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WO1999045078A1 - Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes - Google Patents

Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes Download PDF

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Publication number
WO1999045078A1
WO1999045078A1 PCT/US1998/004352 US9804352W WO9945078A1 WO 1999045078 A1 WO1999045078 A1 WO 1999045078A1 US 9804352 W US9804352 W US 9804352W WO 9945078 A1 WO9945078 A1 WO 9945078A1
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Prior art keywords
dispersion
weight
backbone
branched polymer
ethylenically unsaturated
Prior art date
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PCT/US1998/004352
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English (en)
Inventor
Joseph Albert Antonelli
Scopazzi Christopher
Kerstin Stranimaier
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E.I. Du Pont De Nemours And Company
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Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to PCT/US1998/004352 priority Critical patent/WO1999045078A1/fr
Priority to EP98910190A priority patent/EP1062286A1/fr
Priority to JP2000534615A priority patent/JP2002505370A/ja
Priority to CA002321798A priority patent/CA2321798A1/fr
Priority to BR9815699-3A priority patent/BR9815699A/pt
Publication of WO1999045078A1 publication Critical patent/WO1999045078A1/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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • 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

Definitions

  • This invention relates to improved waterborne dispersions containing an aqueous branched polymer dispersant and a dispersed hydrophobic material.
  • aqueous branched polymer dispersant and a dispersed hydrophobic material.
  • these coating contain a latex as the main film forming component, a crosslinking agent, and other non-latex resins, additives and pigments.
  • the latex to keep it dispersed in an aqueous medium can contain surfactant, and/or the latex polymer contains anionic or cationic groups which when formed into a salt with an acid used for cationic groups or a base used for anionic groups.
  • hydrophobic constituents can be added to the coating composition such as hydrophobic melamine crosslinking resins and hydrophobic polymers.
  • these hydrophobic constituents are very difficult to disperse in an aqueous medium.
  • Water dispersible polymers that are used as dispersants for pigments and used to form pigment dispersions for formulating waterborne coating compositions are known in the art and may be considered as a dispersant for such hydrophobic materials.
  • U.S. Patent 5,231,131, issued July 27, 1993 to Chu et al shows aqueous graft polymer pigment dispersants in which the side chains of the graft copolymer contain carboxyl groups that are neutralized with an inorganic base or an amine.
  • graft copolymers are used as dispersants for pigments
  • relatively large amounts of polymerized ethylenically unsaturated acid monomers are present in the side chains of the graft copolymer to provide water dispersibility but the presence of these acid groups in the graft copolymer makes a coating formed with such a copolymer sensitive to water and would not be suitable for dispersing hydrophobic materials in a coating.
  • a polymer dispersant is needed that will adequately disperse hydrophobic components used in coating compositions such as crosslinking agents like melamine crosslinking agents, hydrophobic polymers like acrylic polymers and polyesters and mixtures of such components and the polymeric dispersant contains relatively small amounts of polymerized acid monomers.
  • the branched polymer has a weight average molecular weight of about 5,000 - 100,000 and contains 20-80% by weight of a hydrophilic backbone and correspondingly 80-20% by weight of macromonomer side chains; wherein the backbone of the branched polymer is of polymerized ethylenically unsaturated monomers and 2-30% by weight, based on the weight of the backbone of polymerized ethylenically unsaturated monomers having an acid- functional group; and wherein at least 10% of the acid-functional groups are neutralized with an amine or an inorganic base and is hydrophilic in comparison to the side chains; and the side chains are of macromonomers of polymerized ethylenically unsaturated monomers that are polymerized into the backbone via an ethylenically unsaturated
  • the novel dispersion of this invention of a hydrophobic material dispersed by the branched polymer is stable and in general is non flocculated or agglomerated and is compatible with a variety of polymeric film forming binders that are conventionally used in waterborne coating compositions and in particular compatible with acrylic polymers that are used in waterborne coatings.
  • the branched polymer dispersant upon curing of the coating composition into which it has been incorporated reacts with other film forming components of the coating composition and becomes part of the film and does not cause deterioration of the film upon weathering as may occur if it remained an unreacted component of the film.
  • the branched polymer is an excellent dispersant, the ratio of polymer to hydrophobic component being dispersed is less than used with conventional dispersants. Further, the branched polymers allow for the use of higher molecular weight polymers that have a lower viscosity in comparison to linear polymers of the same composition that have the same molecular weight.
