WO2016153818A1 - Mélanges de polymère dispersible dans l'eau comprenant des dispersions de polymère de triglycérides époxydés - Google Patents

Mélanges de polymère dispersible dans l'eau comprenant des dispersions de polymère de triglycérides époxydés Download PDF

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Publication number
WO2016153818A1
WO2016153818A1 PCT/US2016/022049 US2016022049W WO2016153818A1 WO 2016153818 A1 WO2016153818 A1 WO 2016153818A1 US 2016022049 W US2016022049 W US 2016022049W WO 2016153818 A1 WO2016153818 A1 WO 2016153818A1
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acrylate
urethane
polymer
polymer dispersion
dispersion
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PCT/US2016/022049
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English (en)
Inventor
George E. AHRENS
Jonathan J. BIRD
Anthony D. Pajerski
Mathew R. HANEY
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Lubrizol Advanced Materials, Inc.
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Publication of WO2016153818A1 publication Critical patent/WO2016153818A1/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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/06—Copolymers with vinyl aromatic monomers
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates

Definitions

  • Blends of conventional polymer dispersions with a polymer derived from epoxidized triglycerides has useful properties for coatings or inks.
  • Prepolymers from functionalized epoxidized triglyceride oils are disclosed that are free-radically co-polymerizable with other monomers. They can form polymers that are self- crosslinkable. Self-crosslinking can be achieved via a reaction sequence where a hydrazine containing moiety is added that can chemically react and bond to a carbon atom of a carbonyl group (e.g. reactive aldehyde or ketone type) attached to the prepolymer.
  • the epoxidized triglyceride can be made copolymerizable with acrylate type monomers by reacting the epoxy group with acrylic or methacrylic acid, wherein the acid group opens the epoxy ring and leaves a residual hydroxyl group from the epoxy ring.
  • the epoxidized triglyceride can be made water dispersible by chemically bonding an anhydride of a di or polycarboxylic acid molecule via an ester linkage with pendant hydroxyl groups on the prepolymer.
  • the prepolymer can be modified with species such as levulinic acid to bond a reactive carbonyl (ketone) group to the triglyceride.
  • Waterborne dispersions are utilized in the coatings industry to provide substrates with aesthetic beauty, solvent and chemical resistance, mar and scuff resistance, and abrasion resistance. Such waterborne dispersions are commonly used for coating wood, masonry, plastic, textile, and metal products and can also be used in ink jet ink compositions. In recent years, waterborne dispersions have come into favor from an environmental standpoint as replacements for oil based coating compositions because they can be formulated with a low level of volatile organic compounds (VOCs) and are preferably free of volatile organic compounds.
  • VOCs volatile organic compounds
  • United States Patent 4,066,591 and United States Patent 4, 147,679 disclose the preparation of waterborne polyurethane dispersions which contain unsaturated functional groups capable of undergoing auto-oxidative crosslinking.
  • United States Patent 4,598, 121 discloses a method for preparing an aqueous polyurethane dispersion, comprising (a) preparing a prepolymer with free NCO groups by reacting an aliphatic or cycloaliphatic polyisocyanate with a polyol, and an anionic compound; (b) dispersing said prepolymer in water; (c) reacting said water-dispersed prepolymer with a diamino hydrazide as a chain lengthening agent; and (d) reacting the prepolymer of step (e) in said dispersion with formaldehyde to effect crosslinking.
  • United States Patent 4,983,662 discloses an aqueous self crosslinkable coating composition comprising an aqueous dispersion of at least one polyurethane and having hydrazine (or hydrazone) functional groups and carbonyl functional groups, disposed therein, to provide a self-crosslinking reaction in which the polyurethane polymer takes part via azomethine formation during and/or after film formation.
  • United States Patent 5,141,983 discloses a ketone-hydrazide crosslinking technology where the ketone, or carbonyl group resides on an acrylic polymer and a polyurethane polymer contains hydrazide functional groups.
  • the composition is obtained by polymerizing the acrylic monomers in the presence of an aqueous polyurethane dispersion.
  • United States Patent 5,571,861 and United States Patent 5,623,016 disclose an aqueous, self-crosslinking polymer dispersion binder(s) comprising polyhydrazides and carbonyl-containing polyurethane-vinyl hybrid polymers and also, if desired, conventional additives useful in base coatings, aqueous coatings, adhesives and printing inks.
  • United States Patent 6,239,209 discloses waterborne urethane-acrylic compositions which are auto-oxidatively crosslinkable.
  • the composition also contains ketone hydrazide type self-crosslinking where the ketone/carbonyl is introduced via the acrylic and the hydrazide functionality is contained on the polyurethane along with the unsaturated oxidatively curable functional groups.
  • United States Patent 6,576,702 discloses waterborne polyurethane dispersions are prepared by reacting (1) at least one polyisocyanate; (2) at least one active hydrogen containing compound, such as a polyol or a polyamide; and (3) preferably also at least one water-dispersibility enhancing compound having water-dispersion enhancing groups, in order to form an isocyanate terminated prepolymer.
  • United States Patent Application Publication No. 2010/0330375 discloses aqueous polyurethane dispersions that are made from urethane prepolymers comprising one or more polyhydroxy compounds from ketone functional molecules derived from an epoxidized natural oil (triglycerides).
  • US2014/0378607 discloses a water dispersible, self- crosslinkable prepolymer composition with a high content of raw materials from renewable resources.
  • the prepolymers are based on epoxidized triglyceride oils reacted with acid containing molecules to generate pendant hydroxyl groups, pendant acid groups, pendant unsaturation, and pendant ketone or aldehyde groups.
  • the prepolymers can be copolymerized with ethylenically unsaturated monomers to form polymer dispersions which form good coatings and are self-crosslinkable.
  • the present invention provides a new use for the copolymer with an adjustable content of raw materials from renewable resources and generally a lower volatile organic content disclosed in US2014/0378607.
