2-ethylhexyl amine is substituted for n-butylamine, a mixture containing 2-hydroxyethyl 2-ethylhexylcarbamate is obtained.
  • Example 16 SYNTHESIS OF HYDROXYPROPYL 2-ETHYLHEXYLCARBAMATES When Example 14 is followed except that a chemically equivalent amount of 2-ethylhexylamine is substituted for n-propylamine, an isomeric mixture of 2-hydroxy-1-propyl 2-ethylhexylcarbamate and 1-hydroxy-2-propyl 2-ethylhexylcarbamate is obtained.
  • CARGILL* 7451 RESIN CROSSLINKED BY A BLOCKED AROMATIC ISOCYANATE PREPOLYMER
  • 2-hydroxy-1-propyl 1-butyl carbamate is substituted for hydroxyethyl butylcarbamate, a mixture is obtained which can be thermally cured to a hard, tough, glossy coating.
  • Example 12 When Example 12 is followed except that a chemically equivalent amount of an isomeric mixture of 1-hydroxy-2-propyl 1-propylcarbamate and
  • Example 9 When Example 9 is followed except that the butylamine is replaced by an equimolar amount of N-propyl ethanolamine, a mixture is obtained which contains 2-hydroxyethyl (propyl)(2-hydroxyethyl)- carbamate.
  • Acetate, Cargill-7451 Resin, Cymel*-303 crosslinker and p-toluenesulfonic acid is thermally cured to give a hard, tough, glossy coating.
  • Example 30 PREPARATION OF BUTYL 2-HYDROXYETHYLCARBAMATE When dibutylcarbonate is treated with 2-aminoethanol a mixture is obtained which contains butyl 2-hydroxyethylcarbamate.
  • Example 31 PREPARATION OF 2-ETHYLHEXYL 4-HYDROXYBUTYLCARBAMATE
  • Example 32 PREPARATION OF BUTYL 6-HYDROXYHEXYLCARBAMATE When dibutylcarbonate is treated with 6-amino-1-hexanol a mixture is obtained which contains butyl 6-hydroxy hexylcarbamate.
  • Cargill-7451 resin and Cymel-327 crosslinker is thermally cured to give a hard, tough, glossy coating.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Des compositions de revêtement à haute teneur en particules solides sont obtenues en mélangeant un polymère organique réticulable, un solvant organique et/ou un diluant organique, au moins un dérivé de carbamate réactif, un agent de réticulation et éventuellement un catalyseur de réticulation. Les compositions de revêtement résultantes peuvent être soit des solutions soit des dispersions en fonction du polymère et du solvant particuliers et du carbamate réactif choisi en tant que cosolvant réactif ou diluant réactif.
PCT/US1986/001611 1985-08-09 1986-08-07 Compositions de revetement a base de carbamate WO1987000851A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US76396185A 1985-08-09 1985-08-09
US763,961 1985-08-09
US77386285A 1985-09-09 1985-09-09
US77386185A 1985-09-09 1985-09-09
US77383085A 1985-09-09 1985-09-09
US773,862 1985-09-09
US773,861 1985-09-09
US79767085A 1985-11-13 1985-11-13
US797,670 1985-11-13
US80773885A 1985-12-11 1985-12-11
US807,738 1985-12-11
US773,830 1991-10-09

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WO1987000851A1 true WO1987000851A1 (fr) 1987-02-12

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EP (1) EP0233253A1 (fr)
CA (1) CA1295767C (fr)
WO (1) WO1987000851A1 (fr)

