WO1995032228A1 - Revetements a base d'eau comprenant des reseaux auto-stabilises - Google Patents

Revetements a base d'eau comprenant des reseaux auto-stabilises Download PDF

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Publication number
WO1995032228A1
WO1995032228A1 PCT/US1995/005765 US9505765W WO9532228A1 WO 1995032228 A1 WO1995032228 A1 WO 1995032228A1 US 9505765 W US9505765 W US 9505765W WO 9532228 A1 WO9532228 A1 WO 9532228A1
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weight
percent
composition
acid
macromonomer
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PCT/US1995/005765
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English (en)
Inventor
Jozef Huybrechts
Paul Bruylants
Kerstin Stranimaier
Michael Fryd
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E.I. Du Pont De Nemours And Company
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Priority to AU24375/95A priority Critical patent/AU2437595A/en
Publication of WO1995032228A1 publication Critical patent/WO1995032228A1/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
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
    • C09D155/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof

Definitions

  • This invention relates to an improved aqueous composition for coating a variety of substrates.
  • this invention is directed to a coating composition comprising a graft copolymer, referred to as a self-stabilized latex, having one of neutralized carboxylic-acid or amine functionality in a graft segment thereof which stabilizes the aqueous graft copolymer dispersion.
  • a typical automobile steel panel or substrate has several layers of finishes or coatings.
  • the substrate is typically first coated with an inorganic rust-proofing zinc or iron phosphate layer over which is provided a primer which can be an electrocoated primer or a repair primer.
  • a primer surfacer can be applied to provide for better appearance and/or improved adhesion.
  • a pigmented basecoat or colorcoat is next applied over the primer.
  • a typical basecoat or colorcoat comprises a pigment, which may include metallic flakes in the case of a metallic fimsh.
  • Coating compositions comprise one or more film-forming polymers.
  • Acrylic polymers are typically linear polymers that cure, upon application, by reaction with crosslinking agents.
  • non-linear graft copolymers has been disclosed.
  • U.S. Patent No. 4,801,653 to Das et al. describes the use of hydroxy functional graft copolymers.
  • Das et al. disclose grafting by a condensation reaction between epoxy groups of a glycidyl ester, contained in an acrylic polymer, and carboxy groups on at least a portion of vinyl monomers which are polymerized in the presence of the acrylic polymer.
  • U.S. Patent No. 4,680,352 to Janowicz et al., U.S. Patent No. 4,722,984 to Janowicz , and PCT WO 87/03605 disclose the use of cobalt (Co) chelates as chain transfer agents in free radical polymerization.
  • the latter patents disclose that macromonomers prepared by cobalt chain transfer can be polymerized to produce graft copolymers which are useful in coating and molding resins, including high solid finishes and aqueous or solvent based finishes.
  • the use of such polymers however, have so far found only limited use in the automotive finishes area, as for example disclosed in U.S. Patent No. 5,010,140.
  • the present invention relates to aqueous coating compositions.
  • VOC volatile organic content
  • Water dispersible polymers are well known in the art and have been used to form waterbased coating compositions, pigment dispersions, adhesives and the like. Graft copolymers containing carboxyl groups and the preparation of these polymers is shown in Japanese Laid Open Patent
  • BASF EP 0363723 describes an acid-functional acrylic copolymer dispersion for use in an OEM clear coat to be crosslinked with a melamine formaldehyde binder.
  • the acrylic copolymer is prepared in a solvent in a two- stage process where the hydrophilic part (acid-functional monomer) is concentrated in one of the two stages.
  • the overall copolymer is afterwards neutralized with an amine and dispersed in water.
  • the difference between a one stage product is the solids/viscosity relation being most favorable for the two stage acrylic.
  • a disadvantage of this technology is the fact that the hydrophilic part needs to be over 60% of acid functional monomer which could give problems in humidity resistance.
  • the present method has the advantage that acid functional copolymer macromonomers could be used which provide advantages in terms of humidity resistance, appearance, and lower minimum film-forming temperatures. Also, little to no cosolvent is needed to prepare the graft copolymer dispersion.
  • Another advantage is that introducing hydroxy functional monomers in the hydrophilic part by this method has no negative effects on the solids/viscosity balance.
  • another advantage is that the two stage acrylic can be prepared in water and needs no cosolvent.
  • Bayer patents EP 0218906 and EP 0324334 describe the synthesis of hydroxy-acid functional acrylic copolymers prepared in solution before neutralizing with an amine and dispersing in water. This has the disadvantage of the solids/viscosity balance referred to above.
  • Bayer EP 0334032 describes the synthesis of an acid-functional urethane oligomer which is used to stabilize a waterborne acrylic copolymer dispersion. This technology does not allow hydroxy-functional groups (for crosslinking) in the hydrophilic stabilizing part.
  • AKZO US 5,098,947 describes urethane modified acrylic copolymer dispersions for waterborne coatings. This technology is also limited by the use of cosolvents in which the urethane part is prepared.
  • the aqueous finishes disclosed in the prior art have significant disadvantages, for example, in terms of humidity resistance, durability, appearance and other properties.
  • the problem of developing aqeuous finishes with improved properties remains and has been the subject of considerable research and development in the automotive coatings industry.
  • the present invention offers significant advantages. Acid or amine functional macromonomers can be used which provide improved humidity resistance and appearance. Lower minimum film-forming temperatures may be used. Little to no cosolvent is needed to prepare the graft copolymer dispersion.
  • the acid-functional or amine-functional graft can also be hydroxy functional for crosslinking with the amino formaldehyde and/or the (un)blocked polyisocyanate crosslinkers.
  • the present invention relates to a waterborne curable composition
  • a waterborne curable composition comprising a blend of a graft copolymer, which contains active functional or reactive groups, and a curing agent.
  • the graft copolymer is prepared from an acrylic copolymer macromonomer having at least 5%, based on the weight of the macromonomer of polymerizable alpha-beta ethylenically unsaturated monomers with carboxylic acid or amino functionality and a weight average molecular weight (MW) of 500 to 30,000.
  • the macromonomer is copolymerized with 98-2% of a blend of other alpha, beta- ethylenically unsaturated monomers to form a graft copolymer with a MW of at least 3000, which after neutralizing with an amine or acid or other neutralizing agent can be dispersed in water.
  • the macromonomer can be neutralized with an amine or acid or other neutralizing agent before dispersing in water, and then forming the graft copolymer by copolymerizing the backbone monomers in the presence of an aqueous dispersion of the macromonomer.
  • the curing agent comprises a melamine formaldehyde or alkylated melamine formaldehyde compound or a blocked or unblocked isocyanate compound in a one-package system or an isocyanate compound, preferably a water-dispersible polyisocyanate, in a two-package system, or other crosslinking agents such as epoxies, silanes, carbodiimides, etc, able to react with crosslinking functionalities on the graft copolymer. It has been found that improved aqueous or waterborne coating systems are obtained by using these graft copolymers. Such compositions have the advantage of providing excellent coating properties desirable for an automotive finish.