  • Those copolymers are copolymers of triglyceride oils, such as soybean oil, linseed oil, or some other natural oil, with a vinyl compound, such as an acrylate or methacrylate, and optionally a vinyl aromatic monomer, such as styrene.
  • copolymers derived from functionalized epoxidized triglycerides copolymerized with various unsaturated monomers including at least acrylate monomers can be used as an additive to conventional polymers for coatings to reduce the need for coalescing agents, plasticizers, etc. In that function they can lower the film formation temperature of the polymer, form a more fused polymer film, help flow and leveling of the coating, help the final gloss reading of the coating, etc.
  • the copolymers can modify the drying times (such as dry to the touch, dry enough to recoat, or dry enough to sand) of coatings derived from acrylate latexes or urethane dispersions.
  • Using varying amounts of the copolymers from functionalized epoxidized triglycerides copolymerized with acrylates monomers allows formulators to create a variety of different coating blends customized to meet volatile organic content (VOC) requirements, film formation temperature requirements or drying characteristics.
  • VOC volatile organic content
  • copolymers of functionalized epoxidized triglycerides can either be high in natural oil content, high in vinyl content, high in ionic species to help dispersibility, or high in crosslinking capability, or mixtures thereof depending on the intended end use. Moreover, a variety of functionality can be incorporated into the copolymer dispersions either through the natural oil and/or the vinyl component.
  • the present invention more specifically, discloses a physical blend of at two different water dispersible polymer compositions, wherein the first polymer is a copolymer comprised of a triglyceride oil having appended thereto (1) hydroxyl groups, (2) moieties which contain at least one aldehyde group or at least one ketone group, (3) moieties which contain at least one vinyl and/or substituted vinyl group, and (4) optionally, epoxy groups.
  • the binder materials are crosslinkable with an external crosslinker or are self-crosslinkable.
  • Figure 1 illustrates the synthesis of a prepolymer (not functionalized yet for water-dispersibility) or macromonomer which utilizes an epoxidized triglyceride oil, such as epoxidized soybean oil, as the starting material.
  • This reaction is carried out by reacting the epoxidized triglyceride oil with (1) a ketone functionalized carboxylic acid or an aldehyde functionalized carboxylic acid, and (2) optionally, a vinyl functionalized carboxylic acid.
  • Figure 2 illustrates the synthesis of a water dispersible self-crosslinkable polymer which utilizes the non-dispersible prepolymer of this invention, as described in Figure 1, as a starting material.
  • the non-dispersible prepolymer is reacted with an anhydride of a di or polycarboxylic acid to prepare a water dispersible prepolymer.
  • Figure 3 illustrates the 60°gloss of polymer films over cedar board of various blends of Example 3 polymer with urethane and acrylic polymers after exposure for 200 to 1000 hours under UV340 lamp light.
  • the water dispersible, self-crosslinkable copolymer compositions of this invention are comprised of a polymerization (e.g. free radical) product of triglyceride oil having appended thereto (1) hydroxyl groups, (2) moieties, which contain at least one carbonyl groups such as an aldehyde group or a ketone group, (3) moieties, which contain at least one vinyl and/or substituted vinyl group, and (4) optionally epoxy groups and water dispersibility enhancing groups.
  • a polymerization e.g. free radical
  • This monomer from epoxidized triglyceride which is generally above 300 g/mole molecular weight is copolymerized with vinyl or substituted vinyl monomers as described below (desirably characterized as being less than 300 g/mole molecular weight before polymerization) to form a copolymer.
  • vinyl group is typically used to define a group with alpha-beta unsaturation wherein the two carbons of the alpha-beta unsaturation have jointly appended to them three hydrogen atoms.
  • substituted vinyl groups to include groups derived from unsaturated aliphatic anhydrides of di or polycarboxylic acids such as maleic anhydride or itaconic anhydride and/or C 1-4 - alkyl substituted acrylic acids.
  • the substituted vinyl groups are derived from reacting the unsaturated aliphatic anhydrides or di or polycarboxylic acid directly with a hydroxyl group attached directly to a carbon of the triglyceride oil or to an epoxy functionality that comprises an oxygen atom and two carbon atoms of the triglyceride oil.
  • substituted vinyl as being free radically copolymerizable with vinyl monomers such as where one of more of the three hydrogens are replaced by Ci-4-alkyl groups (such as derived from methacrylic acid) and/or carboxylic or Ci-4-alkyl carboxylic groups such as derived from maleic anhydride or itaconic anhydride.
  • This prepolymer composition is made by reacting an epoxidized triglyceride oil with a ketone or aldehyde functionalized carboxylic acid and vinyl group containing carboxylic acid. This reaction is illustrated in Figure 1 and is normally carried out in the presence of a catalyst at an elevated temperature which is typically within the range of about 100 °C to about 150 °C.
  • this reaction it is preferred for this reaction to be conducted at a temperature which is within the range of 120 °C to about 135 °C.
  • Zinc, zirconium, chromium, and iron catalysts can be used advantageously in carrying out this reaction.
  • Some additional examples of catalysts that can be used include trialkylamines, phosphines such as triphenylphosphine, and imidiazoles, such as N-methylimidazole, and the like.
  • the triglyceride oils that can be utilized as a starting material are unsaturated vegetable oils, animal fats, or synthetic triglycerides, which are generally considered to be derived from condensation reactions of various fatty acids and glycerol. While the triglycerides are often described as oils, they may be solids at room temperature. The higher the amount of unsaturation present, the higher the degree of epoxidation possible under similar reaction conditions. Reactions of these unsaturated oils with strong oxidizers can convert the carbon to carbon double bond in the fatty acids to epoxides.
  • Peracetic acid is a strong oxidizer that can be used for this purpose. The peracetic acid can be obtained from the reaction of acetic acid with hydrogen peroxide. Acetic acid can be obtained from the well-known process of bacterial fermentation.