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988002766A1 (fr) * 1986-10-07 1988-04-21 Union Carbide Corporation Compositions de revetement a haute teneur en solides et portees par un solvant
EP0302222A2 (fr) * 1987-08-04 1989-02-08 Union Carbide Corporation Compositions de revêtement à forte teneur en matières solides
EP0355712A2 (fr) * 1988-08-26 1990-02-28 Rheox International, Inc. Additif rhéologique pour compositions de revêtement
US4931157A (en) * 1988-02-18 1990-06-05 Ppg Industries, Inc. Epoxy resin advancement using urethane polyols and method for use thereof
WO1994010212A1 (fr) * 1992-10-30 1994-05-11 Ppg Industries, Inc. Compositions filmogenes aqueuses durcissables a l'aminoplaste durcissable produisant des films resistant a l'attaque de l'acide
WO1994010211A1 (fr) * 1992-10-30 1994-05-11 Ppg Industries, Inc. Compositions filmogenes durcissables a l'aminoplaste produisant des films resistant a l'attaque de l'acide
WO1994010213A1 (fr) * 1992-10-30 1994-05-11 Ppg Industries, Inc. Procede de preparation de revetements composites a couches coloree et transparente resistant a l'attaque de l'acide
US5474811A (en) * 1992-10-23 1995-12-12 Basf Corporation Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat
EP0710676A1 (fr) * 1994-11-03 1996-05-08 Basf Corporation Compositions de revêtement durcissables contenant des résines carbamiques et des additifs
EP0710707A2 (fr) * 1994-11-03 1996-05-08 Basf Corporation Compositions de revêtement durcissables contenant des additifs carbamiques
EP0718332A3 (fr) * 1994-12-21 1997-07-16 Basf Corp Composition pour revêtement contenant des composants fonctionnels de carbamate et d'acryleamide
US5663244A (en) * 1994-04-29 1997-09-02 Ppg Industries, Inc. Flexible aminoplast-curable film-forming compositions providing films having resistance to acid etching
US5709950A (en) * 1994-04-29 1998-01-20 Ppg Industries, Inc. Color-plus-clear composite coatings that contain polymers having carbamate functionality
US5756213A (en) * 1995-10-06 1998-05-26 Basf Corporation Curable coating composition having carbonate-containing component
US5760127A (en) * 1995-10-06 1998-06-02 Basf Corporation Curable coating composition
US5766769A (en) * 1995-10-06 1998-06-16 Basf Corporation Curable composition for coatings
US5770650A (en) * 1995-10-06 1998-06-23 Basf Corporation Curable compositions for coatings
US5792810A (en) * 1995-10-06 1998-08-11 Basf Corporation Curable coating composition including compound having carbamate and hydroxyl functionality
US5827930A (en) * 1995-10-06 1998-10-27 Basf Corporation Curable coating composition
US5854385A (en) * 1995-10-06 1998-12-29 Basf Corporation Coating compositions with low molecular weight carbamate or urea component
US5976701A (en) * 1994-04-29 1999-11-02 Ppg Industries Ohio, Inc. Flexible aminoplast-curable film-forming compositions and composite coating
WO1999057207A2 (fr) * 1998-05-01 1999-11-11 Basf Corporation Procede d'elimination du ridage dans des revetements composites associant couleur et transparence, et compositions utilisees dans ce meme procede
WO2001000689A1 (fr) * 1999-06-28 2001-01-04 Basf Corporation Procede de preparation de polymeres a fonction carbamate
WO2001014431A2 (fr) * 1999-08-20 2001-03-01 Ppg Industries Ohio, Inc. Procede de preparation de polymeres a fonctionnalite carbamate
US6235858B1 (en) 1992-10-30 2001-05-22 Ppg Industries Ohio, Inc. Aminoplast curable film-forming compositions providing films having resistance to acid etching
US6303690B1 (en) 1999-12-15 2001-10-16 Basf Corporation Cathodic electrocoat having a carbamate functional resin and a carbamate functional reactive additive
US6362285B1 (en) 1999-12-15 2002-03-26 Basf Corporation Curable coating compositions containing carbamate functional reactive additives
US6380323B1 (en) 1999-12-15 2002-04-30 Basf Corporation Electrocoat resin compositions containing carbamate functional resins having one or more quaternary ammonium groups and at least one carbamate functional reactive additive
US6391968B1 (en) 1999-12-15 2002-05-21 Basf Corporation Curable coating compositions containing carbamate functional polymers and carbamate functional reactive additives
US6498266B1 (en) 1995-10-06 2002-12-24 Basf Corporation Method of preparing a carbamate- or urea-functional compound
US6541577B2 (en) 2000-12-06 2003-04-01 Basf Corporation Carbamate functional polymers and oligomers
US6730289B2 (en) 2001-01-23 2004-05-04 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Cosmetic composition
US6844395B2 (en) 2001-12-17 2005-01-18 Basf Corporation Asymmetric diisocyanate monomers in urethane polymers and oligomers to reduce crystallinity
US7129280B2 (en) 2001-06-21 2006-10-31 Basf Coatings Ag Mixtures which contain carbamate groups and/or allophanate groups and can be cured thermally and by using actinic radiation
US7160973B2 (en) 2001-12-17 2007-01-09 Basf Corporation Urethane polymers that reduce the effect of polylactone linkages
US7517474B2 (en) 2004-04-14 2009-04-14 Basf Aktiengesellschaft Carbamate-functional triazine derivatives
DE102009003283A1 (de) 2009-05-20 2010-11-25 Basf Se Verwendung von carbamatgruppenhaltigen Triazinderivaten