  • the present invention is directed to a coating composition
  • a coating composition comprising: (a) from about 5 to 98 percent, based on the weight of the binder, of a graft copolymer having a weight average molecular weight of 3,000 to 500,000 comprising: (i) 2 to 98 percent by weight of the graft polymer of a polymeric backbone compring ethylenically unsaturated macromonomers, and (ii) 98 to 2 percent, by weight of the graft polymer, of macromonomers attached to said polymeric backbone at a single terminal point of each macromonomer, said macromonomers comprising from about 5 to 100 percent, based on the weight of the macromonomer, of polymerized ethylenically unsaturated monomers containing carboxylic functionality, or instead amine functionality, and having a weight average molecular weight of about 500-30,000, such that the macromonomers are water soluble or dispersable when neutralized (b) 2 to 50 percent, based
  • This above-described graft copolymer may also be employed together with a curable linear or branched film-forming polymers or binder materials, in various proportions.
  • the composition may comprise linear or branched hydroxy-functional acrylic, polyester, or polyurethane copolymers.
  • Further binder materials, in relatively minor amounts, include, for example thickeners, adhesion promoters, etc.
  • the present composition is especially useful for finishing the exterior of automobiles and trucks and parts thereof.
  • the present composition depending on the presence of pigments and other conventional components, may be used as a primer, primer surfacer, basecoat, and/or clearcoat. It is especially advantageous for use in an aqueous clearcoat.
  • the invention also includes a process for coating a substrate with the above coating composition.
  • the claimed composition further includes a substrate having adhered thereto a coating according to the above composition.
  • the graft copolymer and the process for making the graft copolymer are also part of this invention.
  • the present invention offers several significant advantages.
  • graft copolymers with acid groups or amino groups concentrated in one segment require less acid or amino groups to get a stable dispersion, thus leaving fewer moisture sensitive carboxylic or amino groups in the final coating.
  • standard emulsions are stabilized by surfactants which besides remaining in the film as moisture sensitive residues, migrate to the coating interfaces and generate weak boundary layers which lead to poor adhesion and delamination.
  • the surfactants also stabilize foam formed by trapped air during spraying, leading to pinholing.
  • the compositions according to the present invention can be made with lesser amounts of surfactants, preferably no surfactants.
  • the waterborne coatings of the present invention comprise an acrylic-based binder system in an aqueous base.
  • This binder system comprises, in its overall concept, a water soluble or dispersible acrylic graft copolymer which is formed by free radical initiated copolymerization of 2-98% (by weight) alpha-beta unsaturated monomers in the presence of an acrylic macromonomer.
  • the acrylic macromonomer has an average number molecular weight (MN) of between 500 to 30,000 and containing at least 5% of an acid or amine functional alpha-beta unsaturated monomer.
  • acrylic resins form stable solutions or dispersions in water.
  • These resins form particles, either alone or in aggregate with other such resins in the composition, in which the macromonomers are relatively hydrophilic and hence soluble or dispersible in the aqueous carrier, and the polymeric backbone (to which the macromomers are attached) is relatively water insoluble.
  • Such particles may be crosslinked or uncrosslinked, for example by means of diacrylate monomeric units, and suitably have an average particle size of 50 to 1000 nanometers (nm), preferably 100 to 250 nm.
  • the acrylic macromonomer is preferably prepared using a free radical initiator in a solvent with a Co (II) or Co (III) chelate chain transfer agent and contains 5 to 100 percent, preferably at least 10 percent and more preferably 20 to 40 perecent, by weight of a reactive functional monomer, e.g., carboxylic functional monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and their anhydrides (which can be hydrolyzed to the acid after polymerization).
  • a reactive functional monomer e.g., carboxylic functional monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and their anhydrides (which can be hydrolyzed to the acid after polymerization).
  • amine functional monomers may be used, including t-butylamino ethyl methacrylate, diethyl amino ethyl (or dimethyl amino) acrylate, and diethyl amino ethyl methacrylate, and the like.
  • the macromonomer is based on methacrylic acid or diethyl (or dimethyl) amino ethyl methacrylate.
  • the total polymeric and oligomeric components of a coating composition are conventionally referred to as the "binder” or “binder solids” and are dissolved, emulsified or otherwise dispersed in the aqueous liquid carrier.
  • the binder solids generally include all the normally solid polymeric components of the composition.
  • catalysts, pigments, or chemical additives such as stabilizers are not considered part of the binder solids.
  • Non-binder solids other than pigments usually do not amount for more than about 10% by weight of the composition.
  • the coating composition of the present invention suitably contains about 10-90%, more typically 50-70% by weight of the binder, and about 40-90%, more typically 50-70% by weight, of an aqueous carrier.
  • the present composition suitably comprises about 5 to 98 percent, preferably 20 to 90%, based on the weight of the binder, of the specified graft polymer.
  • the composition may comprise 5 to 98% of the specified graft polymer.
  • the graft copolymer contains about 2-98%, preferably 5-
  • the graft copolymer has a weight average molecular weight of about at least 3,000, preferably 20,000 to 500,000, most preferably 20,000 to 300,000.
  • the side chains of the graft copolymer are formed from relatively water soluble macromonomers that have a weight average molecular weight of about 500-30,000 and preferably 2,000-10,000 and contain about 5-100% by weight and preferably 15-40% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid or amine monomers which are then at least partially neutralized. These side chains are relatively hydrophilic and keep the graft polymer well dispersed in the resulting coating composition.
  • the backbone of the graft copolymer is hydrophobic relative to the side chains, but can contain polymerized ethylenically unsaturated acid or amine monomers or salts thereof.
  • the backbone may contain polymerized monomers selected preferably from the group consisting of acrylates and styrene, but can contain up to 50% of methacrylates.
  • Such monomers include alkyl methacrylates and acrylates, cycloaliphatic methacrylates and acrylates and aryl methacrylates and acrylates as are listed hereinafter and also may contain up to 50% by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated non-hydrophobic monomers which may contain reactive functional groups.
  • Examples of such monomers are hydroxy ethyl acrylate, hydroxy ethyl methacrylate, acrylamide, nitro phenol acrylate, nitro phenol methacrylate, phthalimido methyl acrylate, and phthalimido methacrylate.
  • vinyl monomers can be incorporated into the backbone copolymer, e.g., ethylenically unsaturated sulfonic, sulfinic, phosphoric or phosphonic acid and esters thereof also can be used such as styrene sulfonic acid, acrylamido methyl propane sulfonic acid, vinyl phosphonic acid and its esters and the like.
  • the waterborne acrylic graft copolymers contain 0-60 or more preferably 10-40 parts by weight of hydroxy functional acrylic monomers, e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate. All or most of these may be present in the side chains and may serve as crosslinking sites.
  • hydroxy functional acrylic monomers e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate. All or most of these may be present in the side chains and may serve as crosslinking sites.
  • the graft polymer comprises macromonomeric side chains attached to a polymeric backbone.
  • Each macromonomer ideally contains a single terminal ethylenically unsaturated group which is polymerized into the backbone of the graft copolymer and typically contains polymerized monomers of methacrylic acid, its esters, nitriles, amides or mixtures of these monomers.
  • the above-mentioned acids or amines also can be used in the backbone of the graft copolymer, but usually in a lesser amount by weight than in the macromonomeric arms, in order to maintain the water-insolubility of the backbone.