  • Epoxidized vegetable oils are commercially available from a number of sources, including companies such as Dow Chemical and Chemtura.
  • the oxirane oxygen content is generally within the range of about 2 to 14 weight percent and is typically within the range of 5 to 12 weight percent before reaction with the ketone or aldehyde functionalized carboxylic acid. It is, typically, preferred to employ an epoxidized triglyceride oil having an oxirane oxygen content which is within the range of 6 to 10 weight percent.
  • the amount of epoxidized triglyceride is from about 64 to 96 wt.%, more desirably 68-87 wt.%) and preferably 72-83 wt.%> of the functionalized triglyceride.
  • the amount of carbonyl functional carboxylic acid component in the functionalized triglyceride is from about 2 to about 25 wt.%, more desirably from about 8 to 20 wt.%), and preferably from about 10 to 15 wt.%>.
  • the amount of di or poly carboxylic acids or anhydrides thereof incorporated into the functionalized triglyceride is from about 1 to about 15 wt.%, more desirably from about 3 to 10 wt.%, and preferably from about 4 to 8 wt.%> of the functionalized triglyceride.
  • the amount of vinyl group and/or substituted vinyl group containing carboxylic acid in the functionalized triglyceride is from about 1 to about 10 wt.%, more desirably from about 2 to 6 wt.% and preferably from about 2.5 to 5 wt.% wherein all weights are based on the weight of the functionalized triglyceride.
  • the carbonyl, e.g. ketone or aldehyde, functionalized carboxylic acid utilized will normally be of the formula: o o
  • A represents a hydrocarbyl moiety containing from 1 to 20 carbon atoms and wherein R represents a hydrogen atom or an alkyl group containing from 1 to 8 carbon atoms.
  • the ketone or aldehyde functionalized carboxylic acid will typically be of the formula: o o
  • n represents an integer from 1 to 8 and wherein R represents a hydrogen atom or a methyl group. In most cases, n will represent an integer from 2 to 4 with n typically representing 2.
  • a preferred carbonyl, e.g. ketone or aldehyde, containing carboxylic acid is levulinic acid ( ⁇ -ketovaleric acid; acetylpropionic acid, 4-oxopentanoic acid) or pyruvic acid (a-ketopropionic acid; acetylformic acid).
  • the proportion of carbonyl functional groups in the free radically polymerized polymer is preferably 3 to 200 milliequivalents per lOOg polymer (more preferably 6 to 100 milliequivalents per lOOg polymer). It is possible to use ketone functional diols or polyols from synthetic sources in combination with those obtained from mainly renewable raw materials.
  • vinyl group containing carboxylic acids are utilized in making the prepolymer of this invention, they will normally be of the structural formula: wherein R 1 , R 2 , and R 3 can be the same or different and represent hydrogen atoms or alkyl groups containing from 1 to 8 carbon atoms.
  • Preferred vinyl group containing carboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid, and the like.
  • the synthesis of the water dispersible, self-crosslinkable prepolymer composition involves the reaction of the epoxidized vegetable oil with a ketone or aldehyde functionalized carboxylic acid and then reaction with an anhydride of a polycarboxylic acid, such as maleic anhydride, to produce an aqueous self-crosslinkable copolymer dispersion, optionally in the presence of a catalyst.
  • a diluent such as acetone, methyl ethyl ketone, or preferably a vinyl monomer, is normally added to keep the viscosity within a commercially acceptable range.
  • This reaction is depicted in Figure 2 and is normally conducted at an elevated temperature in the presence of a catalyst.
  • the catalyst can be a tertiary amine (such as a trialkylamine), a phosphonium compound, an inorganic metal salt, a metal alkoxide or a metal chelate.
  • a tertiary amine such as a trialkylamine
  • a phosphonium compound such as an inorganic metal salt
  • an inorganic metal salt such as a metal alkoxide or a metal chelate.
  • Some representative examples of catalysts that can be used include trimethylamine, triethylamine, tri-n-propylamine, tri-iso- propylamine, tri-n-butylamine, tri-t-butylamine, pyridine, isoquinoline, quinoline, ⁇ , ⁇ -dimethylcyclohexylamine, N-ethylmorpholine, dimethylaniline, dimethylbenzylamine, alkoxides, chelates, or halides of Al, B, Be, Fe(III), Sb(
  • the anhydrides of di or polycarboxylic acids that can be utilized in preparing the water dispersible prepolymer can be aliphatic or aromatic.
  • Some representative examples of such anhydrides include maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride, pyromellitic anhydride, mellitic anhydride, trimellitic anhydride, and the like.
  • the preferred anhydrides for this use are maleic anhydride, itaconic anhydride, succinic anhydride, trimellitic anhydride, and phthalic anhydride.
  • the most preferred anhydrides are maleic anhydride and itaconic anhydride.
  • anhydrides after a ring opening reaction, as depicted in Figure 2, can function as a dispersing agent for the water dispersible prepolymer after being ionized.
  • an external surfactant is utilized as a dispersing agent.
  • the water dispersible, self-crosslinkable prepolymer composition will generally have a number average molecular weight which is within the range of about 1,500 to about 19,000.
  • the said prepolymer will typically have a number average molecular weight which is within the range of about 2,000 to 9,000, and will more typically have a number average molecular weight which is within the range of about 2,500 to about 5,000.
  • the higher molecular weight can result from coupling multiple epoxidized oils (e.g., though ester linkages from the carboxylic acid groups of the maleic anhydride) into a prepolymer.
  • the moieties which contain at least one carbonyl, e.g. aldehyde group or ketone group, are of the formula:
  • A represents a hydrocarbyl moiety containing from 1 to 20 carbon atoms and wherein R 1 represents a hydrogen atom or an alkyl group containing from 1 to 8 carbon atoms. In many cases these moieties are of the formula: o o
  • n represents an integer from 1 to 8 and wherein R represents a hydrogen atom or a methyl group. In most cases, n will represent an integer from 2 to 4 with n typically representing 2.