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520167A (en) * 1984-02-17 1985-05-28 American Cyanamid Co. Hydroxyalkyl carbamate diluent for coating compositions and compositions containing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520167A (en) * 1984-02-17 1985-05-28 American Cyanamid Co. Hydroxyalkyl carbamate diluent for coating compositions and compositions containing the same

Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US4931157A (en) * 1988-02-18 1990-06-05 Ppg Industries, Inc. Epoxy resin advancement using urethane polyols and method for use thereof
EP0355712A2 (fr) * 1988-08-26 1990-02-28 Rheox International, Inc. Additif rhéologique pour compositions de revêtement
EP0355712A3 (fr) * 1988-08-26 1992-01-15 Rheox International, Inc. Additif rhéologique pour compositions de revêtement
US5474811A (en) * 1992-10-23 1995-12-12 Basf Corporation Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat
US5814410A (en) * 1992-10-30 1998-09-29 Ppg Industries, Inc. Method for preparing color-clear composite coatings having resistance to acid etching
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US6235858B1 (en) 1992-10-30 2001-05-22 Ppg Industries Ohio, Inc. Aminoplast curable film-forming compositions providing films having resistance to acid etching
US6228974B1 (en) 1992-10-30 2001-05-08 Ppg Industries Ohio, Inc. Aminoplast curable film-forming compositions providing films having resistance to acid etching
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US6103816A (en) * 1992-10-30 2000-08-15 Ppg Industries Ohio, Inc. Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching
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US5663244A (en) * 1994-04-29 1997-09-02 Ppg Industries, Inc. Flexible aminoplast-curable film-forming compositions providing films having resistance to acid etching
US5798145A (en) * 1994-04-29 1998-08-25 Ppg Industries, Inc. Flexible aminoplast-curable film-forming compositions providing films having resistance to acid etching
US5709950A (en) * 1994-04-29 1998-01-20 Ppg Industries, Inc. Color-plus-clear composite coatings that contain polymers having carbamate functionality
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US6165618A (en) * 1994-11-03 2000-12-26 Basf Corporation Curable coating compositions containing carbamate resin and additives
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US5770650A (en) * 1995-10-06 1998-06-23 Basf Corporation Curable compositions for coatings
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US5760127A (en) * 1995-10-06 1998-06-02 Basf Corporation Curable coating composition
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US6362285B1 (en) 1999-12-15 2002-03-26 Basf Corporation Curable coating compositions containing carbamate functional reactive additives
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CA1295767C (fr) 1992-02-11

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