  • the backbone and the macromonomers have acid in both parts of the graft copolymer, or alternatively amine groups, depending on whether the system in cationic or anionic.
  • ethylenically unsaturated monomers in addition to the minimum 5% of acid or amine monomers, up to 90% by weight, based on the weight of the macromonomer, of other polymerized ethylenically unsaturated monomers can be present in the macromonomer, for example, but not limited to acrylic and methacrylic acid esters of straight-chain or branched monoalcohols of 1 to 20 carbon atoms.
  • the majority of these monomers should be methacrylate, perferably 60-80% of the total macromonomer, e.g.
  • alkyl methacrylates having 1-12 carbons in the alkyl group can be used such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2- ethyl methacrylate, nonyl methacrylate, lauryl methacrylate and the like can be used.
  • Cycloaliphatic methacrylates can be used such as trimethylcyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, isobornyl methacrylate, 2- ethylhexyl methacrylate, and the like.
  • Aryl methacrylates such as benzyl methacrylate also can be used.
  • Ethylenically unsaturated monomers containing hydroxy functionality include hydroxy alkyl acrylates and hydroxy alkyl methacrylates, wherein the alkyl has 1 to 12 carbon atoms.
  • Suitable monomers include hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy isopropyl acrylate, hydroxy butyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, hydroxy isopropyl methacrylate, hydroxy butyl methacrylate, and the like, and mixtures thereof.
  • Reactive functionality may also be obtained from monomer precursors, for example, the epoxy group of a glycidyl methacrylate unit in a polymer.
  • Such an epoxy group may be converted, in a post polymerization reaction with water or a small amount of acid, to a hydroxy group, or with ammonia and/or a primary amine to give a hydroxy amine.
  • Suitable other olefinically unsaturated comonomers include: acrylamide and methacrylamide and derivatives as alkoxy methyl (meth) acrylamide monomers, such as methacrylamide, N-isobutoxymethyl methacrylamide, and N-methylol methacrylamide; maleic, itaconic and maleic anhydride and its half and diesters; vinyl aromatics such as styrene and vinyltoluene; polyethylene glycol monoacrylates and monomethacrylates; aminofunctional (meth) acrylates as, e.g., diethylaminoethylmethacrylate and t- butylaminoethylmethacrylate; glycidyl functional (meth) acrylates as gly
  • the graft polymer may be prepared by polymerizing ethylenically unsaturated monomers in the presence of macromonomers each having a terminal ethylene unsaturation for grafting.
  • the resulting graft polymer can be envisioned as being composed of a backbone having a plurality of macromonomer "arms" attached thereto.
  • both the macromonomer arms and the backbone may have reactive functionalities capable of reacting with a crosslinking compound or polymer, although it is optional to have such reactive functionalities only on the macromonomers.
  • the macromonomers referred to as having carboxylic or amine functionality may be part of a mixture of macromonomers of which a portion do not have any carboxylic or amine functionality or variable amounts of carboxylic or amine functionality. It is also understood that, in preparing any macromonomers, there is a usually a normal distribution of functionality. To ensure that the resulting macromonomer only has one terminal ethylenically unsaturated group which will polymerize with the backbone monomers to form the graft copolymer, the macromonomer is polymerized by using a catalytic chain transfer agent.
  • the monomers are blended with an inert organic solvent which is water miscible or water dispersible and a cobalt chain transfer agent and heated usually to the reflux temperature of the reaction mixture.
  • an inert organic solvent which is water miscible or water dispersible
  • a cobalt chain transfer agent is heated usually to the reflux temperature of the reaction mixture.
  • additional monomers and cobalt catalyst and conventional polymerization catalyst are added and polymerization is continued until a macromonomer is formed of the desired molecular weight.
  • Preferred cobalt chain transfer agents or catalysts are described in
  • the macromonomer is preferably formed in a solvent or solvent blend using a free radical initiator and a Co (II or III) chelate chain transfer agent, although it can be formed in aqueous solution or emulsion when using diaquabis(borondifluoro-2,3-dioxyimiobutane groups.
  • Azo-initiators (0.5-5% weight on monomer) can be used in the synthesis of the macromonomers in the presence of 2-5,000 ppm (on total monomer) of Co (II) chelate in the temperature range between 50- 180° Q more preferably azo type initiators as, e.g., 2,2'-azobis (2,4 dimethylpentanenitrile), 2,2'-azobis (2-methylpropanenitrile), 2,2'-azobis (2-methylbutanenitrile), 1,1'- azo (cyclohexane carbonitrile) and 4,4-azobis (4-cyanopentanoic) acid.
  • azo type initiators e.g., 2,2'-azobis (2,4 dimethylpentanenitrile), 2,2'-azobis (2-methylpropanenitrile), 2,2'-azobis (2-methylbutanenitrile), 1,1'- azo (cyclohexane carbonitrile) and 4,4-azobis (4-cyanopentanoic)
  • the macromonomer After the macromonomer is formed as described above, its solution can be used "as is" or solvent can be optionally stripped off and the backbone monomers are added to the macromonomer along with additional solvent and polymerization catalyst.
  • Any of the aforementioned azo type catalysts can be used as can other suitable catalysts such as peroxides, peresters and hydroperoxides. Typical of such catalysts are di-tertiarybutyl peroxide, di- cumylperoxide, tertiaryamyl peroxide, cumenehydroperoxide, di(n-propyl) peroxydicarbonate, peroxyesters such as amyl peroxyacetate and the like.
  • Redox catalysts e.g., sodium persulfate/ascorbic acid can also be used. Polymerization is continued usually at the reflux temperature of the reaction mixture until a graft copolymer is formed of the desired molecular weight.
  • Typical solvents that can be used to form the macromonomer or the graft copolymer are aromatics, aliphatics, ketones such as methyl ethyl ketone, isobutyl ketone, ethyl amyl ketone, acetone, alcohols such as methanol, ethanol, n-butanol, isopropanol, esters such as ethyl acetate, glycols such as ethylene glycol, propylene glycol, ethers such as tetrahydrofuran, ethylene glycol mono butyl ether and the like, and as mentioned above, water and mixtures thereof with water miscible solvents.
  • the graft polymer can be made by copolymerizing the macromonomer in solvent with the rest of the monomer blend, to form a graft copolymer, thereafter neutralizing it and dispersing in water. Solvents can eventually be stripped off after the water dispersion has been formed.
  • suitable inorganic bases include ammonium hydroxide, sodium hydroxide, and potassium hydroxide.
  • Typical amines that can be used include amino methyl propanol, amino ethyl propanol, dimethyl ethanol amine, triethylamine, dimethylethanolamine, dimethylaminomethylpropanol and aminomethylpropanol and the like.
  • One preferred amine is amino methyl propanol and the preferred inorganic base is ammonium hydroxide.
  • neutralizing agents for amines organic or inorganic acids, e.g. acetic acid, formic acid, lactic acid, hydrochloric acid, etc. may be used.
  • the conversion of the graft polymer into a water dispersion can be done by admixing the graft polymer solution with an appropriate neutralizing agent and diluting with water, or the polymerized graft copolymer solution can be stirred slowly into a solution of water and the neutralizing agent.
  • the degree of neutralization of the dispersion can be from 10 to 150% of the total amount of reactive groups, preferably from 80-105%.