  • the moieties which contain at least one vinyl and/or substituted vinyl group, are of a formula selected from the group consisting of:
  • n represents an integer from 0 to 8
  • R 1 , R 2 , and R 3 can be the same or different and represents hydrogen atoms or alkyl groups containing from 1 to 8 carbon atoms.
  • n will represent in integer from 0 to 4 with n typically being 0.
  • Normally, on average from 1 to about 4 functional groups will be appended to each molecule of triglyceride oil with it being more typical for 2 or 3 functional groups to be appended to each molecule of triglyceride oil.
  • the prepolymer is neutralized by reaction with at least one neutralizing agent and dispersed in aqueous medium.
  • the acrylic polymer or copolymer can be derived from a variety of unsaturated monomers such as from acrylate, alkyl (alk)acrylate, vinyl chloride, vinylidene chloride, vinyl esters such as vinyl acetate, styrene, butadiene, acrylonitrile, and unsaturated acid containing monomers.
  • unsaturated monomers such as from acrylate, alkyl (alk)acrylate, vinyl chloride, vinylidene chloride, vinyl esters such as vinyl acetate, styrene, butadiene, acrylonitrile, and unsaturated acid containing monomers.
  • the copolymer from copolymerizing the functionalized triglyceride with acrylates and other monomers will in one embodiment desirably comprise from about 20 to about 65 or 75 wt.% of functionalized epoxidized oil residue, more desirably from about 30 to 55 wt.% and preferably from about 35 to 50 wt.% based on the weight of the copolymer.
  • the amount of acrylates, alkacrylates, and/or vinyl esters (the total for two or three is present and the conjunction "and" is used) is from about 5 to 40 wt.%), more desirably from about 10 to 30 wt.%> and preferably from about 12 to 25 wt.%).
  • the amount of styrene or C 1-4 alkyl substituted styrene is desirably from about 0 or 5 to 20, 25, or 30 wt.%, more desirably from about 5 to 25 wt.%.
  • the amount of polyfunctional crosslinkers (such as di, tri, or tetraacetate of a polyol or divinyl benzene) is from about 0 to about 5 wt.%, and more desirably from about 0.5 to 3 wt.% of the copolymer.
  • other unsaturated free radically polymerizable monomers can be used in amounts from about 0 to about 20 or 30 wt.% of the copolymer.
  • unsaturated free radically polymerizable monomers defined as other than acrylate, alkacrylate, vinyl ester, styrene, and polyfunctional monomers
  • the above compositional ranges for each monomer component can be combined with ranges for other monomer components to create desirable copolymer compositions.
  • R 7 is an alkyl group containing 1 to about 15 carbon atoms, an alkoxyalkyl group containing a total of 1 to about 10 carbon atoms, a cyanoalkyl group containing 1 to about 10 carbon atoms, or a hydroxy alkyl group containing from 1 to about 18 carbon atoms.
  • the alkyl structure can contain primary, secondary, or tertiary carbon configurations and normally contains 1 to about 10 carbon atoms with 2 to 8 carbon atoms being preferred.
  • acrylic esters examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, and the like.
  • Preferred examples include ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, and the like.
  • the various alkyl alkacrylates are of the formula: wherein R 8 is an alkyl group containing 1 to about 15 carbon atoms, an alkoxyalkyl group containing a total of 1 to about 10 carbon atoms, a cyanoalkyl group containing 1 to about 10 carbon atoms, or a hydroxy alkyl group containing from 1 to about 18 carbon atoms (as described above) and wherein R 9 is an alkyl containing from 1 to about 4 carbon atoms, desirably, 1 or 2 carbon atoms with methyl being especially preferred.
  • alkyl (alk)acrylates examples include methyl methacrylate, ethyl methacrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxy ethyl acrylate, ethoxypropyl acrylate, and the like.
  • Derivatives include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like. Mixtures of two or more of the above monomers can also be utilized.
  • the vinyl esters can generally be represented by the formula:
  • R C II— O CH CH 2
  • R 10 is an alkyl group generally having from 1 to about 10 or 12 carbon atoms with from about 1 to about 6 carbon atoms being preferred.
  • suitable vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, and the like.
  • Vinyl esters with larger R 10 groups include the vinyl versatate monomers, such as Veo VA-P, Veo Va-10, and Veo Va-11.
  • styrenic monomers are often referred to as vinyl substituted aromatic compounds (styrenic monomers) and include styrene, alkyl substituted styrene 1-vinylnaphthalene, 2-vinylnaphthalene, and the alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof, in which the total number of carbon atoms, in the combined, substituents is generally from 8 to about 12.
  • Examples of such compounds include 3 -methyl styrene vinyltoluene; alpha-methyl styrene; 4-n-propylstyrene, 4-t-butylstyrene, 4-dodecyl- styrene, 4-cyclohexylstyrene; 2-ethyl-4-benzylstyrene; 4-methoxy- styrene; 4-dimethylaminostyrene; 3,5-diphenoxystyrene; 4-p-tolylstyrene; 4-phenyl styrene; 4,5-dimethyl-l-vinylnaphthalene; 3-n-propyl-2 -vinyl- naphthalene, and the like.
  • Styrene is typically preferred.
  • Unsaturated acid containing monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl acrylate and the like. Acrylic acid is preferred.
  • Half esters of the above di-carboxylic acids can also be used as monomers wherein the ester portion is desirably an alkyl having from 1 to about 10 carbon atoms and specific examples include mono methyl maleate, mono methyl fumerate, mono methyl itaconate, and the like.
  • co-polymerizable (ethylenically unsaturated) monomers may be utilized to make copolymers including styrenic monomers (as a co-monomer in the acrylate latex), vinyl chloride type monomers, acrylonitrile type monomers, various vinyl ester monomers, various acrylamides monomers, various alkynol acrylamides and the like.