  • the acid content of the backbone of the branch polymer can readily be adjusted to maximize dispersion properties of the polymer without increasing molecular weight and not detract from the performance properties of a coating composition into which a dispersion of this polymer has been incorporated. Finishes of aqueous coatings formulated with dispersions containing these branched polymers are hard, water and humidity resistant.
  • the branched polymer used to formulate the dispersion of this invention is prepared from a macromonomer which forms the side chains of the branched polymer and comprises polymerized alpha-beta ethylenically unsaturated monomers and has one terminal ethylenically unsaturated moiety and has a weight average molecular weight (MW) of 1,000-30,000, preferably 6,000 to 15,000.
  • MW weight average molecular weight
  • About 20-80% (by weight), preferably 30-70%, of the macromonomer is copolymerized with 80-20%, preferably 70-30%, of a blend of other alpha, beta-ethylenically unsaturated monomers which form the backbone of the branched polymer, at least 2%, preferably 2-30% by weight, most preferably 3-15%, of the alpha, beta ethylenically unsaturated monomers of the backbone have carboxylic acid functionality, to form a branched polymer with a MW of 5,000-100,000, preferably 5,000-40,000, which after neutralizing with an amine or other neutralizing agent can be dispersed in water.
  • aqueous or waterborne coating compositions are obtained by using these branched polymers as dispersants for hydrophobic materials such as certain crosslinking agents and hydrophobic polymers.
  • These coating compositions also contain a film forming binder usually an acrylic polymer.
  • Such compositions have the advantage of providing excellent coating properties desirable for automotive finishes.
  • the side chains of the branched polymer are hydrophobic relative to the backbone and therefore contain less than 1% by weight , preferably essentially zero percent by weight, based on the weight of the branched polymer, of polymerized ethylenically unsaturated acid-functional monomers which are listed hereinafter.
  • the side chains contain polymerized hydrophobic monomers such as alkyl methacrylates and acrylates, cycloaliphatic methacrylates and acrylates and aryl methacrylates and acrylates and styrene as are listed hereinafter and also may contain up to 30% by weight, based on the weight of the branched polymer, of polymerized ethylenically unsaturated non-hydrophobic monomers which may contain functional groups.
  • polymerized hydrophobic monomers such as alkyl methacrylates and acrylates, cycloaliphatic methacrylates and acrylates and aryl methacrylates and acrylates and styrene as are listed hereinafter and also may contain up to 30% by weight, based on the weight of the branched polymer, of polymerized ethylenically unsaturated non-hydrophobic monomers which may contain functional groups.
  • Examples of such monomers are hydroxy ethyl acrylate, hydroxy ethyl methacrylate, acrylamide, nitro phenol acrylate, nitro phenol methacrylate, phthalimido methyl acrylate, phthalimido methacrylate, acryloamido propane sulfonic acid, and mixtures thereof.
  • the acrylic macromonomer may be prepared using a free radical initiator in a solvent with a Co (II) or Co (III) chelate chain transfer agent.
  • the backbone of the branched polymer contains at least 2 percent by weight of an acid functional (neutralized) monomer as, e.g., acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like. Methacrylic and acrylic acid are preferred.
  • acids that can be used are ethylenically unsaturated sulfonic, sulfinic, phosphoric or phosphonic acid and esters thereof; typically, styrene sulfonic acid, acrylamido methyl propane sulfonic acid, vinyl phosphonic or phosphoric acid and its esters and the like also can be used.
  • the backbone of the branched polymer preferably contains 2-30% by weight methacrylic acid or acrylic acid and preferably, 3 to 15% by weight and has a MW of 1,000-70,000.
  • the acid functional groups on the branched polymer are neutralized with an inorganic base or an amine.
  • the backbone is thus relatively hydrophilic in comparison to the side chains and the branched polymer keeps the hydrophobic constituents well dispersed in the resulting coating composition.
  • relative hydrophobicity or hydrophilicity of the backbone and side chains of the branched polymer could be further adjusted by varying the percent of acid and/or hydroxy functional monomers versus more hydrophobic monomers such as 2-ethyl hexyl methacrylate.
  • the branched polymer contains overall (including both backbone and macromonomer arms) about 0 to 40, preferably 5 to 40, and more preferably 10 to 30, percent of hydroxy functional acrylic monomers as, e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like.
  • hydroxy functional acrylic monomers as, e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like.
  • hydroxy functional acrylic monomers as, e.g., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- hydroxypropyl methacrylate, 2-hydroxy
  • the branched polymer comprises macromonomer 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 branched polymer and typically contains polymerized monomers of styrene, esters and or nitriles and/or amides of methacrylic or acrylic acid or mixtures of these monomers.
