WO2002010297A2 - Dispersions polymeres aqueuses stables et formulations contenant des polymeres de latex pour former des revetements a base d'eau - Google Patents

Dispersions polymeres aqueuses stables et formulations contenant des polymeres de latex pour former des revetements a base d'eau Download PDF

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Publication number
WO2002010297A2
WO2002010297A2 PCT/US2001/023896 US0123896W WO0210297A2 WO 2002010297 A2 WO2002010297 A2 WO 2002010297A2 US 0123896 W US0123896 W US 0123896W WO 0210297 A2 WO0210297 A2 WO 0210297A2
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alkyd
polymer
blend
water
aqueous
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PCT/US2001/023896
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WO2002010297A3 (fr
Inventor
Michael D. Coad
Jean Elizabeth Marie Fletcher
Joseph Leo Nothnagel
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Eastman Chemical Company
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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids

Definitions

  • the present invention relates to stable aqueous polymer dispersions and blends of those dispersions with latexes. More particularly, aqueous alkyd polymer dispersions are prepared by forming polymer salts in a hydrophilic organic solvent and removing the hydrophilic organic solvent from a solvent blend of water and the hydrophilic organic solvent at temperatures which minimize the mean particle size of the polymers in the resulting aqueous dispersions of the polymers and/or removing the organic solvent from the polymer/organic solvent/water blend such that inversions do not occur.
  • the alkyd polymer dispersions are blended with a latex to form a waterborne coating with improved properties.
  • aqueous polymer dispersions One process for the preparation of aqueous polymer dispersions is emulsification in which hydrophilic assistants (emulsifiers and/or protective colloids) are used in order to ensure the stability of the dispersion. These assistants can make the films produced from the dispersions somewhat sensitive to water.
  • Another way to disperse polymers i ⁇ ater is to use ionic components in the polymeric vehicle.
  • One approach is to make a polymer such as an alkyd having carboxyl groups, or other ionizable groups and acid number in amounts effective such that when the carboxyl groups are converted into salts with a neutralizer such as an amine,' they will permit the polymer or oligomer to be dispersed in a mixed solvent system which includes an organic solvent and water.
  • the salt such as an amine salt, of the oligomer or polymer disperses into the mixed water/organic solvent system with the formulation of a dispersion or solution.
  • a water reducible system This is commonly known as a water reducible system.
  • These systems commonly have high acid values.
  • Organic solvent has typically been removed from water reducible systems through two routes .
  • the first route utilizes low temperature boiling solvents that are water miscible and often form low temperature boiling azeotropes with water. These types of processes result in the loss of neutralizer and require addition of make-up neutralizer in the process. Further, use of insufficient solvent in these systems results in the polymer salt being insoluble with addition of water. Hence, an inversion takes place as solvent is stripped from the system.
  • the second route typically utilizes organic solvents that boil at temperatures greater than 100 "C. and also often form azeotropes with water. Distillation proceeds at higher temperatures which, if the salt is an amine, will result in loss of amine, cause undesirable particle size variation in the dispersion and undesirably increase the average particle size of the resin in the dispersion. If distillation continues too long and too much amine is stripped, the dispersion will become unstable and fall apart. To keep viscosities low, in some water reducible systems molecular weights of polymers have been kept low. As a result, these systems have required large amounts of cross-linker and cross-linking to achieve coatings performance .
  • carboxyl functional polymers such as alkyds
  • water- reducible resins e.g., McWhorter Technologies ' s Duramac ® WR 74-7495
  • the paint formulator neutralizes the carboxyl groups with a volatile amine to form water soluble salts and disperses the resin in water. The resin entangles and collapses into large agglomerates and is then formulated into the final paint.
  • the stability of the resin once dispersed in water is 2-4 weeks at 120°F. at which time changes may be observed in viscosity, pH shift (due to hydrolysis of the resin) , seeds and separation.
  • the finished paints are typically 25% volume solids at a pH of 8.5.
  • the final pH is critical for the stability of these systems, as excess amine is required to keep these agglomerates in a dispersed phase.
  • paint formulators Due to the desire to reduce the impact of volatile organic solvent emissions on the environment, paint formulators have desired technologies that utilize lower levels of VOC.
  • Conventional solventborne resins range from 4.5 to 6.0 lbs VOC per gallon, high solids solventborne resins from 2.3 (bakes) to 4.0 lbs VOC per gallon, water- reducible resins hover around 2.8 lbs VOC per gallon, and latex at 0-1.8 lbs VOC per gallon.
