TW201723101A - Blends of water dispersible polymer with dispersions of polymers from epoxidized triglycerides - Google Patents

Abstract

The present invention provides an route to form a polymer blend from two polymers dispersed in aqueous media with enhanced characteristics, such as reduced amounts of coalescing solvents or lower minimum film formation temperature, etc. wherein one polymer is low Tg polymer derived from epoxidized triglyceride oil functionalized by reacting with carboxylic acid species carrying water dispersing groups, polymerizable unsaturation, and carbonyl groups capable of ketone-hydrazine crosslinking. The second polymer is desirably a conventional acrylate, urethane, or urethane-acrylate hybrid polymer dispersion.

Description

Blend of water dispersible polymer with polymer dispersion from epoxidized triglyceride

Blends of conventional polymer dispersions having polymers derived from epoxidized triglycerides have properties that are useful as coatings or inks. The present invention discloses prepolymers derived from functionalized epoxidized triglyceride oils which are capable of free radical copolymerization with other monomers. It can form a self-crosslinkable polymer. Self-crosslinking can be achieved via a reaction sequence in which a hydrazine-containing moiety is added, which can chemically react and bond carbon atoms attached to the carbonyl group (e.g., reactive aldehyde or ketone form) of the prepolymer. The epoxidized triglyceride can be copolymerized with an acrylate type monomer by reacting an epoxy group with acrylic acid or methacrylic acid, wherein the acid group opens the epoxy ring and remains from the epoxy ring. Hydroxyl. The epoxidized triglyceride can be rendered water dispersible by chemically bonding an anhydride of a di- or polycarboxylic acid molecule via an ester linkage to the pendant hydroxyl group of the prepolymer. The prepolymer can be modified with a species such as 4-levulinic acid to bond a reactive carbonyl (ketone) group to the triglyceride.

Aqueous dispersions are used in the coatings industry to provide aesthetic, solvent and chemical resistant, damage and scratch resistant, and abrasion resistant substrates. This aqueous dispersion is often used to coat wood, stone, plastic, fabric, and metal products, as well as inkjet ink compositions. In recent years, aqueous dispersions have been popular for their environmental standpoint in replacing oily coating compositions because they can be formulated to a low degree of volatile organic compounds (VOCs) and preferably are free of volatile organic compounds.

The preparation of an aqueous polyurethane dispersion containing an unsaturated functional group capable of undergoing auto-oxidative crosslinking is disclosed in U.S. Patent No. 4,066,591 and U.S. Patent No. 4,147,679.

U.S. Patent No. 4,598,121 discloses a method of preparing an aqueous polyurethane dispersion comprising (a) reacting an aliphatic or cycloaliphatic polyisocyanate with a polyol and an anionic compound to prepare a free NCO group. a prepolymer; (b) dispersing the prepolymer in water; (c) reacting the water-dispersed prepolymer with a diamine hydrazine as a chain extender; and (d) in the dispersion The prepolymer of step (e) is crosslinked by reaction with formaldehyde.

U.S. Patent No. 4,983,662 discloses an aqueous self-crosslinkable coating composition comprising at least one aqueous dispersion of a polyurethane having ruthenium (or osmium) functional groups and a carbonyl functional group disposed therein to provide Wherein the polyurethane polymer is subjected to a self-crosslinking reaction involving the formation of azomethine during and/or after film formation.

U.S. Patent No. 5,141,983 discloses a ketone-oxime cross-linking technique in which a ketone or carbonyl residue is located in an acrylic polymer and is polymerized. The urethane polymer contains a guanidine functional group. This composition is obtained by polymerizing an acrylic monomer in the presence of an aqueous polyurethane dispersion.

An aqueous self-crosslinking polymer dispersion adhesive comprising a polyfluorene and a carbonyl-containing polyurethane-vinyl hybrid polymer, if desired, is disclosed in U.S. Patent No. 5,571,861 and U.S. Patent No. 5,623,016. Conventional additives are used in base coatings, waterborne coatings, adhesives, and printing inks.

U.S. Patent No. 6,239,209 discloses aqueous urethane-acrylic compositions which are autoxidisable and crosslinkable. In a specific embodiment, the composition also contains a ketone oxime type self-crosslinking in which a ketone/carbonyl group is introduced via an acrylic system, and a ruthenium functional group is contained in the polyamine group together with an unsaturated oxidizable hardening functional group. Acid ester.