  • polymerized ethylenically unsaturated monomers can be present in the macromonomer and backbone, for example (but not limited to), acrylic and methacrylic acid esters of straight-chain or branched monoalcohols of 1 to 20 carbon atoms.
  • Alkyl acrylates and methacrylates having 1-12 carbons in the alkyl group can be used such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, nonyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethyl hexyl methacrylate, nonyl methacrylate, lauryl methacrylate and the like can be used.
  • Cycloaliphatic acrylates methacrylates can be used such as trimethylcyclohexyl acrylate, t-butyl cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate, and the like.
  • Aryl acrylates and methacrylates such as benzyl acrylate and 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.
  • 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 fumaric anhydride and its half and diesters; vinyl aromatics such as styrene, alpha methyl styrene and vinyl toluene; and polyethylene glycol monoacrylates and monomethacrylates.
  • the above monomers also can be used in the backbone of the branched polymer.
  • the branched polymer may be prepared by polymerizing ethylenically unsaturated monomers in the presence of macromonomers each having a terminal ethylene unsaturation.
  • the resulting branched 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 functionality capable of reacting with a crosslinking compound or polymer, although it is optional to have such reactive functionality only or essentially only or substantially only on the backbone.
  • the backbone or macromonomers referred to as having functionality may be part of a mixture of macromonomers of which a portion do not have any functionality or variable amounts of functionality.
  • 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.
  • 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.
  • cobalt chain transfer agents or catalysts are described in US
  • 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.
  • solvents are aromatics, aliphatics, ketones, glycol ethers, acetates, alcohols as, e.g., methyl ethyl ketone, isopropyl alcohol, n-butyl glycol ether, n-butyl diethylene glycol ether, propylene glycol methyl ether acetate, propylene glycol methyl ether, and N-butanol.
  • Peroxy- and azo-initiators (0.5-5% weight, based on the weight of the monomer) can be used in the synthesis of the macromonomers in the presence of 2- 5,000 ppm (on total monomer) or Co (II) chelate in the temperature range between 70-160°C, more preferably azo-type initiators as, e.g., 2,2'-azobis (2,4 dimethylpentane nitrile), 2,2'-azobis (2-methylpropane nitrile), 2,2'-azobis (2- methylbutane nitrile), l,l'-azo (cyclohexane carbonitrile) and 4,4'-azobis (4- cyanopentanoic) acid.
  • azo-type initiators e.g., 2,2'-azobis (2,4 dimethylpentane nitrile), 2,2'-azobis (2-methylpropane nitrile), 2,2'-azobis (2- methylbutane nitrile),
  • solvent is 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 and hydroperoxides. Typical of such catalysts are di-tertiarybutyl peroxide, di-cumyl peroxide, tertiary amyl peroxide, cumene hydroperoxide, di(n-propyl) peroxydicarbonate, peresters such as amyl peroxyacetate and the like.
  • peroxy type initiators include, e.g., t-butyl peroxide or Triganox ® B from AKZO, t-butyl peracetate or Triganox ® FC50 from AKZO, t-butyl perbenzoate or Triganox ® C from AKZO, and t-butyl perpivalate or Triganox ® 25 C-75 from AKZO.
  • Typical solvents that can be used to form the macromonomer or the branched polymer are ketones such as methyl ethyl ketone, isobutyl ketone, ethyl amyl ketone, acetone, alcohols such as methanol, ethanol, 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.
  • small amounts of difunctional alpha-beta unsaturated compounds can be used as, e.g., ethylene glycol dimethacrylate or hexane diol diacrylate.
  • branched polymer After the branched polymer is formed, it is neutralized with an amine or an inorganic base such as ammonium hydroxide or sodium hydroxide and then water is added to form a dispersion.
  • Typical amines that can be used include AMP (2-amino-2- methyl-1-propanol), dimethyl- AMP, amino methyl propanol, amino ethyl propanol, dimethyl ethanol amine, triethylamine and the like.
  • One preferred amine is amino methyl propanol and the preferred inorganic base is ammonium hydroxide.
  • the conversion into a water dispersion may be accomplished preferably by stripping our 30 to 60% of the solvent followed by admixing with an organic amine or ammonia and diluting with water, or by admixing with a solution of water and amine after the solvent stripping.
  • the branched polymer solution, after stripping can be stirred slowly into a solution of water and the amine.
  • the degree of neutralization of the dispersion can be from 10 to 150% of the total amount of acid groups, preferably from 40-100%.
  • the final pH of the dispersion can accordingly be about 4-10, preferably 7-9.
  • the solvents can be stripped-off eventually afterwards.
  • the overall branched polymer water borne dispersion should be characterized by an acid value of from 5 to about 150 (mg KOH/g resin solids), more preferably from 10 to about 70 and still more preferably from 15 to about 35, and an hydroxyl number of about 0 to about 250 (mg KOH/g resin solids), more preferably from 40 to 150.