  • each technology suffers from one or more deficiencies when compared to conventional solventborne alkyds.
  • the present invention is directed to an aqueous blend of an alkyd dispersion and a latex polymer which forms coatings.
  • the blend provides an air dried coating.
  • the blend is effective for providing an air dried primer that is recoatable with a wide range of topcoats .
  • the blend of alkyd dispersion and latex polymer is effective for providing a primer coating with superior humidity and salt spray resistance, low VOC levels, very fast dry times, early water spotting resistance and block resistance, and excellent application properties.
  • the blend of the present invention provides synergistic effects in film coating performance as compared to films formed from alkyd dispersions or latex polymers alone.
  • coatings made with alkyd dispersions alone wet out metal substrates, and demonstrate conventional alkyd-like properties such as good chemical resistance and good salt spray corrosion resistance.
  • coatings made with alkyd dispersions alone exhibit blistering when exposed to constant humidity, have slow dry times, and have poor block and poor early water resistance.
  • coatings made with latex alone demonstrate fast dry times, good block resistance, and higher volume solids, but have poor early water resistance.
  • latex coatings can be formulated to have good salt spray corrosion resistance or good humidity resistance, but not both.
  • the alkyd dispersion/latex blend of the present invention is effective for providing desirable properties of both alkyds and latexes.
  • the coatings of the present invention are made by blending about 10 weight percent to about 60 weight percent, based on the total resin solids of the blend, of latex with an alkyd dispersion, and in a very important aspect, about 30 weight percent to about 50 weight percent, based on the total resin solids of the blend, of a latex is blended with an alkyd dispersion.
  • the alkyd dispersion/latex blend of the present invention is effective for providing a film coating with a humidity resistance of at least about 336 hours, an air dry time of about 10 to about 40 minutes at about 25'C, and a salt spray corrosion resistance of at least about 336 hours.
  • the air dry time is not more than about 30 minutes, and preferably not more than about 10 to about 30 minutes.
  • the alkyd/latex blends of the present invention are effective for use as primers that can be recoated with a wide variety of topcoats, including solventborne topcoats.
  • the present invention is directed to an alkyd dispersion made from a process effective for providing a stable water dispersion of alkyd polymer that is substantially free of emulsifiers.
  • the aqueous dispersions of the invention have less than about 2 weight percent organic solvent, at least about 30 weight percent solids, and a viscosity of less than about 20.0 poise at about ambient temperature.
  • processing temperatures are minimized, mean particle size of the resins in the dispersions are kept to size of not more than about 300 nm and the dispersion process is inversionless.
  • an ionic functional alkyd polymer is synthesized in a hydrophilic organic solvent, or synthesized neat and subsequently mixed with hydrophilic organic solvent.
  • the alkyd polymer which is formed has an acid value of at least about 4, but the acid value of the polymer which results from the condensation reaction to make the alkyd is not more than about 40 and has a solubility of at least about 50 weight percent in the hydrophilic solvent, based on the weight of the polymer and solvent, and the hydrophilic solvent has a solubility in water of at least about 5 weight percent, at processing temperatures, based on the weight of the solvent and water mixture.
  • the acid value of fully converted monomers into a polymer at each stage of polymerization does not exceed about 40.
  • the alkyd is an acrylated alkyd
  • the alkyd portion of the polymer has an acid value of not more than 40 and the acrylated portion of the polymer also has an acid value of not more than about 40. This is important because the water resistance of the coating deteriorates if the acid value is more than about 40.
  • the neutralizer may be any salt-forming base compatible with the ionizable functional polymer such as sodium hydroxide or an amine.
  • the neutralizer is an amine type which is selected from the group consisting of ammonia, triethanol amine, dimethyl ethanol amine, and 2-amino-2 -methyl-1- propanol. Not all of the ionizable groups on the polymers need to be reacted with the base (or neutralized) .
  • the alkyd polymer is neutralized before it is blended with water so that water dispersible neutralized ionizable groups are distributed throughout the polymer, and in an important aspect, are generally evenly distributed throughout the alkyd polymer.
  • organic solvent and water are removed or stripped from the blend at a duration, temperature and pressure effective for providing an aqueous dispersion having a resin mean particle size of not greater than about 300 nm, a polymer concentration of at least about 30 weight percent and an organic solvent concentration of less than 2 weight percent.