  • the vinyl chloride type monomers include vinyl chloride, vinylidene chloride, and the like.
  • R 4 is desirably an alkyl having from 1 to about 10 carbon atoms.
  • R 4 is desirably an alkyl having from 1 to about 10 carbon atoms.
  • Specific examples include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and the like with methyl vinyl ether being preferred.
  • the acrylonitrile type monomers that can be utilized include acrylonitrile, or methacrylonitrile, or ethacrylonitrile, and the like.
  • the acrylamide monomers which can be polymerized to form a copolymer generally have the following formula:
  • R 5 o wherein R 5 represents a hydrogen atom or a methyl group and wherein R 6 is represents a hydrogen atom or an alkyl group (straight chained or branched) containing from 1 to about 18 carbon atoms.
  • Specific examples include acrylamide, ethyl acrylamide, butyl acrylamide, tert-octyl acrylamide, tert-butyl methacrylamide, and the like.
  • the one or more acrylamides can be utilized in large amounts such as up to about 20 percent by weight of the copolymer and desirably from about 0.5 to about 10 percent by weight.
  • acrylamides can also be utilized.
  • acrylamides include AMPS, i.e., 2-acrylamido-2-methylpropanesulfonic acid, DMAPMA, i.e., dimethylaminopropyl methacryamide, and the like.
  • Carbonyl containing unsaturated comonomers may be copolymerized with the above monomers to make acrylic or vinyl polymers.
  • acrylamidopivalaldehyde methacrylamidopivalaldehyde, 3-acrylamidomethyl- anisaldehyde, diacetone acrylate, acetonyl acrylate, diacetone methacrylate, acetoacetoxyethylmethacrylate, 2-hydroxypropylacrylate acetylacetate, and butanediol acrylate acetylacetate. More details on using these monomers are provided in United States Patent 4,983,662. The teachings of United States Patent 4,983,662 are incorporated herein by reference for the purpose of describing the use of such monomers in greater detail.
  • the vinyl monomers can be intentionally grafted or copolymerized with the water dispersible prepolymer component of this invention by using active hydrogen containing vinyl monomers in the formation of the prepolymer or the vinyl polymers.
  • active hydrogen containing vinyl monomers include 2-hydroxyethyl acrylate (2HEA) and 2-hydroxyethyl methacrylate (2HEMA).
  • Conventionally free radical initiators known to the art and to the literature, can be utilized to initiate polymerization of the various above-noted monomers or co-monomers to form a polymer or copolymer.
  • Such free radical initiators generally, include the persulfates, the peroxides, and azo compounds, as well as redox combinations and radiation sources.
  • Examples of preferred persulfate initiators include potassium persulfate, sodium persulfate, or ammonium persulfate, and the like.
  • the free radical polymerization can be an emulsion, bulk, solution, or dispersion polymerization.
  • any type of peroxide, azo, redox system, or related initiator system can be utilized.
  • Peroxide systems include dicumyl peroxide, cumene hydroperoxide, t-butyl perbenzoate, bis(t-butylperoxy) diisopropyl benzene, diisopropyl benzene hydroperoxide and n-butyl 4,4-bis(t-butylperoxy) valerate, as well as benzoyl peroxide, and t-butyl hydroperoxide, and the like. Cumene hydroperoxide, t-butyl hydroperoxide and diisopropyl benzene hydroperoxide are preferred.
  • Azo initiators include 2,2'-azobis(isobutyronitrile)(AIBN) and related azo initiators.
  • Chain-transfer agents can be utilized, such as, various mercaptans, for example, thioethanol mercaptan, hydroxyl ethyl mercaptan, various reaction products of alkyl esters of mercaptan with acidic acid or with thiogylcolic acid, and the like wherein the alkyl group has from about 2 to about 20 carbon atoms.
  • chain transfer agent is beta mercapto propionic acid and its esters such as butyl-3-mercaptoproprinate.
  • chain transfer agents can include dithiocarbamates or di or trithiocarbonates.
  • the prepolymer is dispersed in an aqueous medium to form a dispersion.
  • Dispersing the prepolymer in aqueous medium can be done by any conventional technique, in the same way that polyurethane prepolymers made by bulk or solution polymerization are dispersed in water as described in United States Patent Application Publication No. 2010/0330375 Al .
  • the teachings of United States Patent Application Publication No. 2010/0330375 Al are incorporated herein by reference. Normally, this will be done by combining the prepolymer blend, with water with mixing. Where solvent polymerization is employed, the solvent and other volatile components can optionally be distilled off from the final dispersion, if desired.
  • the hydrazine functional moiety, for crosslinking with the ketone group, can be added at this stage or later.
  • Two essential components to the current invention are the copolymer from functionalized triglyceride and a second more conventional polymer, both separately made or dispersed in water and then combined. It is desirable that the polymers be separately dispersed such that separate polymer compositions exist in separate particles that are then blended together.
  • the conventional polymer dispersions may be acrylate type polymer dispersions (such as those made by emulsion polymerization), urethane dispersions in water made from processes where a urethane or prepolymer is first made and then dispersed in water and then chain extended, or hybrids of acrylate and urethane polymers dispersed in water.
  • the second (more conventional polymer dispersion) is crosslinkable either with an external crosslinker added shortly before using the coating or an internal crosslinker that can be added during formulations of a coating or ink from the polymers.
  • both the copolymer from acrylates and functionalized triglycerides and the conventional polymer dispersion are crosslinkable with an internal crosslinker (added at time of formulation of polymers into final formulation).
  • an internal crosslinker is crosslinkable (either with internal crosslinker or external crosslinker).
  • internal crosslinking refers to crosslinkers that are incorporated into the polymer during polymerization (such as polyacrylates or ketone and hydrazine/hydrazide functionality).
  • external crosslinkers for additives (such a polyisocyanates) that can be added to the coating shortly before application. External crosslinkers tend to be too reactive to be mixed with the binder at the binder manufacture or coating formulation stage.