  • Particularly useful branched polymers include the following: a branched polymer having a backbone of polymerized acrylate or methacrylate monomers, styrene monomers, methacrylic or acrylic acid monomers, and hydroxy-fiinctional acrylate or methacrylate monomers, and side chains of a macromonomer having a weight average molecular weight of about 2,000-30,000 and containing about 50% by weight, based on the weight of the backbone, of polymerized alkyl methacrylate or acrylate monomers, hydroxy-fiinctional acrylate or methacrylate monomers and 2-30 % by weight, based on the weight of the backbone, of polymerized methacrylic acid or acrylic acid.
  • a branched polymer having the above backbone of side chains comprising polymerized methyl methacrylate, butyl acrylate, methacrylic acid, styrene, and hydroxyethyl acrylate.
  • a branched polymer having the above backbone and macromonomers comprising polymerized 2-ethylhexyl acrylate, butyl methacrylate, and hydroxyethyl methacrylate.
  • the branched polymer is used as a dispersing resin to form an aqueous dispersion of a wide variety of hydrophobic materials that are commonly used in waterborne coating compositions.
  • Typical hydrophobic materials include hydrophobic melamine resins, hydrophobic polyesters, hydrophobic acrylic polymers, hydrophobic polyurethanes, blocked organic polyisocyanates and mixtures of any of the above.
  • Typical hydrophobic melamines include partially or fully alkylated melamine formaldehyde resins having 1-4 carbon atoms in the alkylated group and that can be monomeric or polymeric having a degree of polymerization of about 1-3.
  • Typical alcohols that are used to alkylate these melamines are methanol, ethanol, propanol, butanol, isobutanol and the like.
  • Typical commercially available melamine resins are as follows: “Cymel” 373, “Cymel” 385, "Resimine” 745, BM 7512 from Monsanto Corporation, HM 2608 from Monsanto Corporation, and BM 9539 from Monsanto Corporation.
  • Typical hydrophobic acrylic resins comprise polymers of alkyl methacrylates and acrylate, hydroxy alkyl acrylates and methacrylates and styrene such as a polymer of styrene, butyl methacrylate, butyl acrylate and hydroxy propyl acrylate.
  • Typical hydrophobic polyester resins are the esterification product of an aromatic dicarboxylic acid or an anhydride thereof and a polyol such as a polyester of phthalic anhydride, isophathalic acid, neopentyl glycol and trimethylol propane.
  • Typical blocked organic polyisocyanates that can be used are aliphatic polyisocyanates, aromatic polyisocyanate, cycloaliphatic polyisocyanates blocked with alcohols, ketimines, oximes and the like.
  • Typical hydrophobic polyurethanes include hydrophobic polyesters reacted with a polyisocyanate, hydrophobic acrylic polymers having reactive hydroxyl groups reacted with a polyisocyanate.
  • Cellulose acetate butyrate polymers such as CAB's from Eastman Chemical Company can be dispersed in aqueous compositions with the branched polymer and formulated into a waterborne coating composition.
  • the preferred method for forming the waterborne dispersion of this invention is to add with agitation the hydrophobic material to be dispersed to a solvent solution of the branched polymer before it is neutralized and dispersed in water and the neutralizing agent of amine or base is added with agitation. Water then is added and mixed in to form the aqueous dispersion.
  • the resulting dispersion has a yield stress of about 0-1,000 Pa (Pascals), a low (20 sec-1) shear viscosity of about 100-10,000 m Pas (milli Pascal seconds) and a high shear (1000 sec -1) viscosity of about 10-1,000 m Pas measured on a Rotvfisco viscometer.
  • An alternative method for forming the water borne dispersion of this invention is to neutralized the branched polymer with amine or base and add water with constant agitation and the hydrophobic material to be dispersed to form a dispersion.
  • Waterborne coatings in which the dispersions of the present invention are used may optionally contain a latex of an acrylic-based polymer.
  • These latexes are stable dispersions in water, typically as a dispersed latex polymer has an average particle size diameter of 10 nm to 1 micron, preferably 20 to 400 nm.
  • These coating compositions contain about 10-70%, more typically 15-50% by weight of binder, and about 30-90%, more typically 50-85% by weight, of an aqueous carrier.
  • the carrier is at least 50% water, preferably 75 to 95% water.
  • Suitable waterborne coatings are prepared by blending other useful components in accordance with normal paint formulation techniques. 10
  • a coating composition which will crosslink under elevated baking temperatures of about 60-180°C for abut 5-60 minutes, about 10 to 40%, preferably 15 to 30% 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 can be used or a dispersion of a hydrophobic alkylated melamine formaldehyde resin of this invention can be used.
  • These crosslinking agents are generally partially alkylated melamine formaldehyde compounds and may be monomeric or polymeric as described above.
  • These coating compositions containing a melamine crosslinking agent preferably 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.
  • the dispersion of this invention is aqueous, a solvent can be utilized, preferably in minimal amounts, to facilitate formulation and application of the coating compositions formulated with these dispersions.
  • An organic solvent is utilized which is compatible with the components of the composition.
  • coating composition utilizing the dispersion of the present invention may contain a variety of other optional ingredients, including pigments, fillers, plasticizers, antioxidants, surfactants and flow control agents.