  • the neutralizer is an amine or ammonia
  • the mean particle size of the resin is maintained with a stripping temperature of not more than about 65 'C at a pressure which permits such a stripping temperature.
  • the viscosity of the system remains in the range of about 0.1 poise to about 20 poise (measured at a temperature of about 25'C), and preferably about 1 to about 20 poise, throughout the process, and a high viscosity spike normally attributed to dispersion processes does not occur. Because a high viscosity spike is never encountered during processing of the dispersion, a higher solids contents can be achieved. In a very important aspect of the invention, at 25'C the dispersion will generally have a viscosity of less than about 10 poise. In the alternative, the temperature of the strip is below the temperature at which substantial loss of neutralizer would otherwise occur.
  • the mean particle size of the resin does not exceed more than about 300 nm, with a typical mean particle size range of about 40 nm to about 200 nm.
  • polymers which can be dispersed in accordance with the present invention include alkyd .polymers and alkyd hybrids .
  • the alkyd polymers being dispersed are generally homogeneous polymers, that is generally one type of alkyd polymer.
  • the solids levels may be at least about 40 weight percent.
  • the resins have a number average molecular weight (M n ) of about 2,000 to about 10,000 and an acid value of at least about 4, but not more than about 40 as described above.
  • the alkyd has a M n of about 2,000 to about 10,000 and an acid value of at least about 4.
  • the acid value is about 10 to 40, preferably about 15 to about 25.
  • the polymer being dispersed in accordance with the invention is a hybrid between a condensation polymer and an addition polymer.
  • the solids level of the dispersion may be at least about 30 weight percent, and preferably from about 30 to about 50.
  • the hybrid polymers have a number average molecular weight of at least about 2,000 and an acid value of at least about 4, but not more than about 40 as described above.
  • the invention provides formulated coatings that include aqueous polymer dispersions of the alkyd polymer and/or hybrid alkyd polymer described herein, a latex, and optionally a drier selected from the group consisting of cobalt, manganese, vanadium, and rare earth salts of organic carboxylic acids, 1,10- phenanthroline, and mixtures thereof.
  • aqueous alkyd polymer dispersions included in the alkyd/latex blend are carboxyl functional alkyd resins with a number average molecular weight of about 2,000 to about 10,000 and an acid value of from about 10 to about 40.
  • Polymeric vehicle means all polymeric and resinous components in the formulated coating, i.e., before film formation, including but not limited to the water dispersible salt of a polymer.
  • the polymeric vehicle may include a cross-linking agent.
  • Coating binder means the polymeric part of the film of the coating after solvent has evaporated, and with a thermosetting polymeric vehicle after cross-linking.
  • Formated coating means the polymeric vehicle and solvents, pigments, catalysts and additives which may optionally be added to impart desirable application characteristics to the formulated coating and desirable properties such as opacity and color to the film.
  • aqueous medium as used herein means water and a mixture of water and hydrophilic organic solvent in which the content of water is at least 10% by weight.
  • hydrophilic solvents examples include alkylalcohols such as isopropanol, methanol, ethanol, n-propanol, n-butanol, secondary butanol, tert-butanol and isobutanol, ether alcohols such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, methyl carbitol and ethyl carbitol, ether esters such as methyl cellosolve acetate and ethyl cellosolve acetate, dioxane, dime hylformamide, diacetone alcohol, methyl ethyl ketone, acetone, and tetrahydrofurfuryl alcohol.
  • Ionizable group refers to functional groups on the polymer that effect water dispersibility of the polymer. Examples of ionizable groups include -COOH, -S0 3 H, -P0 4
  • Neutralizer refers to compositions' which can react with ionizable groups on the polymer to affect water dispersibility.
  • Examples of neutralizers useful in the present invention include amines, ammonia, and metal hydroxides including NaOH and KOH.
  • the neutralizers are amines and ammonia.
  • Cross-linker means a di- or polyfunctional substance whose functional groups are capable of forming covalent bonds .
  • the reaction product of an amine or ammonia with a carboxyl group produces a "salt".
  • “Substantially solventless” means a polymeric vehicle or formulated .coating composition having not more than about five weight percent organic solvent.
  • solvent means an organic solvent
  • Organic solvent means a liquid which includes but is not limited to carbon and hydrogen which liquid has a boiling point in the range of not more than about 250 'C at about one atmosphere pressure.
  • Hydrophilic solvent means a solvent that has a solubility in water of at least about 5 weight percent.