  • An advantage of the current disclosure is that two separate polymer dispersions are made and can be stored and then at a later time they can be blended in a variety of weight ratios to get optimal performance as a coating or an ink.
  • the first copolymer of acrylate monomers and functionalized triglyeride (dispersed in water) is utilized in a polymer amounts from about 10 to about 90 weight percent (more desirably 20 to 80 weight percent) (based on the total polymers in the blend).
  • the copolymer of acrylates and functionalized triglycerides is used in polymer amounts from about 30 to about 60, 65, or 70 wt.%, and more preferably in an amount from about 35 to about 55, 60 or 65 wt.%.
  • the conventional polymer (that is dispersed in water) is used in a polymer amount from about 10 to about 90 wt.% (more desirably from about 20 to 80 wt.%) of the blend, and in more desirable embodiments from about 30, 35 or 40 to about 70 wt.%, and preferably from about 40 or 45 to about 65 wt.% of the polymer blend in the two dispersions (based on the combined amounts of polymers plus any optional added polymers).
  • the conventional polymer as a dispersion in water can be any polymer but it is preferred to be an acrylate polymer, a urethane polymer or an acrylate-urethane hybrid polymer.
  • the acrylate polymers in general are made by polymerizing the acrylate monomers in an emulsion polymerization or can be made by other processes (other than emulsion polymerization) and then dispersed in water similar to a urethane dispersion forming process.
  • the urethane polymers are well known to the art and are typically made by a variety of processes where urethane forming monomers (polyisocyanates, polyols, optionally polyamines, etc.) are mixed and reacted (optionally using catalysts) to form prepolymers or polyurethanes. These prepolymers or polyurethanes are functionalized to make them water dispersible and then are dispersed in water. After dispersion in water the prepolymers can be chain extended with polyols or polyamines to former higher molecular weight polyurethanes.
  • hybrids of acrylate and urethane polymers are also well known to the art and are formed similarly to the polyurethane dispersion with the added step of adding acrylate monomers at some stage during or after the preparation of the urethane dispersion and thereafter polymerizing the acrylate monomers into a polyacrylate.
  • the conventional polymers often are formulated into coatings.
  • solvents or plasticizers are considered volatile organic components by regulatory agencies, such as the US Environmental Protection Agency (EPA).
  • EPA US Environmental Protection Agency
  • VOC volatile organic compounds
  • the US EPA defines volatile organic compounds for regulatory purposes as any compound of carbon (excluding carbon monoxide, carbon dioxide, carbonic acid, etc. along with named compounds with low environmental risk and high commercial benefit to society) which participates in atmospheric photochemical reactions.
  • VOC volatile organic content
  • USA EPA Method 24 of less than 300g/liter of coating, more desirably less than 150 g/liter, and preferably less than 50 or 25 g/liter to meet the current regulatory requirements or to reach to exceed anticipated future regulatory requirements.
  • Often meeting these VOC limits means using less solvent or plasticizer, using solvents or plasticizers that are excluded from the regulatory definition of VOC, or otherwise modifying the formulation or polymer to meet VOC requirements.
  • both the copolymer from acrylates and the functionalized triglyceride and the conventional polymer dispersion are crosslinkable, both polymers use the same chemical type of crosslinking mechanism. In another embodiment, the copolymer and the conventional polymer use different types of crosslinking mechanisms.
  • Ketone-hydrazine crosslinking also known as azomethine crosslinking
  • Ketone-hydrazine crosslinking uses a combination of reactive carbonyl groups (aldehyde or ketone groups) and hydrazine or hydrazide groups to form a covalent chemical bond.
  • This type of crosslinking is often used in the copolymer of acrylate and functionalized triglyceride.
  • Another crosslinking mechanism is urethane or urea linkage which can be formed from reactive isocyanate groups and hydroxyl groups or primary or secondary amine groups. The isocyanate containing species can be added just before use or the isocyanate groups can be blocked with an isocyanate blocking groups.
  • Ketoxime type crosslinking is also available where a ketoxime group reacts with hydroxyl groups on the polymer to form a covalent bond. If one desires, conjugated unsaturated groups can be incorporated into a composition and these conjugated unsaturated groups can oxidatively crosslinked (often accelerated by a metal drier) to provided crosslinking. All of these crosslinking systems can be used with the copolymer and conventional polymers of this composition.
  • the preferred hydrazine functional moiety refers to a low molecular weight molecule or oligomers having one or more hydrazine or hydrazone groups.
  • a hydrazine functional group is meant the functional group of formula - HNH2.
  • the hydrazone functional group is a group derived from such a hydrazine group by reaction with a monoketone or monaldehyde containing at least 2 carbon atoms.
  • Hydrazine functional moieties can also be dihydrazides and other polyhydrazides, as expressed below, in that these molecules have the specified - HNH2 group.
  • hydrazine itself (H2N- H2) at elevated concentrations, raises concerns about worker exposure, hydrazide (- HNH2) containing molecules are less of an exposure issue and offer the opportunity to build molecular weight and/or crosslink molecules/oligomers/polymers after polyurethane dispersion coagulation/film formation at or around room temperature.
  • Volatile amines can play a significant role in the reactions using hydrazine functional moieties as the amines are/can be used in polyurethane dispersions to adjust the pH to the basic side before coalescence and allow the pH to shift to the acid side as the water and volatile amines evaporate. This pH shift and water evaporation promotes the reaction of hydrazine or hydrazide groups with available ketone or aldehyde groups (providing molecular weight buildup and or crosslinking).
  • the dispersion can be made without such compounds, i.e., substantially free of surfactants, if desired.
  • a surface active agent such as a sulfate or a phosphate, can beneficially be included in the prepolymer composition.
  • the prepolymer includes water-dispersibility enhancing compounds which produce pendant carboxyl groups
  • these carboxyl groups can be converted to carboxylate anions for further enhancing the water-dispersibility of the prepolymer.