  • Typical pigments that are used are metallic oxides such as titanium dioxide, iron oxides of various colors, zinc oxide, 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, benzimilazolinones, and metallic flake pigments such as aluminum flake, nickel flake, pearlescent pigments and the like.
  • 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.
  • the stabilizer may be added for example to a dispersion of this invention containing hydrophobic material or may be added directly to the coating composition or to pigment dispersions used to formulate the coating composition.
  • 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. 11
  • 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.
  • Such coating 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 and thickeners such as the Acrylsol ® copolymers from Rohm & Haas.
  • Coating compositions formulated with the dispersion of this invention have 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. These coating composition can be used to coat plastic substrates such as polyester reinforced fiberglass, reaction injection-molded urethanes and partially crystalline polyamides. These coating compositions may be used a pigmented monocoats, as clear coats, as the pigmented base coat of a clear coat/base coat or as both the clear coat and the base coat.
  • Coating compositions formulated with the dispersion of this invention 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 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 color coat 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 color coat/clearcoat finish is then baked as mentioned above to provide a dried and cured finish.
  • the present invention is also applicable to non-baking refinish systems, as will be readily appreciated by those skilled in the art.
  • 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.
  • a branched polymer was prepared by first preparing a macromonomer and then polymerizing the macromonomer with monomers that form the backbone of the branched polymer. A dispersion was then prepared from the branched polymer. Preparation of the macromonomer
  • a macromonomer of 5% IBMA (isobutyl methacrylate), 20% HEMA (hydroxyethyl methacrylate), and 75% 2EHMA (2-ethyl hexyl methacrylate), for use in a preparing a branched polymer was prepared as follows: to a 2-liter flask fitted with an agitator, condenser, heating mantle, nitrogen inlet, thermocouple and an addition port was added 15.25 g of IBMA monomer, 228.94 g of 2-EHMA monomer, 61.07g of HEMA monomer and 251.3 g of propylene glycol monomethyl ether. The mixture was agitated and heated to reflux (128 - 135 °C) under nitrogen.
  • the batch was then held at reflux for an additional 60 mins. at which time a mixture of 0.3 g of t-butyl peroctoate and 33.35 g of ethyl acetate were added as a single add and then the reaction mixture was cooled.
  • the macromonomer thus prepared has a number average molecular weight of 5322 and a weight average molecular weight of about 7627 as determined by GPC, weight solids are 61.9% and Gardner viscosity of U.
  • the percent terminal vinyl unsaturation is greater than 95 as determined by thermogravimetric analysis.
  • HSA butyl acrylate monomer
  • BA butyl acrylate monomer
  • MAA methacrylic acid monomer
  • MAA 8.2 g t-butyl peracetate
  • 86.54 g butyl acetate over 180 minutes holding 13
  • the branched polymer has a number average molecular weight of 14,710 and a weight average molecular weight of 37,190. Weight solids are 53.3% and Gardner viscosity is Y.
  • the ration of backbone to macromonomer arms is about 60/40.
  • the composition of the backbone is MMA/STY BA/HEA/MAA in the weight ratio of 27/20/26/20/7.
  • EXAMPLE 2 Another waterborne dispersion of the branched polymer of Example 1 but with a different butylated melamine was prepared. 133.93 g of hydrophobic butylated melamine (HM 2608 from Monsanto) was used. A white, stable dispersion of the branched polymer and butylated melamine was obtained having a total weight solids 35% (24.5% branched polymer and 10.5% butylated melamine), Gardner viscosity A, pH 8.31 and a particle size of 45 nanometers as determined by quasi electric light scattering. No phase separation of the butylated melamine was noted on standing at room temperature over 30 days.
  • EXAMPLE 3 A third waterborne dispersion of the branched polymer of Example 1 and a different butylated melamine was prepared. 110.92 g of hydrophobic butylated melamine (BM 9539 from Monsanto) was used. A white, stable dispersion of the branched polymer and butylated melamine was obtained having a total weight solids 14
  • the number average molecular weight of the branched polymer was 9080 and the weight average molecular weight was 17800.
  • the weight solids are 64.4% and the Gardner viscosity is ⁇ Th e composition of the backbone is MMA/STY/HEA/BA/MAA in the weight ratio of 35/20/15/20/10 and the weight ratio of backbone to macromonomer about 40/60.
  • the polyester was a 69.8% solids solution in methyl amyl ketone and the polyester has a hydroxyl number of 58, and a number average molecular weight of 2115 and a weight average molecular weight of 5066. After the polyester was added the composition was agitated for 15 minutes and then 840. lg deionized water was slowly added over a 30 minute period with good agitation and the dispersion was cooled to room temperature. A white, stable dispersion of the branched polymer and the polyester was obtained having a total weight solids 25% (17.5% branched 15