  • the final pH of the dispersion can accordingly be about 4-10, preferably 7-10 for an anionic system and 4-7 for a cationic system.
  • Anionic, cationic or non-ionic surfactants can be used, but preferably not since they might hurt humidity resistance afterwards. As indicated above, not having to use a surfactant is one of the significant advantages of the present invention.
  • the graft copolymer can be formed directly into water, wherein the macromonomer is neutralized and dissolved or dispersed into water.
  • the graft copolymer is formed by copolymerizing the rest of the monomer blend in the presence of the macromonomer water solution or dispersion. This procedure has the advantage that less or no cosolvent is used in the overall process and solvent stripping can be eliminated. Another advantage is that higher molecular weight graft polymers can be obtained than in solvent polymerization.
  • Mixtures of suitably compatible macromonomers can be used as long as all are either cationic or anionic in water.
  • Water-soluble free radical initiators can be used, suitably in the temperature range of 20-98°C, e.g., peroxides, such as ammoniumpersulfate, redox initiators such as t-butylhydroperoxide/ascorbic acid.
  • peroxides such as ammoniumpersulfate
  • redox initiators such as t-butylhydroperoxide/ascorbic acid.
  • chain transfer agents other than the cobalt chelates can be used as, e.g., mercaptans: mercaptoethanol, t- dodecylmercaptan, N-dodecylmercaptan.
  • small amounts of difunctional alpha-beta unsaturated compounds can be used as, e.g., ethyleneglycol dimethacrylate or hexanedioldiacrylate. This can result in crosslinked particles.
  • the overall graft copolymer water borne dispersion should be characterized by an acid or amine value of from 10 to about 150 (mg KOH/g resin solids), more preferably from 15 to about 70, and an hydroxyl number of about 0 to about 250 (mg KOH/g resin solids), more preferably from 40 to 150.
  • binder systems are utilized to produce waterborne coatings by blending with other suitable components in accordance with normal paint formulation techniques.
  • the graft copolymers of the present invention are useful as film forming vehicles in the preparation of waterborne coating compositions such as, for example, basecoat or clearcoat compositions useful in automotive applications.
  • the resultant coating compositions have low volatile organic content, preferably to a maximum of 3.50 pounds/gallon.
  • the graft copolymer is combined with a crosslinking agent in the amount of 2 to 50 percent by weight of binder, preferably 10 to 40 percent by weight of binder. If the binder is used in a formulation that is cured with a curing agent containing N-methylol and/or N-methylol ether groups, the curing agent should be dispersed in the water based graft copolymer dispersion to form a stable overall dispersion.
  • curing agents examples include amino resins obtained by reacting an aldehyde, such as formaldehyde, with a compound containing amino group such as melamine, urea and benzoguanamine and total or partial etherification of the N-methylol group with an alcohol such as, e.g., methanol, n-butanol, isobutanol.
  • aldehyde such as formaldehyde
  • a compound containing amino group such as melamine, urea and benzoguanamine
  • an alcohol such as, e.g., methanol, n-butanol, isobutanol.
  • compositions which will crosslink under elevated baking temperatures of about 60-180°C for abut 5-60 minutes about 10 to 60%, preferably 10 to 25% by weight, based on the weight of the binder, of a water- soluble water dispersible alkylated melamine formaldehyde crosslinking agent having 1-4 carbon atoms on the alkylated group is preferred.
  • crosslinking agents are generally partially alkylated melamine formaldehyde compounds and may be monomeric or polymeric and if polymeric have a degree of polymerization of about 1-3.
  • Typical alcohols used to alkylate these resins are methanol, ethanol, propanol, butanol, isobutanol, and the like, preferred alkylated melamine crosslinking agents that are commercially available include CymelTM 373, 385, 1161, 350, or 1168 (Monsanto) or ResimineTM 714, Resimine- 730 and 731, ResimineTM 735 and 745 (Cyanamide).
  • Coating compositions of this invention containing a melamine crosslinking agent can contain about 0.1 to 1.0%, based on the weight of a binder, of a strong acid catalyst or a salt thereof to lower curing temperatures and time.
  • Paratoluene sulfonic acid is a preferred catalyst or its ammonium salt.
  • Other catalysts that can be used are dodecyl benzene sulfonic acid, phosphoric acid and amine or ammonium salts of these acids.
  • water dispersable polyisocyanates include biuret and cyclotrimers of hexamethylene dusocyanate, isophorone dusocyanate and tetramethyl xylylene dusocyanate. These isocyanates may be modified to such an extent that they contain ionic groups to ease dispersion into water.
  • a cure promoting catalyst is utilized in conjunction with the isocyanate crosslinking or curing agent.
  • Preferred catalysts are organometallics, suitably dibutyl tin dilaurate, dibutyl tin di-2-ethylhexoate, zinc octoate, zinc napthenate, vanadium acetyl acetonate, or zirconium acetyl acetonate, in an effective curing amount, typically from about 0.1 to 2% by weight of binder.
  • Such catalysts are optional, for example, elevated temperature and or time may suffice to cure the composition.
  • Typical isocyanate crosslinking agents which may be used for curing the composition include both compounds and polymers, blocked or unblocked.
  • suitable polyisocyanates include monomeric polyisocyanates such as toluene dusocyanate and 4,4'-methylene-bis(cyclohexylisocyanate), isophorone dusocyanate and
  • NCO-prepolymers such as the reaction products of monomeric polyisocyanate such as those mentioned above with polyester or polyether polyols.
  • Particularly useful isocyanates are isophorone dusocyanate and the biuret-form 1,6-hexamethylene dusocyanate commercially available from Bayer as "Desmodur” N or the like.
  • crosslinking agents include 4,4'-biphenylene dusocyanate, tetramethyl dusocyanate, ethylethylene dusocyanate, 1,3-cyclopentylene dusocyanate, 1,3-phenylene dusocyanate, 1,5-naphthalene dusocyanate, bis(4-isocyanatocyclohexyl)methane, and the like.
  • Trifunctional isocyanates may be used, for example, triphenylmethane triisocyanate, 1,3,5-benzene triisocyanate, 2,4,6-toluene triisocyanate, an adduct of trimethylol and tetramethyl xylene dusocyanate sold under the tradename "Cythane 3160,” “Desmodur” N 3390 which is the trimer of hexamethylene dusocyanate, and the like.
  • a polyisocyanate acrylic copolymer derived from isocyanatoethyl methacrylate commercially available as TMI
  • TMI polyisocyanate acrylic copolymer derived from isocyanatoethyl methacrylate
  • the polyisocyanate may optionally be blocked.
  • suitable blocking agents are those materials which would unblock at elevated temperatures, for example, lower aliphatic alcohols such as methanol, oximes such as methylethyl ketone oxime, and lactams such as epsiloncaprolactam.
  • Blocked isocyanates can be used to form stable one-package systems.
  • Polyfunctional isocyanates with free isocyanate groups can be used to form two-package room temperature curable systems. In these systems, the product and isocyanate curing agent are mixed just prior to their application.
  • film-forming polymers preferably 0 to 55 percent by weight (and concomitantly 45 to 100% by weight of the graft copolymer), based on the weight of the binder, may also be used in conjunction with the graft copolymer.