  • a typical way the dispersions of the present invention can be made is by forming a prepolymer blend in the substantial absence of water and then dispersing the blend in an aqueous medium with mixing.
  • Other ways of making aqueous dispersions can also be used to make the dispersions of this invention, including shear mixing, the acetone process, the continuous process polymerization, and the reverse feed process.
  • a bisulfite or sulfite it is frequently desirable to include a bisulfite or sulfite to improve the stability of the dispersion.
  • sodium sulfite, potassium sulfite, ammonium sulfite, calcium sulfite, magnesium sulfite, zinc sulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite, calcium bisulfite, magnesium bisulfite, or zinc bisulfite can be included in the dispersion.
  • the sulfite or bisulfite will typically be added to the dispersion in a post polymerization step because it can interfere with the polymerization by acting as a chain transfer agent.
  • the sulfite or bisulfite will typically not be added in more than a stoichiometric amount, based upon the number of ketone groups in the polymer.
  • the sulfite or bisulfite will typically be added at a level which is within the range of 0.1 weight percent to 0.5 weight percent, based upon the solids content of the dispersion.
  • the prepolymer is dispersed by shear forces with emulsifiers (external emulsifiers, such as surfactants, or internal emulsifiers having nonionic, anionic, cationic and/or zwitterionic groups as part of or pendant to the polymer backbone, and/or as end groups on the polymer backbone).
  • emulsifiers such as surfactants, or internal emulsifiers having nonionic, anionic, cationic and/or zwitterionic groups as part of or pendant to the polymer backbone, and/or as end groups on the polymer backbone.
  • a prepolymer is formed with or without the presence of acetone, MEK, and/or other polar solvents that are non-reactive and easily distilled.
  • the prepolymer is further diluted in said solvents as necessary, and optionally chain extended with an active hydrogen-containing compound. Water is added and then the solvents are distilled off.
  • prepolymer In the continuous process polymerization procedure a prepolymer is formed and then pumped through high shear mixing head(s) and dispersed into water. This is accomplished by multiple streams consisting of prepolymer (or neutralized prepolymer), optional neutralizing agent, water, and/or surfactant.
  • the aqueous self-crosslinkable copolymer dispersion can then optionally be diluted with additional water to any concentration (solids content) that is desired.
  • the aqueous self-crosslinkable copolymer dispersion can then be used in the preparation of water based coatings and inks, such as paints, varnishes, clear-coats, ink jet inks, and paper coatings, employing techniques that are well-known to those skilled in the art.
  • Desired pigments, plasticizers, coalescing solvents, fillers, wetting agents, stabilizers, defoamers, dryers, antibacterial agents, fungicides, insecticides, antifouling agents, and anticorrosive agents can be mixed directly into the aqueous self-crosslinkable copolymer dispersion.
  • Pigments are normally added to paint formulations to impart color and hiding to the coating.
  • Titanium dioxide is an example of a widely used pigment which imparts hiding and a white color.
  • Mineral pigments such as oxides of iron and chromium
  • organic pigments such as phthalocyanine
  • active anticorrosive pigments such as zinc phosphate
  • the fillers employed in making water based coating formulations are normally inexpensive materials which are added to attain the desired consistency and non-settling characteristics. Fillers can also improve a coating's physical properties, such as resistance to cracking and abrasion. Some representative examples of widely utilized fillers include chalks, clays, micas, barites, talcs, and silica.
  • Fungicides and algaecides are commonly added to interior and exterior house paints and are of particular value in coating formulations that will be used in warm climates.
  • Antifouling compounds are commonly added to marine paints to inhibit marine growth.
  • a film forming, water based composition can be prepared utilizing a mixture of the aqueous self-crosslinkable copolymer dispersion, optionally with a suitable coalescing solvent and plasticizer. It is preferred for the coalescing solvent to be at least water immiscible and, even more preferably, for it to be water insoluble.
  • ethylene glycol monobutyl ether ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and/or dipropylene glycol monobutyl ether are preferred.
  • the solvent and plasticizer can be mixed directly with the resin in its water emulsion.
  • Plasticizers are used to control the hardness of the coating and/or to impart flexibility. Poor adhesion can be encountered when water based coatings are applied to some substrates. Adhesion can frequently be improved by the addition of one or more plasticizers to the water based coating formulation.
  • plasticizer which is liquid at room temperature such as 25 °C and have a sufficiently high boiling point, preferably at least 100 °C, and even more preferably, at least 150 °C, so that they do not volatilize from the coating composition when applied to a substrate.
  • the plasticizer should enhance the water insolubility of a dried coating of the coalesced resin. It is important for the plasticizer, or mixture of plasticizers, to be compatible with the resin itself.
  • plasticizers can be used in the practice of this invention. They can, for example, be of the type listed in the Federation Series on Coatings Technology, Unit Twenty-two, entitled “Plasticizers,” published April, 1974, so long as they fulfill the melting point, boiling point and compatibility requirements.
  • plasticizers that can be used include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol n-butyl ether, diethylene glycol hexyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-
  • the reaction between the ketone group of the prepolymer and hydrazine functional moiety is delayed until after particle coagulation and coalescence, but the technology is not limited thereby.
  • the ketone group and the hydrazine functional moiety react to form azomethine linkages as taught in United States Patent 4,210,565 and United States Patent 4,983,662, the teachings of which are incorporated herein by reference.
  • this reaction between the ketone groups of the prepolymer and the hydrazine functional moiety proceeds at a reasonable rate at 20 °C to 25 °C such that lower molecular weight species associated with these moieties are converted at 20 °C to 25 °C (ambient drying temperature) to higher molecular weight and/or crosslinked species that aid rather than detract from polymer hardness, strength, solvent resistance, and related properties of wear resistance.
  • a poly-ketone functional triglyceride was prepared by combining items 1-5 of the ingredients below in a 4 neck flask equipped with a thermometer, overhead stirrer and dry air inlet.