  • Volatile organic compounds VOCs are defined by the U.S. Environmental Protection Agency at 40 C.F.R. 51.000 of the Federal Regulations of the United States of America.
  • a “high solids” or “high solids formulated coating composition” when referring to an aqueous formulated coating composition means a composition containing more than about 30 percent calculated volume solids, and in an important aspect of the present invention, about 35 percent to about 50 percent calculated volume solids.
  • “Film” is formed by application of the formulated coating composition to a base or substrate, evaporation of solvent, if present, and cross-linking if necessary.
  • Air dried formulated coating composition means a formulated coating composition that produces a satisfactory film without heating or baking, but which provides a satisfactory film at ambient temperature with or without oxidative cross linking.
  • “Baked formulated coating composition” means a formulated coating composition that provides optimum film properties upon heating or baking above ambient temperature, which composition may include cross linking agents such as melamines .
  • “Dispersion” in respect to a polymeric vehicle, formulated coating composition, or components thereof means that the composition must include a liquid and particles detectable by light scattering.
  • Dissolved in respect to a polymeric vehicle, formulated coating composition or components thereof means that the material which is dissolved does not exist in a liquid in particulate form where particles larger than single molecules are detectable by light scattering.
  • Solubility means a liquid or solid that can be partially or fully dissolved in a liquid.
  • miscible means liquids with mutual solubility.
  • Acid number or “acid value” means the number of milligrams of potassium hydroxide required for neutralization of or reaction with ionizable groups present in 1 g of material, such as resin.
  • “Hydroxyl number” or “hydroxyl value” which is also called “acetyl value” is a number which indicates the extent to which a substance may be acetylated; it is. the number of milligrams of potassium hydroxide required for neutralization of the acetic acid liberated on saponifying 1 g of acetylated sample.
  • “Thermosetting polymeric vehicle” is a polymeric vehicle which irreversibly cross-links for a teaching binder to form a film.
  • Substantially free of emulsifier means a composition with not more than about 0.5 weight percent emulsifiers.
  • Aqueous dispersions of the present invention are substantially free of emulsifier.
  • the term "inversion” refers to a phase change where a mobile phase becomes a dispersed phase. For example, an inversion takes place when sufficient oil is added to an oil in water phase such that phases invert to change from a oil in water phase to a water in oil phase.
  • an inversionless system the corresponding increase in viscosity associated with dispersions does not occur.
  • the viscosity of the system during processing remains less than about 20 poise, and in a very important aspect, less than about 10 poise at 25'C.
  • ⁇ latex ⁇ j refers to a polymer made by free radical emulsion polymerization which results in an aqueous dispersion that is stabilized with sufficient levels of surfactant.
  • Commercial examples of latexes include Aquamac ® 440, Aquamac ® 500, ' and Aqua ac ® 580 (all available from McWhorter Technologies) .
  • a ⁇ universal primer ⁇ refers to a primer that can be topcoated with virtually any type of topcoating, both solventborne and waterborne, one and two components. Further, a universal primer can be topcoated at any time after the primer flashes off, with no evidence of lifting or loss of adhesion (to substrate or intercoat) . • A universal primer can also be topcoated with good enamel holdout. The following limitations exist when using currently available universal primers .
  • Chlorinated resins work as universal primers, but are limited in desirability due to high costs and the environmental concerns associated with chlorinated resins.
  • a good universal primer according to the invention has no lift window, good intercoat adhesion, good adhesion to substrate and enamel holdout is fair to good.
  • an alkyd polymer is synthesized neat or in an organic hydrophilic solvent which has limited to infinite solubility in water.
  • Polymers useful in the present invention include generally homogenous alkyds having a number average molecular weight of about 2,000 to about 10,000, preferably a number average molecular weight of 2,000 to 6,000, and alkyd hybrid polymers having a molecular weight of at least about 2,000.
  • alkyds are synthesized neat and then dropped into solvent.
  • the alkyd polymers have an acid value of not more than about 40 as described above, and in a very important aspect, where the ionizable groups are -COOH, about 10 to about 40, preferably 15 to 25.
  • the ionizable group is derived from SSIPA (5- (sodiosulfo) isophthalic acid)
  • the acid value may be as low as about 4.
  • the low acid values of the alkyds are important not only to the aqueous dispersions of the alkyds, but also to the aqueous blends of alkyd and latex polymers.
  • One of these polymers may have high acid value, and one with a low acid value to obtain a stable/core shell particulate blend with the hydrophillic ionizable groups forming the outer shell of the polymer and a polymer without carboxyl or ionizable groups forming a ⁇ coreg of the particulate polymer.