  • Other film forming polymers may be linear or branched and may include acrylics, acrylourethanes, polyesters, polyester urethanes, polyethers, and polyether urethanes that are compatible with the graft polymer.
  • An organic cosolvent is also typically utilized in the present composition, preferably in minimal amounts, less than 20% by weight of carrier, to facilitate formulation and application of the coating compositions of the present invention.
  • An organic solvent is utilized which is compatible with the components of the composition.
  • compositions according to the present invention may • contain a variety of other optional ingredients, including pigments, pearlescent flakes, fillers, plasticizers, antioxidants, surfactants and flow control agents.
  • an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers can be added in the amount of about 0.1-5% by weight, based on the weight of the binder.
  • Such stabilizers include ultraviolet light absorbers, screeners, quenchers, and specific hindered amine light stabilizers.
  • an anitoxidant can be added, in the about 0.1-5% by weight, based on the weight of the binder.
  • Typical ultraviolet light stabilizers that are useful include benzophenones, triazoles, triazines, benzoates, hindered amines and mixtures thereof. Specific examples of ultraviolet stabilizers are disclosed in U.S. Patent 4,591,533, the entire disclosure of which is incorporated herein by reference.
  • the composition may also include conventional formulation additives such as flow control agents, for example, Resiflow® S (polybutylacrylate), BYK 320 and 325 (high molecular weight polyacrylates); rheology control agents, such as fumed silica, microgels, and non-aqueous dispersion polymers, and the like.
  • flow control agents for example, Resiflow® S (polybutylacrylate), BYK 320 and 325 (high molecular weight polyacrylates); rheology control agents, such as fumed silica, microgels, and non-aqueous dispersion polymers, and the like.
  • the present composition can be pigmented and used as the colorcoat, monocoat, primer, or primer surfacer.
  • the composition has excellent adhesion to a variety of metallic or non-metallic substrates, such as previously painted substrates, cold rolled steel, phosphatized steel, and steel coated with conventional primers by electrodeposition.
  • the present composition can be used to coat plastic substrates such as polyester reinforced fiberglass, reaction injection-molded urethanes and partially crystalline polyamides.
  • typical pigments that can be added to the composition include the following: metallic oxides such as titanium dioxide, zinc oxide, iron oxides of various colors, carbon black, filler pigments such as talc, china clay, barytes, carbonates, silicates and a wide variety of organic colored pigments such as quinacridones, copper phthalocyanines, perylenes, azo pigments, indanthrone blues, carbazoles such as carbazole violet, isoindolinones, isoindolones, thioindigo reds, benzimidazolinones, metallic flake pigments such as aluminum flake and the like.
  • metallic oxides such as titanium dioxide, zinc oxide, iron oxides of various colors, carbon black
  • filler pigments such as talc, china clay, barytes, carbonates, silicates and a wide variety of organic colored pigments such as quinacridones, copper phthalocyanines, perylenes, azo pigments, indanthrone blues, carbazoles such
  • the pigments can be introduced into the coating compositon by first forming a mill base or pigment dipersion with any of the aforementioned polymers used in the coating composition or with another compatible polymer or dispersant by conventional techniques, such as high speed mixing, sand grinding, ball milling, attritor grinding or two roll milling.
  • the mill base is then blended with the other constituents used in the coating composition, to obtain the present coating compositions.
  • the coating composition can be applied by conventional techniques such as spraying, electrostatic spraying, dipping, brushing, flowcoating and the like.
  • the preferred techniques are spraying and electrostatic spraying.
  • the present composition may be used as an ambient cure, especially for refinish, or at elevated temperature.
  • the composition is typically baked at 100-150°C for about 15-30 minutes to form a coating about 0.1-3.0 mils thick.
  • the composition is used as a clearcoat, it is applied over the colorcoat which may be dried to a tack-free state and cured or preferably flash dried for a short period before the clearcoat is applied.
  • the colorcoat/clearcoat finish is then baked as mentioned above to provide a dried and cured finish.
  • topcoat is applied to the basecoat without curing or completely drying the basecoat.
  • the coated substrate is then heated for a predetermined time period to allow simultaneous curing of the base and clear coats.
  • This example illustrates the use of a Co (II) chelate in the synthesis of the following macromonomers.
  • the chelate is BF2 bridged Co (II) (l,2-diphenyl-l,2-dioxoiminoethane)2 (H2 ⁇ )2 chelate, as described in example 44B of EP 0199436.
  • Mixture 1 (of Table 1 below) was heated at reflux ( ⁇ 80° C) in a reaction vessel that was kept under nitrogen.
  • Mixture 2 was added over 4 hours. Simultaneously with the addition of mixture 2, mixture 3 was added over 90 min. followed immediately by mixture 4.
  • Mixture 5 was added, for rinsing, followed by a 5 min. hold. Afterwards, mixture 6 was added over 30 min. followed by another rinsing step and held for 60 min. During the total process, the temperature was kept at reflux.
  • Table 1 various combinations of monomers were used in Examples 1 to 4.
  • Vazo® 52 initiator 0.1 0.1 Methyl ethyl ketone 1.9 1.9
  • EXAMPLE 3 This example again illustrates the use of a Co (II) chelate in the synthesis of the following macromonomers which comprise carboxylic-acid and hydroxy functionality.
  • the chelate is the same as in the above Examples 1-2, as described in EP 0199436.
  • a glass reactor with two inlets, one for the monomer feed and one for the initiator feed was employed.
  • the reaction mixture was kept at reflux temperature throughout the process, while the following components were introduced into the reactor as explained below.
  • Part 1 was heated to reflux, under nitrogen, until dissolved. Part 2 was then added over 2 hours. Part 3 was used for rinsing. The mixture was then held at reflux for 1 hour. Part 4 was fed over 1 hour. Part 5 was used for rinsing, and then the reaction mixture was held at reflux for one hour.
  • the reaction product was characterized, including AN (acid number), MN (number average molecular weight, and MW (weight average molecular weight), as follows:
  • EXAMPLE 4 This example illustrates the use of a Co (II) chelate (in which the equatorial ligands are BF2 bridged 2,3-dioximinobutane groups as described in EP 0199436) in the synthesis of an acid functional macromonomer, which is then dissolved in water. The following components were reacted in a glass reactor as explained below.
  • Co (II) chelate in which the equatorial ligands are BF2 bridged 2,3-dioximinobutane groups as described in EP 0199436
  • Part 1 was heated, under nitrogen, at reflux. Part 2 was then added over 3 hours. Part 3 was used for rinsing and the mixture was held at reflux for 10 minutes. Part 4 was added over 1 hour and Part 5 was used for rinsing. The mixture was then held at reflux for 10 minutes and cooled to 80°C. Part 6 was then added and mixed for 10 minutes, followed by Part 7 (deionized water) for rinsing.
  • the product exhited the following characteristics:
  • This example illustrates the use of a sulfur chain transfer agent in the synthesis of an acid functional polymer.
  • this example illustrates the prepareation of an n-butyl methacrylate/methacrylic acid (96/14) copolymer with a sulfur chain transfer agent.
  • Part 1 (solvent) was heated to reflux.