  • the Epoxidized Soybean Oil (ESO) can be sourced as JenkinolTM 680 from Acme Hardesty or PlasthallTMESO from Hallstar. With stirring and under a nitrogen blanket, the temperature of the reaction mixture was raised to 110 to 114 °C and held at this temperature for 1 hour. The temperature was then raised to 121 - 125 °C and held at this temperature for 2 hours or until the acid number was ⁇ 1.0 (mg/g). The final material was clear with an amber tint and a viscosity of -1,510 cps at 70 °C at an acid number of 0.9mg/g. TABLE 1 for forming Functionalized Triglyceride
  • Example 2 of functionalizing a ketone and acrylate functionalized triglyceride with an ionic dispersing group.
  • a dispersible functionalized triglyceride was prepared by first homogenizing a ketone/acrylate functionalized triglyceride prepared as described in above example (Item 1) with maleic anhydride and methyl methacrylate (MMA) (items 1-3) by heating to 60-70 °C until the solid maleic anhydride is homogenized (melted). This is followed by the addition of triethanol amine (TEA) (item 4) and the mixture held at 70 °C for 60 minutes. At this point most if not all of the anhydride has been consumed as evident in the FTIR spectrum not showing any significant peaks at 1779 and 1849 cm "1 (However, some anhydride peak might be buried under other absorption peaks such as those for ester groups).
  • Example 3 of Copolymerizing Acrylates with Ionic group/Ketone/ Acrylate Functionalized Triglyceride The resulting ionic group/ketone/acrylate functionalized triglyceride (180 parts of which) at -25 °C was dispersed in 373 parts of water having an initial temperature of -20 °C that provides a dispersion of a low particle size with a translucent appearance.
  • 58.6 parts of styrene 12.3 parts methyl methacrylate and 5.8 parts of di -vinyl benzene (DVB 80) was added and allowed to homogenize into the dispersion; this resulted in an increase in particle size as evident by the dispersion having an opaque appearance.
  • DVD 80 di -vinyl benzene
  • the resulting dispersion was free radical polymerized by adding 0.03 parts of a 1% Fe-EDTA and 8.0 parts of 3.5% t-butyl hydrogen peroxide which was allowed to mix into the dispersion prior to slowly adding 10.0 parts of 2.0% erythorbic acid at an initial temperature of 21 °C. This resulted in an initiation and polymerization of the vinyl functional monomers with an observed exotherm from 21 to 42 °C. The particle size was found to drop and the viscosity rise as the vinyl polymerization progressed. The vinyl polymerization was followed by the slow addition of 1.6 parts of sodium bisulfite versus 100 parts polymer solids as a 25 wt.% aqueous solution.
  • the final dispersion (copolymer of acrylate and functionalized triglyceride dispersion) had a sediment level of ⁇ 0.1%, with a solids level of 40.2 wt.%, a viscosity of 38 cps (at 25 °C at a pH of 7.0 with a particle size of 52.3 nm.
  • CST 2968 an acrylic copolymer emulsion with 42 wt.% solids, pH 8.1, and a MffT of 57 °C
  • Turboset® 2027 TST 2027
  • Turboset® Ultra Eco TSTULECO
  • SantocureTM 970 SCR 970
  • Carboset® CR-765 CR-765
  • MffT minimum film formation temperature test
  • Blended formulas show improvements in powder generation during sanding without clogging the sandpaper (cobbing is a measurement of sandpaper clogging). People sanding wood finishes like seeing the generation of dust or powder - this shows them that they are actually removing a small amount of the surface and smoothing it out. Example 3 does a good job of improving the development of powder generation of finishes that had poor powder generation. None of the finishes developed cobs on the sand paper - sometimes when more dust/powder is generated the dust agglomerates on the surface of the sand paper and clogs it up - the balls of agglomerates are called cobs.
  • Dry Time Using a Recorder The recorder measures the different stages of drying which are interpreted as set to touch, surface dry, and through dry. Wet films are cast on glass and the recorder is placed in the film to determine the amount of time the film takes to achieve each step in the drying process according to ASTM D5895.
  • the next step can be sanding a sealer, applying another coat of finish, or packaging the final product.
  • the QUV 1000 hours exposure to UV340 lamp light - done in four hour cycles - 4 hours light exposure and 4hours darkness with moisture.
  • the gloss readings were made with a Byk-Gardner tri-gloss meter according to the supplier instructions. Solid cedar was used as the substrate for the results in Figure 3.
  • the Figure 3 results show that blends of polyurethane dispersions and Example 3 result in higher gloss retention than the individual polyurethanes by themselves.
  • SCR970 is thermoplastic and TSTULECO and TST2027 are self-crosslinking polyurethane dispersions - both types show improvements in gloss retention.
  • Acrylic emulsions - both thermoplastic and self-crosslinking were also tested in blends in this study but did not exhibit the same improvements in gloss retention.
  • the same exposure using mahogany as the substrate shows results similar the data in the graph above.

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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une voie pour former un mélange polymère à partir de deux polymères dispersés dans un milieu aqueux pourvu de caractéristiques améliorées, telles que des quantités réduites de solvants de coalescence ou un minimum de température de formation de film inférieure, etc., un polymère étant un polymère à faible Tg dérivé d'une huile de triglycéride époxydé fonctionnalisé en la faisant réagir avec une espèce d'acide carboxylique portant des groupes permettant la dispersion dans l'eau, une insaturation polymérisable, et des groupes carbonyles capables de réticuler la cétone-hydrazine. Le second polymère est, de préférence, un acrylate classique, un uréthane, ou une dispersion polymère hybride d'uréthane-acrylate.
PCT/US2016/022049 2015-03-20 2016-03-11 Mélanges de polymère dispersible dans l'eau comprenant des dispersions de polymère de triglycérides époxydés WO2016153818A1 (fr)

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