  • the acid value of the fully converted monomers into a polymer at each stage of polymerization does not exceed about 40.
  • the alkyd is an acrylated alkyd
  • the alkyd portion, of the polymer has an acid value of not more than about 40 and the acrylated portion of the polymer also has an acid value of not more than about 40. This is important because if or when the polymer curls or otherwise forms a particle it does not exhibit a high density of ionizable groups which will reduce the water resistance of the resulting coating.
  • the particles formed by the alkyd do not exhibit a charge density of more than about 4xl0 ⁇ 5 moles of carboxylic acid groups per m 2 .
  • the alkyd polymers are blended with or synthesized in a solvent selected from the group consisting of alkylalcohols such as isopropanol, methanol, ethanol, n-propanol, n-butanol, secondary butanol, tert-butanol and isobutanol, ether alcohols such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, methyl carbitol and ethyl carbitol, ether esters such as methyl cellosolve acetate and ethyl cellosolve acetate, dioxane, dimethylformamide, diacetone alcohol, methyl ethyl ketone, acetone, and tetrahydrofurfuryl alcohol.
  • the polymers of the invention have a solubility at processing temperatures in the hydrophilic solvent, of at least about 50 weight percent, more preferably
  • Stage one provides an alkyd resin in a hydrophilic solvent which can be stored, and which can be further processed in stage two.
  • the alkyd polymer has a M n of about 2,000 to about 10,000, preferably about 2,000 to about 6,000.
  • the acid value is about 10 to about 40, preferably an acid value of about 15 to about 25, and where the ionizable group (s) includes - S0 3 H, and/or phosphate (-P0 4 H 2 ) the acid value can be as low as about 4.
  • An alkyd resin is an oil modified polyester resin and broadly is the product of the reaction of a di- or polyhydric alcohol and a di- or poly- basic acid or acid derivative in the presence of an oil, fat or carboxylic acid derived from such oil or fat which acts as a modifier.
  • Such modifiers are typically drying oils which can be added at a high level of modification (long oils) or as a small level of modification (short oils) .
  • the dihydric or polyhydric alcohol employed is suitably an aliphatic alcohol; suitable alcohols include triols and tetraols such as trimethylolpropane, trimethylolethane, tris (hydroxyethyl) isocyanurate, glycerine, and pentaerythritol, and dihydric alcohols or diols that may include neopentyl glycol, dimethylol hydantoin, ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexane dimethanol, Esterdiol 204 (trademark of Union Carbide), 1,3-propane diol, 1, 6-hexanediol, and dimethylol propionic acid (DMPA) .
  • DMPA dimethylol propionic acid
  • polyhydric alcohols may have -COOH groups. Mixtures of the alcohols may also be employed
  • the dibasic or polybasic acid, or corresponding anhydrides employed may be selected from a variety of aliphatic and aromatic carboxylic acids. Suitable acids and acid anhydrides include, by way of example, adipic acid, phthalic anhydride, isophthalic acid, bis 3,3', 4,4 ' -benzophenone tetracarboxylic anhydride, and trimellitic anhydride. Mixtures of the acids may also be employed, particularly to provide a desired content of carboxyl groups .
  • the alkyd polymers or resins that can be dispersed in accordance with the present invention may include polymers which are hybrids of alkyd polymers and other polymers .
  • the hybrid polymers may be any combination of one or more alkyd polymer and one or more addition polymers which combination has an acid value within the aforesaid range and a number average molecular weight of at least about 2,000.
  • the hybrid polymers are alkyds which also include acrylated portions. The acrylated portions, however, do not exceed about 20 weight percent of the entire polymer.
  • no portion or segment of the hybrid has an acid value of more than about 40.
  • Hybrid polymers also include epoxy modified alkyds, styrene modified alkyds, and vinyl toluene modified alkyds .
  • the alkyd polymer salt is formed in situ in the organic solvent with water being mixed with the polymer salt/organic solvent combination.
  • neutralizer is added to an organic solvent solution containing the resin in an amount effective for neutralizing the resin to provide sufficient salt to render the resin dispersible in water.
  • Neutralizers useful in the present invention include but are not limited to ammonia, triethanol amine, dimethyl ethanol amine, 2 -amino-2-methyl -1-propanol, NaOH and KOH.
  • the amount of neutralizer added is dependent on chemistry type, acid value and molecular weight.