  • Part 2 (including monomer mixture) was added over 3 hours at reflux, and Part 3 was used for rinsing. The mixture was held at reflux for 10 minutes and then Part 4 (additional initiator) was added over 1 hour.
  • Part 5 was used for rinsing, and the mixture was again held at reflux for 10 minutes, followed by cooling to 80°C.
  • Part 6 (including amine and deionized water) was then added and mixed for 10 minutes, followed by rinsing with the additional deionized water of Part 7.
  • the product exhibited the following characteristics.
  • EXAMPLE 6 This example illustrates the preparation of a graft acrylic copolymer dispersion.
  • this example illustrates the preparation of a graft polymer comprising 70% by weight methyl methacrylate/n-butyl acrylate (in the ratio of 20/80) reacted with 30% macromonomer (abbreviated "macro") of n-butyl methacrylate/methacrylic acid (in the weight ratio of 86/14).
  • macromonomer abbreviated "macro"
  • Vazo® 67 initiator 0.1 n-Butylglycolether 0.9
  • Part 1 was heated to 90-95°C. Part 2 was added simultaneously over 4 hours, after which Part 3 was used for rinsing. The mixture was held at reflux for 1 hour. The product was a stable dispersion, with no settling on storage, and exhibited the following properties.
  • MN 8800 peak molecular weight
  • COMPARATIVE EXAMPLE 7 For comparison to Example 6, this example illustrates the preparation of a acylic coplymer, but in which the macromonomer used in Example 4 was replaced with the macromonomer of Example 5 which has approximately the same molecular weight and monomer composition.
  • This acrylic copolymer shows a bimodal distribution, with the lower molecular weight corresponding to unreacted oligomer from Example 6 showing no incorporation. This proves that the macromonomer of Example 5 is not copolymerized to provide stabilization of the overall composition. The dispersion is therefore not stable and settles out.
  • EXAMPLE 8 This example illustrates the preparation of another graft acrylic copolymer dispersion consisting, by weight, of 92.5% backbone made from styrene / n-butyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate (in the weight ration 20 / 43.5 / 7 / 22) and 7.5% macromonomer (from Example 1) made from methyl methacrylate/ methacrylic acid (in the weight ratio 4.5 / 3).
  • the graft copolymer was formed in solution before dispersion in water as follows.
  • Part 1 was heated and low boiling solvent stripped off until a reflux of 137-139° C was obtained.
  • Part 2 was then added over 3 hours at a reflux of 137-139°C.
  • Part 3 was used for rinsing and Part 4 then added over 30 min. Again, the reactor inlet was rinsed and the contents held at reflux for 30 min. Finally, 5.83 parts were stiipped off.
  • the reactor contents were then cooled to 60-70°C and neutralized with dimethyethanolamine in the amount of 2.30 parts.
  • the graft copolymer was dispersed in deionized water in the amount of 85.20 parts and the pH adjusted to 85.20 (total 187.5 parts).
  • the graft copolymer product exhibited the following characteristics:
  • Viscosity 10.000 cps pH 9
  • This example illustrates the preparation of another graft acrylic copolymer dispersion consisting, by weight, of 90% backbone made from styrene / n-butyl methacrylate / n-butyl acrylate / 2-hydroxyethyl acrylate (in the weight ratio of 20 / 40 / 8 / 22) and 10% macromonomer (from Example 1) made from methyl methacrylate / methacrylic acid (in the weight ratio of 6 / 4).
  • the graft copolymer formed in solution before dispersion in water. The following components were used:
  • Part 1 was heated and low boiling solvent stripped off until a reflux of 137-139° C was obtained. Part 2 was then added over 3 hours at 137-139°C. Part 3 was used for rinsing and then Part 4 was added over 30 min. Part 5 was used for 5 rinsing and then the reaction mixture was held at reflux for 30 min. Finally 7.1 parts were stripped off. The reaction mixture was cooled to 60-70°C and dimethylethanolamine in the amount of 3 parts was used to neutralize the mixture. Deionized water in the amount of 84.5 parts was used to disperse the graft copolymer and the pH adjusted to 8-8.3 (total parts 187.5).
  • the graft 0 polymer product was characterized as follows:
  • EXAMPLE 10 o This example illustrates the preparation of another graft acrylic copolymer dispersion consisting, by weight, of 75% backbone made from styrene / n-butyl methacrylate / n-butyl acrylate / 2-hydroxyethyl acrylate (in the weight ratio of 20 / 39.5 111 18.5) and 15% macromonomer (from Example 2) made from methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic 5 acid (in the weight ratio of 7.8 / 4.2 / 3).
  • the following components were used wherein the graft copolymer was formed in solution before dispersion in water. Part 1 Part- » bv Weight n-Butylglycolether 11.2 n-Butyldiethyleneglycol ether 3.7
  • Part 1 was heated and low boiling solvent stripped off until a reflux of 137-139° C was obtained. Part 2 was then added over 3 hours at 137-139°C. Part 3 was used for rinsing and then Part 4 was added over 30 min. Part 5 was used for rinsing and then the reaction mixtuie was held at reflux for 30 min. Finally 11.5 parts were stripped off. The reaction mixture was cooled to 60-70°C and dimethylethanolamine in the amount of 2.30 parts was used to neutralize the mixture. Deionized water in the amount of 85.20 parts was used to disperse the graft copolymer and the pH adjusted to 8-8.3 (total parts 187.5). The graft polymer product was characterized as follows:
  • This example illustrates the preparation of a graft acrylic copolymer consisting by weight 95% backbone made from styrene / n-butyl acrylate / 2-hydroxypropyl methacrylate (in the weight ratio of 21140128) and 5% macromonomer (from Example 1) made from methyl methacrylate / methacrylic acid (in the weight ratio 3 / 2).
  • This graft copolymer was formed in a water dispersion using the following components:
  • Part 1 was heated to 95°C, plus or minus 2 degrees, and adjusted to a pH of 7.5- 7.8.
  • Part 2A monomers
  • 2B azo solution
  • Part 3 deionized water
  • Part 4 was then added over 60 min and the reactor inlet rinsed marh Part 5.
  • the mixture was then again held at 95 +/- 2°C for 30 min. and finally rinsed with Part 6 (water).
  • the reaction product was characterized as follows:
  • Viscosity 500 cps pH 8.1
  • EXAMPLE 12 This example illustrates the preparation of a graft acrylic copolymer consisting by weight 90% backbone made from styrene / n-butyl acrylate / 2-hydroxypropyl methacrylate (in the weight ratio of 47 / 38 / 25) and 10% macromonomer (from Example 2) made from methyl methacrylate / hydroxyethyl methacrylate or HEMA / methacrylic acid (in the weight ratio 5.2 / 2.8 / 2).
  • This graft copolymer was foimed in a water dispersion using the following components: Part i
  • Part 1 was heated to 95°C, plus or minus 2 degrees, and adjusted to a pH of 7.5- 7.8.
  • Part 2A monomers
  • 2B azo solution
  • Part 3 deionized water
  • Part 4 was then added over 60 min and the reactor inlet rinsed marh Part 5.
  • the mixture was then again held at 95 +/- 2°C for 30 min. and finally rinsed with Part 6 (water).