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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une dispersion aqueuse convenant à l'élaboration de compositions de peinture à l'eau contenant un matériau hydrophobe en dispersion, un support aqueux, un dispersant aqueux et un polymère ramifié (liant). Ce polymère ramifié, qui présente une masse moléculaire moyenne en poids d'environ 5.000-100.000 pour une teneur massique en ossature hydrophile de 20-80 % avec simultanément une teneur massique de 80-20 % en chaînes latérales de macromonomères. L'ossature est constituée de monomères éthyléniquement insaturés polymérisés pour 2-30 % de la masse des monomères éthyléniquement insaturés polymérisés portant un groupe à fonction acide. De plus, 10 % au moins des groupes à fonction acide, qui sont neutralisés par une amine ou une base inorganique, sont hydrophiles par rapport aux chaînes latérales. Enfin, les chaînes latérales sont des macromonomères de monomères éthyléniquement insaturés polymérisés formant par polymérisation l'ossature via un groupe éthyléniquement insaturé. Les macromonomères présentent une masse moléculaire moyenne en poids d'environ 1.000-30.000, le rapport pondéral hydrophile / liant se situant approximativement entre 1/100 et 200/100.
PCT/US1998/004352 1998-03-06 1998-03-06 Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes WO1999045078A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/US1998/004352 WO1999045078A1 (fr) 1998-03-06 1998-03-06 Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes
EP98910190A EP1062286A1 (fr) 1998-03-06 1998-03-06 Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes
JP2000534615A JP2002505370A (ja) 1998-03-06 1998-03-06 疎水性材料用の水性枝分かれポリマー分散剤
CA002321798A CA2321798A1 (fr) 1998-03-06 1998-03-06 Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes
BR9815699-3A BR9815699A (pt) 1998-03-06 1998-03-06 Dispersão à base de água e seu processo de preparação