  • the ionizable group is carboxyl
  • from about 30 to about 70 percent of the carboxyl groups are neutralized to obtain the solids level and low VOC level of the dispersions of the invention, but all of the carboxyl groups may be neutralized.
  • neutralizer is mixed with the alkyd polymer in an amount effective to provide at least about 70 parts polymer salt in less than about 30 parts solvent wherein with subsequent mixing with water, the neutralized polymer will provide a dispersion which comprises not more than.about 60 weight percent water, based on the weight of the dispersion.
  • the alkyd requires between about 60% to about 100% neutralization to stabilize the dispersion.
  • the process provides a mean particle size of not more than about 300 nm, with a typical mean particle size in the range of about 40 nm to about 200 nm as measured by laser light scattering.
  • the alkyd polymer can be preneutralized by making the polymer metal, amine or ammonia salts of the monomer's ionizable groups such as -COOH, -S0 3 H, -P0 4 H 2 , and mixtures thereof.
  • the polymer made from these "preneutralized" monomers would have an acid value, as measured by titration, of at least about 4 and not more than about 40 as described above if the ionizable groups which form part • of the polymer were not already neutralized.
  • monomers have a polyfunctionality such as a difunctionality which permits them to form polymers that also have the salt form of the ionizable groups.
  • a and B are -OH and/or -COOH which can form a polyester in a condensation reaction and C is selected from the group consisting of -COOX, -S0 3 X and -P0 4 Y 2 , where X is an alkali metal such as sodium or potassium and one Y may be H, but at least one or both Ys are alkali metals such as sodium or potassium.
  • Alkyd polymers can be made with 5- (sodiosulfo) isophthalic acid which would result in condensation polymers which are condensed through the carboxyl groups of the acid with free -S0 3 Na groups. The same could be done with 5- (potassiosulfo) isophthalic acid.
  • the neutralized polymer should be soluble in the hydrophilic solvent, and in an important aspect, the neutralized polymer is at least 50 weight percent soluble in the hydrophilic solvent.
  • the neutralized polymer when -S0 3 H is included as an ionizable group, as low as about 10 percent of the ionizable groups may be neutralized to obtain the solids level and low VOC level of the dispersions of the invention.
  • water having a temperature of about 25'C. to about 65 'C. is added to the neutralized resin solution.
  • the initial ratio of solvent to water is about 1 to about 3.5 for alkyd polymer.
  • the initial ratio of solvent to water is important to ensure that inversion does not take place during subsequent stripping of solvent .
  • the amount of water to be added may be greater than that required to obtain the desired solids of the final dispersion. Some water loss typically occurs during solvent distillation. The system requires sufficient solvent at the beginning to solubilize the salt prior to water addition.
  • polymer in hydrophilic solvent is added to water that already contains a neutralizer.
  • the organic solvent and water if required are removed or stripped from the neutralized resin/water/solvent mixture.
  • a reduced atmospheric pressure may be applied to the mixture to aid in the removal of solvent and,water.
  • vacuum may range from about 22 inches to about 29 inches of mercury gauge. With lower temperatures, a higher vacuum must be used to remove solvent. Lower reaction temperatures result in less foaming, as the higher vacuum coupled with the surface tension of the bubbles helps to break the bubbles.
  • solvent/water is stripped with heat being supplied through the use of a heat exchanger. Use of a heat exchanger may reduce distillation times and temperatures and further minimize destruction of the salt.
  • solids levels of at least about 40 weight percent to about 50 weight percent can be attained for alkyds.
  • solvent that is removed can be purified and reused.
  • a simple flash or multiple stage distillation is sufficient to clean the solvent of any contamination.
  • the water dispersion of the alkyd polymers does not require emulsifying agents and does not have more than about 2 weight percent, based on the weight of the composition, of organic solvent after the distillation of the solvent.
  • the aqueous dispersion contains from about 0.2 to about 2 weight percent organic solvent.
  • the water dispersion of the alkyd polymers includes the alkyd polymers, as well as the water dispersible amine salt of the alkyd polymer.
  • the ionizable group is a carboxyl
  • the aqueous dispersion of the invention does not have less than 30 percent of the free carboxyl groups of the polymer neutralized or converted into a salt. As the acid number of the polymer goes down, the higher the percent of the carboxyl groups on the polymer must be neutralized. Where the ionizable groups are -COOH, to maintain the dispersion below an acid value of about 15, about 100% of the carboxyl groups on the polymer should be neutralized to the salt.