  • EXAMPLE 13 This example illustrates the preparation of a graft acrylic copolymer consisting by weight of 90% backbone made from styrene / n-butyl acrylate / 2-hydroxypropyl methacrylate (in the weight ration of 22 / 40 / 28) and 10% macromonomer (from Example 1) made of methyl methacrylate / methacrylic acid (in the weight ratio of 6 / 4).
  • This graft copolymer was formed in a water dispersion using the following components:
  • Part 1 was heated to reflux at 95 +/- 2°C and the pH adjusted to 7.5-7.8.
  • Part ' 2 A (monomers) and Part 2B (azo solution) was added simultaneously over 4 hours at 95°C +/- 2°C.
  • Part 3 deionized water
  • Part 4 was added over 60 min. and rinsed with part 5 solvent.
  • Part 6 deionized water
  • This example illustrates the preparation of a graft acrylic copolymer consisting by weight of 80% backbone made from styrene / n-butyl acrylate / 2-hydroxypropyl methacrylate (in the weight ration of 22 / 36 / 22) and 20% macromonomer (from Example 2) made of methyl methacrylate / hydroxyethyl methacrylate / methacrylic acid (in the weight ratio of 10.4 / 5.6 / 4).
  • This graft copolymer was formed in a water dispersion using the following components:
  • Part 1 was heated to reflux at 95 +/- 2°C and the pH adjusted to 7.5-7.8.
  • Part 2A monomers
  • Part 2B azo solution
  • Part 3 deionized water
  • Part 4 was added over 60 min. and rinsed with part 5 solvent.
  • Part 6 deionized water
  • MW 52500 EXAMPLE 15 This example illustrates another graft copolymer prepared according to the present invention, comprising 90% backbone made from styrene / n-butyl methacrylate / n-butyl acrylate / n-isobutoxymethyl methacrylamide (in the weight ratio of 20 / 40 / 8 / 22) and 10% macromonomer (from Example 1) made from methyl methacrylate / methacrylic acid (in the weight ratio of 6 / 4).
  • This hydroxy-free graft copolymer was formed in solution. It was prepared using the following components:
  • Part 1 was heated to 137-139°C and low boiling solvent was stripped off.
  • Part 2 was added over 3 hours maintaining reflux at 137-39°C, rinsing with Part 3.
  • Part 4 was added over 30 min. and rinsed with Part 5.
  • the reaction mixture was then held at reflux for 30 min. and 7.7 parts of low boiling solvent was stripped off.
  • the reaction mixture was then cooled to 60-70°C and neutralized with 3.0 parts of dimethylethanolamine, followed by dispersion in 84.5 parts deionized water (for a total of 187 parts).
  • the reaction product was characterized as follows:
  • the graft copolymer was formed in a water dispersion of the macromonomer.
  • the graft copolymer was prepared in a glass reactor using the following components:
  • Part 1 The pH of Part 1 was adjusted to 7.5-7.8 and the mixture was heated to reflux at 90°C.
  • Part 2 A including monomers
  • Part 2B azo solution
  • Part 3 was used for rinsing and then the reactor contents were held at reflux for 60 min, followed by pH adjustment to 8.0.
  • Deionized water (Part 4) was added.
  • the reaction product was characterized as follows:
  • COMPARATIVE EXAMPLE 17 As a comparison for Example 16, a copolymer was prepared in one step, using no macromonomer, from a monomer mixture comprising styrene / methyl methacrylate / n-butyl aciylate / 2-hydroxybutyl aciylate / methacrylic acid (in the weight ratio of 35 / 4.5 / 30 / 27.5 / 3). The dispersion was not stable.
  • This example illustrates the preparation of a graft copolymer comprising 92.5% backbone made from styrene / n-butyl acrylate / 2- hydroxypropyl methacrylate (in the weight ratio of 25 / 40 / 27.5) and 7.5% macromonomer (from Example 1) made from methyl methacrylate / methacrylic acid (in the weight ratio of 4.5 / 3).
  • the azo solution used in the above Example 16 was replaced with 0.2 parts ammoniumpersulfate (AP) in 21.5 parts in deionized water.
  • the resulting stable graft polymer was characterized as follows:
  • This example illustrates a graft copolymer according to the present invention comprising 94% backbone made from styrene / methyl methacrylate / n-butyl acrylate / methaciylamide / 2-hydroxyethyl acrylate (in • the weight ratio of 27 / 14.5 / 46 / 4 / 2.5) and 6% macromonomer (from Example 1) made from methyl methacrylate / methacrylic acid (in the weight ratio of 3.6 / 2.4).
  • Part 1 was heated to 90°C and the pH adjusted to from 7.0 to 7.75.
  • Part 2A monomers
  • Part 2B azo-amide solution
  • Part 3 water
  • Part 4 was added over 60 min, followed by rinsing with water (Part 5).
  • the product was characterized as follows:
  • Part 1 was adjusted to a pH of 7 to 7.5 and heated to 90 +/1 2°C.
  • Part 2A azo- macor solution
  • Part 2B monomers
  • Part 3 deionized water
  • Part 4 was added over 60 minute, followed by rinsing with methyl ethyl ketone (Part 5), pH adjustment to about 7.5 and the addition of some deionized water (Part 6).
  • the reaction products were characterized as follows:
  • EXAMPLES 24-27 These examples illustrate a one component waterborne paint formulation cured by baking.
  • the following examples were formulated at an acrylic/ melamine formaldehyde ratio of 75/25 using a methylated melamine formaldehyde binder CymelTM 325 from Cyanamid.
  • EXAMPLES 28-29 The following examples of automotive finish compositions were formulated at a acrylic/melamine foimaldehyde weight ratio of 75/25 using a butylated melamine foimaldehyde binder Luwipal 8735 from BASF.
  • Pendulum hardness 172 166 168
  • EXAMPLES 31-35 These examples illustrate a two component waterborne paint composition according to the present invention, which composition is formulated for air dry (low bake) curing. These examples were formulated using BasonatTM PLR 8878X, which is a trifunctional isocyanate commercially available from BASF and which is water dispersible. After mixing the BasonatTM PRL 8878X crosslinker at an isocyanate/hydroxyl equivalent ratio of 1/1, the viscosity (cps), hardness (Persoz) and % NCO remaining (on a film of +/- 30 micoms via IR analysis) was measured after 1 day and 14 days.
  • BasonatTM PLR 8878X which is a trifunctional isocyanate commercially available from BASF and which is water dispersible.

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Abstract

L'invention concerne une composition de revêtement à base d'eau contenant un copolymère greffé. Pour obtenir ce copolymère, on fixe par une extrémité des macromolécules à fonctions acide carboxylique ou amine neutralisées, à l'ossature polymère. Ces compositions permettent d'améliorer le fini des carrosseries.