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/004352 WO1999045078A1 (fr) 1998-03-06 1998-03-06 Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes

Publications (1)

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WO1999045078A1 true WO1999045078A1 (fr) 1999-09-10

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PCT/US1998/004352 WO1999045078A1 (fr) 1998-03-06 1998-03-06 Dispersant a base de polymere aqueux ramifie pour materiaux hydrophobes

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EP (1) EP1062286A1 (fr)
JP (1) JP2002505370A (fr)
CA (1) CA2321798A1 (fr)
WO (1) WO1999045078A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001277438A (ja) * 2000-03-30 2001-10-09 Unitika Ltd 易接着性プラスチックフィルムおよびその製造方法
EP1167478A1 (fr) * 2000-06-30 2002-01-02 Kansai Paint Co., Ltd. Résine comme agent de dispersion de pigments
EP1295922A2 (fr) * 2001-08-22 2003-03-26 Kansai Paint Co., Ltd. Résines agents de dispersion de pigments
US6656595B2 (en) 2000-10-13 2003-12-02 Kansai Paint Co., Ltd. Pigment dispersing resins
WO2008080906A1 (fr) * 2006-12-28 2008-07-10 Nuplex Resins B.V. Dispersions polymères à base d'eau
EP2025690A1 (fr) * 2007-07-27 2009-02-18 Bayer MaterialScience AG Dispersions secondaires d'un produit de polymérisation aqueux de revêtements
CN113413643A (zh) * 2021-07-26 2021-09-21 中建西部建设建材科学研究院有限公司 一种混凝土搅拌站废浆高效沉降方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4691963B2 (ja) * 2004-11-12 2011-06-01 東洋紡績株式会社 ガスバリア性積層フィルム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4407236A1 (de) * 1993-03-04 1994-09-08 Toa Gosei Chem Ind Wäßrige Beschichtungszusammensetzung
WO1995019999A1 (fr) * 1994-01-21 1995-07-27 E.I. Du Pont De Nemours And Company Dispersion polymere ramifiee, aqueuse
EP0728780A2 (fr) * 1995-02-24 1996-08-28 Röhm Gmbh Polymères greffés à propriétés émulsifiantes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4407236A1 (de) * 1993-03-04 1994-09-08 Toa Gosei Chem Ind Wäßrige Beschichtungszusammensetzung
WO1995019999A1 (fr) * 1994-01-21 1995-07-27 E.I. Du Pont De Nemours And Company Dispersion polymere ramifiee, aqueuse
EP0728780A2 (fr) * 1995-02-24 1996-08-28 Röhm Gmbh Polymères greffés à propriétés émulsifiantes

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001277438A (ja) * 2000-03-30 2001-10-09 Unitika Ltd 易接着性プラスチックフィルムおよびその製造方法
JP4584399B2 (ja) * 2000-03-30 2010-11-17 ユニチカ株式会社 易接着性プラスチックフィルムおよびその製造方法
EP1167478A1 (fr) * 2000-06-30 2002-01-02 Kansai Paint Co., Ltd. Résine comme agent de dispersion de pigments
US6548174B2 (en) 2000-06-30 2003-04-15 Kansai Paint Co., Ltd. Pigment dispersing resins
US6656595B2 (en) 2000-10-13 2003-12-02 Kansai Paint Co., Ltd. Pigment dispersing resins
EP1295922A2 (fr) * 2001-08-22 2003-03-26 Kansai Paint Co., Ltd. Résines agents de dispersion de pigments
EP1295922A3 (fr) * 2001-08-22 2004-11-17 Kansai Paint Co., Ltd. Résines agents de dispersion de pigments
WO2008080906A1 (fr) * 2006-12-28 2008-07-10 Nuplex Resins B.V. Dispersions polymères à base d'eau
US8519026B2 (en) 2006-12-28 2013-08-27 Nuplex Resins B.V. Waterborne polymeric dispersions
EP2025690A1 (fr) * 2007-07-27 2009-02-18 Bayer MaterialScience AG Dispersions secondaires d'un produit de polymérisation aqueux de revêtements
US8119729B2 (en) 2007-07-27 2012-02-21 Bayer Materialscience Ag Aqueous secondary polymer dispersions for the production of coatings
CN113413643A (zh) * 2021-07-26 2021-09-21 中建西部建设建材科学研究院有限公司 一种混凝土搅拌站废浆高效沉降方法

Also Published As

Publication number Publication date
CA2321798A1 (fr) 1999-09-10
EP1062286A1 (fr) 2000-12-27
JP2002505370A (ja) 2002-02-19

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