  • the dispersions of the invention do not have more than about 1 pound per gallon of dispersion (120 g/1) VOCs, and in a very important aspect the dispersion has about 0.2 pounds per gallon of dispersion VOCs.
  • alkyd dispersions prepared according to the present invention are useful for blending with latex.
  • the resulting blend is effective for use as a universal primer, especially when the blend comprises from about 30 to about 50 weight percent latex based upon the weight of the total resin solids in the aqueous blend.
  • the latex is made from styrene and acrylic monomers which provides a styrenated acrylic latex
  • the aqueous dispersions of the salts of the carboxyl functional alkyd resins with a number average molecular weight of about 2,000 to about 10,000, preferably about 2,000 to about 6,000, having an acid number of about 15 to about 25, having less than about 2% volatile organic solvent at about 30 to about 50% solids in water and a mean particle size of about 40 to about 300nm are blended with latex.
  • Formulation of blends of alkyd dispersions and latex provide a film coating with a humidity resistance of at least about 336 hours, an air dry time of about 10 to about 40 minutes, and a salt spray corrosion resistance of at least about 336 hours.
  • the primer coatings of the present invention can be recoated with a wide variety of topcoats.
  • topcoats that can be used over the primers of the invention include coatings made from the following: conventional solventborne alkyds, high solids solventborne alkyds, two component acrylic urethanes, solventborne polyester bakes, water reducible alkyds, and latexes.
  • TMP trimethylolpropane
  • BA benzoic acid
  • IPAc isophthalic acid
  • FASCAT 4100 Elf AtoChem
  • trimellitic anhydride (TMA) was added to the flask and the temperature was maintained at 170 degrees centigrade.
  • NVM Percent Solids
  • Viscosity (cps) about 7200
  • NVM Percent Solids
  • a dispersed alkyd resin produced in a manner similar to that in Example 1 was formulated into a paint as follows:
  • the alkyd dispersion contains an alkyd with a molecular weight of 2800 and an acid value of 25, resulting in a monomodal particle size of 86 nm (median) ⁇ 21 nm, 85 nm (mode) and a pH of 6.79.
  • the resulting paint had a viscosity of 38 seconds in a #2 Zahn cup, and was applied to matte cold rolled steel panels through a conventional siphon air spray gun. Calculated VOC was approximately 24 grams per liter.
  • EXAMPLE 3 FORMULATION OF AN ALKYD DISPERSION/LATEX BLEND PRIMER PAINT
  • a dispersed alkyd resin produced in a manner similar to that in Example 1 was formulated into a paint as follows:
  • the first two items were premixed before addition to the vessel:
  • a dispersed alkyd resin produced in a manner similar to that in Example 1 was formulated into a paint as . follows:
  • the alkyd dispersion and latex blend (Aquamac ® 440) was tested as a universal primer with the following general results.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention porte sur des dispersions polymères alkyde aqueuses, stables, et sur des mélanges de ces dispersions avec des latex. Le mélange de la dispersion alkyde et du polymère de latex est efficace pour former un revêtement de base présentant une bonne résistance à l'humidité et une résistance à la corrosion due aux embruns salés, un faible taux de contaminants organiques volatils, des temps de séchage très rapides, une résistance aux taches dues à l'eau et une bonne résistance en général, ainsi que d'excellentes propriétés d'application.