PCT/US1995/005765 1994-05-19 1995-05-09 Revetements a base d'eau comprenant des reseaux auto-stabilises WO1995032228A1 (fr)

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WO1997034934A1 (fr) * 1996-03-21 1997-09-25 E.I. Du Pont De Nemours And Company Initiation d'une chaine de polymere radicalaire avec des molecules inertes non saturees
US5710227A (en) * 1994-06-13 1998-01-20 Rohm And Haas Company High temperature polymerization process for making terminally unsaturated oligomers
US5770646A (en) * 1996-10-29 1998-06-23 E. I. Du Pont De Nemours And Company Aqueous branched polymer dispersant for hydrophobic materials
US5955532A (en) * 1997-07-17 1999-09-21 E. I. Du Pont De Nemours And Company Aqueous coating composition of a self-stabilized crosslinked latex
EP0972783A1 (fr) * 1998-07-15 2000-01-19 Taisei Chemical Industries Ltd Procédé de préparation de résines amphotères fonctionnant comme dispersant
WO2000020476A1 (fr) * 1996-10-17 2000-04-13 E.I. Du Pont De Nemours And Company Copolymere greffe ayant un groupe fonctionnel uree ou imide en tant qu'agent dispersant de pigments
US6248826B1 (en) 1998-07-24 2001-06-19 Rohm And Haas Company Emulsion copolymers from terminally unsaturated acrylic acid oligomers
US6511744B2 (en) 2000-02-19 2003-01-28 Basf Aktiengesellschaft Pressure sensitive adhesives
WO2003102891A2 (fr) * 2002-06-03 2003-12-11 E.I. Du Pont De Nemours And Company Copolymere greffe comportant un groupe urethane/uree en tant que dispersant de pigment
US6723775B2 (en) 2000-09-14 2004-04-20 Rohm And Haas Company Method for preparing graft copolymers and compositions produced therefrom
WO2006007999A2 (fr) * 2004-07-16 2006-01-26 Dsm Ip Assets Bv Compositions aqueuses a base de copolymeres greffes vinyliques
WO2007147561A1 (fr) * 2006-06-23 2007-12-27 Dsm Ip Assets B.V. Compositions aqueuses de copolymères greffés vinyliques réticulables
US20150017359A1 (en) * 2013-07-11 2015-01-15 Ppg Industries Ohio, Inc. Coating compositions with improved adhesion to containers
US9371588B2 (en) 2012-06-21 2016-06-21 Instituto Mexicano Del Petroleo Procedure summary of water-based polymer resin doped titanium dioxide nanotubes as application corrosion coating
EP3960306A1 (fr) 2020-08-31 2022-03-02 Axalta Coating Systems GmbH Composition de revêtement supérieur
CN115003721A (zh) * 2020-01-24 2022-09-02 巴斯夫涂料有限公司 包含含硅烷的交联剂的水性电泳涂料

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US5231131A (en) * 1991-12-24 1993-07-27 E. I. Du Pont De Nemours And Company Aqueous graft copolymer pigment dispersants

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DE3909756A1 (de) * 1988-03-28 1989-10-12 Toa Gosei Chem Ind Zweikomponenten-acryl-urethan-beschichtungsmaterial
EP0455028A1 (fr) * 1990-04-28 1991-11-06 Bayer Ag Utilisation de copolymères en émulsion dans des revêtements transparents aqueux et peinture transparente aqueuse
US5231131A (en) * 1991-12-24 1993-07-27 E. I. Du Pont De Nemours And Company Aqueous graft copolymer pigment dispersants

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5710227A (en) * 1994-06-13 1998-01-20 Rohm And Haas Company High temperature polymerization process for making terminally unsaturated oligomers
WO1997034934A1 (fr) * 1996-03-21 1997-09-25 E.I. Du Pont De Nemours And Company Initiation d'une chaine de polymere radicalaire avec des molecules inertes non saturees
WO2000020476A1 (fr) * 1996-10-17 2000-04-13 E.I. Du Pont De Nemours And Company Copolymere greffe ayant un groupe fonctionnel uree ou imide en tant qu'agent dispersant de pigments
US5770646A (en) * 1996-10-29 1998-06-23 E. I. Du Pont De Nemours And Company Aqueous branched polymer dispersant for hydrophobic materials
US5955532A (en) * 1997-07-17 1999-09-21 E. I. Du Pont De Nemours And Company Aqueous coating composition of a self-stabilized crosslinked latex
EP0972783A1 (fr) * 1998-07-15 2000-01-19 Taisei Chemical Industries Ltd Procédé de préparation de résines amphotères fonctionnant comme dispersant
US6174963B1 (en) 1998-07-15 2001-01-16 Taisei Chemical Industries, Ltd. Method for producing amphoteric resin having dispersing function
US6248826B1 (en) 1998-07-24 2001-06-19 Rohm And Haas Company Emulsion copolymers from terminally unsaturated acrylic acid oligomers
US6511744B2 (en) 2000-02-19 2003-01-28 Basf Aktiengesellschaft Pressure sensitive adhesives
US6809141B2 (en) 2000-09-14 2004-10-26 Rohm And Haas Company Segmental copolymers and aqueous dispersions and films therefrom
US7001949B2 (en) 2000-09-14 2006-02-21 Rohm And Haas Company Aqueous dispersions of comb copolymers and coatings produced therefrom
US6864309B2 (en) 2000-09-14 2005-03-08 Rohm And Haas Company Method for preparing graft copolymers and compositions produced therefrom
US6723775B2 (en) 2000-09-14 2004-04-20 Rohm And Haas Company Method for preparing graft copolymers and compositions produced therefrom
WO2003102891A3 (fr) * 2002-06-03 2004-06-03 Du Pont Copolymere greffe comportant un groupe urethane/uree en tant que dispersant de pigment
WO2003102891A2 (fr) * 2002-06-03 2003-12-11 E.I. Du Pont De Nemours And Company Copolymere greffe comportant un groupe urethane/uree en tant que dispersant de pigment
WO2006007999A3 (fr) * 2004-07-16 2006-08-17 Dsm Ip Assets Bv Compositions aqueuses a base de copolymeres greffes vinyliques
WO2006007999A2 (fr) * 2004-07-16 2006-01-26 Dsm Ip Assets Bv Compositions aqueuses a base de copolymeres greffes vinyliques
WO2007147561A1 (fr) * 2006-06-23 2007-12-27 Dsm Ip Assets B.V. Compositions aqueuses de copolymères greffés vinyliques réticulables
US9371588B2 (en) 2012-06-21 2016-06-21 Instituto Mexicano Del Petroleo Procedure summary of water-based polymer resin doped titanium dioxide nanotubes as application corrosion coating
US9738793B2 (en) 2012-06-21 2017-08-22 Instituto Mexicano Del Petroleo Procedure summary of water-based polymer resin doped titanium dioxide nanotubes as application corrosion coating
US20150017359A1 (en) * 2013-07-11 2015-01-15 Ppg Industries Ohio, Inc. Coating compositions with improved adhesion to containers
CN105473672A (zh) * 2013-07-11 2016-04-06 Ppg工业俄亥俄公司 具有对容器的改进的附着力的涂料组合物
CN105473672B (zh) * 2013-07-11 2017-08-15 Ppg工业俄亥俄公司 具有对容器的改进的附着力的涂料组合物
CN115003721A (zh) * 2020-01-24 2022-09-02 巴斯夫涂料有限公司 包含含硅烷的交联剂的水性电泳涂料
EP3960306A1 (fr) 2020-08-31 2022-03-02 Axalta Coating Systems GmbH Composition de revêtement supérieur

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