PCT/US2001/023896 2000-08-02 2001-07-30 Dispersions polymeres aqueuses stables et formulations contenant des polymeres de latex pour former des revetements a base d'eau WO2002010297A2 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7052540B2 (en) 2004-03-11 2006-05-30 Eastman Chemical Company Aqueous dispersions of carboxylated cellulose esters, and methods of making them
EP1696010A1 (fr) * 2005-02-23 2006-08-30 Deutsche Amphibolin-Werke Von Robert Murjahn Stiftung & Co. KG Résines alkydes pour revêtements à haute teneur en matières solides
WO2009121887A1 (fr) * 2008-03-31 2009-10-08 Dsm Ip Assets Bv Composition aqueuse de revêtement de polyester auto-oxydable
US20100166967A1 (en) * 2008-12-29 2010-07-01 David Michael Fasano High gloss extended alkyd emulsion paints
US20110207850A1 (en) * 2009-10-30 2011-08-25 Dow Global Technologies Llc Coating composition, and a process for producing the same
US8298281B2 (en) 2006-07-18 2012-10-30 Cordis Corporation Twisted anchoring barb for stent of abdominal aortic aneurysm (AAA) device
US20140024742A1 (en) * 2011-04-08 2014-01-23 Rohm And Haas Chemicals Llc Coating composition, and a process for producing the same
WO2014018818A1 (fr) * 2012-07-26 2014-01-30 The Sherwin-Williams Company Compositions de revêtement
WO2016073260A1 (fr) * 2014-11-03 2016-05-12 Arkema Inc. Latex comprenant une dispersion d'alkyde à modification acrylique soluble dans l'eau, et son procédé de production

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US3494882A (en) * 1967-08-09 1970-02-10 Celanese Coatings Co Water reducible gloss enamels
US4420575A (en) * 1982-07-26 1983-12-13 Plasti-Kote Company, Inc. Water reducible aerosol paints
WO1999007759A1 (fr) * 1997-08-12 1999-02-18 Eastman Chemical Company Dispersions alkydes sulfonees aqueuses acryliques modifiees

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3494882A (en) * 1967-08-09 1970-02-10 Celanese Coatings Co Water reducible gloss enamels
US4420575A (en) * 1982-07-26 1983-12-13 Plasti-Kote Company, Inc. Water reducible aerosol paints
WO1999007759A1 (fr) * 1997-08-12 1999-02-18 Eastman Chemical Company Dispersions alkydes sulfonees aqueuses acryliques modifiees

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7052540B2 (en) 2004-03-11 2006-05-30 Eastman Chemical Company Aqueous dispersions of carboxylated cellulose esters, and methods of making them
EP1696010A1 (fr) * 2005-02-23 2006-08-30 Deutsche Amphibolin-Werke Von Robert Murjahn Stiftung & Co. KG Résines alkydes pour revêtements à haute teneur en matières solides
US8298281B2 (en) 2006-07-18 2012-10-30 Cordis Corporation Twisted anchoring barb for stent of abdominal aortic aneurysm (AAA) device
US9416295B2 (en) 2008-03-31 2016-08-16 Dsm Ip Assets B.V. Aqueous autoxidisable coating composition
WO2009121887A1 (fr) * 2008-03-31 2009-10-08 Dsm Ip Assets Bv Composition aqueuse de revêtement de polyester auto-oxydable
WO2009121889A1 (fr) * 2008-03-31 2009-10-08 Dsm Ip Assets Bv Composition de revêtement comprenant un composant auto-oxydable
US9574105B2 (en) 2008-03-31 2017-02-21 Dsm Ip Assets B.V. Coating composition comprising autoxidisable component
US20100166967A1 (en) * 2008-12-29 2010-07-01 David Michael Fasano High gloss extended alkyd emulsion paints
US8470910B2 (en) * 2008-12-29 2013-06-25 Rohm And Haas Company High gloss extended alkyd emulsion paints
US20110207850A1 (en) * 2009-10-30 2011-08-25 Dow Global Technologies Llc Coating composition, and a process for producing the same
US8709607B2 (en) * 2009-10-30 2014-04-29 Dow Global Technologies Llc Coating composition, and a process for producing the same
EP2694606B1 (fr) 2011-04-08 2015-07-15 Dow Global Technologies LLC Composition de revêtement et son procédé de production
AU2011364953B2 (en) * 2011-04-08 2016-04-21 Dow Global Technologies Llc A coating composition, and a process for producing the same
US20140024742A1 (en) * 2011-04-08 2014-01-23 Rohm And Haas Chemicals Llc Coating composition, and a process for producing the same
US9631115B2 (en) * 2011-04-08 2017-04-25 Dow Global Technologies Llc Coating composition, and a process for producing the same
AU2016204918B2 (en) * 2011-04-08 2018-04-19 Dow Global Technologies Llc A coating composition, and a process for producing the same
AU2018206714B2 (en) * 2011-04-08 2020-03-26 Dow Global Technologies Llc A coating composition, and a process for producing the same
WO2014018818A1 (fr) * 2012-07-26 2014-01-30 The Sherwin-Williams Company Compositions de revêtement
WO2016073260A1 (fr) * 2014-11-03 2016-05-12 Arkema Inc. Latex comprenant une dispersion d'alkyde à modification acrylique soluble dans l'eau, et son procédé de production
US10294320B2 (en) 2014-11-03 2019-05-21 Arkema Inc. Latex comprising water-soluble acrylic modified alkyd dispersion and method of production thereof

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