U.S. Patent No. 6,576,702 discloses an aqueous polyurethane dispersion prepared by reacting (1) at least one polyisocyanate; (2) at least one active hydrogen-containing compound such as a polyol or a polyamine; And (3) in order to form an isocyanate-terminated prepolymer, at least one water-dispersion strengthening compound having a water-dispersible strengthening group is preferred.

U.S. Patent Application Publication No. 2010/0330375 discloses a urethane prepolymer comprising one or more polyhydroxy compounds, and an aqueous polyamine group made from a ketone functional molecule derived from an epoxidized natural oil. Formate dispersion.

US2014/0378607 (W02013/112530) discloses a water dispersible, self-crosslinkable prepolymer composition having a high content of starting material from a source of regeneration. The prepolymer is based on epoxidation A glyceride oil, which reacts with an acid-containing molecule to produce a pendant hydroxyl group, a pendant acid group, a pendant unsaturated group, and a pendant ketone or aldehyde group. The prepolymer can be copolymerized with an ethylenically unsaturated monomer to form a polymer dispersion which forms a good coating and is self-crosslinkable.

The present invention provides a novel use of an adjustable amount of a raw material from a source of regeneration, typically a copolymer of low volatile organic content, as disclosed in U.S. Patent Application Serial No. 2014/0378,607. These copolymers are triglyceride oils (such as soybean oil, linseed oil, or some other natural oils) with vinyl compounds (such as acrylates or methacrylates), and optionally with vinyl aromatic monomers ( A copolymer such as styrene.

Aqueous dispersions of conventional polymers used as dispersions in water are difficult to meet two conflicting needs. Users of this polymer desire the final film to be hard, abrasion resistant, and resistant to water and organic solvents. However, in order to form a good film from the polymer, the polymer must be soft and fluid at the film formation temperature (usually room temperature 20-25 ° C) selected by the end user. The formulator has used coalescents and plasticizers to soften the polymer and lower the film formation temperature. The coalescing agent tends to be considered to be an undesirable volatile organic content after film formation. The plasticizer remains in the film after film formation and detracts from the final hardness, abrasion resistance, and solvent resistance. It is now desirable to have a composition that lowers the film formation temperature but is not considered a coalescent or plasticizer.

The above-mentioned copolymer derived from functionalized epoxidized triglyceride, copolymerized with various unsaturated monomers including at least one acrylate monomer (desirably characterized by a molecular weight of less than 300 g/mole before polymerization) can be used as a coating material. Conventional polymer additive, while reducing coalescent, plastic Demand for chemicals, etc. Its function is to reduce the film formation temperature of the polymer, form a more fused polymer film, help the flow and leveling of the coating, and contribute to the final gloss reading of the coating. It has been observed that the copolymer can modify the drying time of the coating derived from the acrylate latex or urethane dispersion (e.g., dry to contactable, dry enough to recoat, or dry enough to contact the sand). Using varying amounts of copolymers derived from functionalized epoxidized triglycerides copolymerized with acrylate monomers, the formulator can make a variety of different coating blends that are customizable to meet volatile organic content (VOC) requirements. Film formation temperature requirements, or drying characteristics.

The functionalized epoxidized triglyceride copolymer may be one of a high natural oil content, a high vinyl content, a high ionic species to facilitate dispersibility, or a high crosslinking force, depending on the intended end use. Multiple. Further, various functional groups may be added to the copolymer dispersion via natural oil and/or vinyl components.

More particularly, the present invention discloses a physical blend of at least two different water-dispersible polymer compositions, wherein the first polymer is a copolymer comprising triglyceride oil with (1) a hydroxyl group, (2) a moiety containing at least one aldehyde group or at least one ketone group, (3) a moiety containing at least one vinyl group and/or a substituted vinyl group, and (4) an epoxy group as the case may be. In a preferred embodiment, one, two, or all of the binder material may be crosslinked with an external crosslinking agent or may be self-crosslinkable.

Figure 1 depicts the synthesis of a prepolymer (not yet functionalized for water dispersion) or a macromonomer using an epoxidized triglyceride oil such as epoxidized soybean oil as a starting material. Epoxidized triglyceride The oil is carried out by reacting (1) a ketone-functional carboxylic acid or an aldehyde-functional carboxylic acid, and (2) optionally a vinyl-functional carboxylic acid.

Figure 2 depicts the synthesis of a water-dispersible self-crosslinkable polymer using the non-dispersible prepolymer of the present invention as disclosed in Figure 1 as a starting material. In this reaction, the non-dispersible prepolymer is reacted with an anhydride of a di- or polycarboxylic acid to prepare a water-dispersible prepolymer.

Figure 3 depicts the 60° gloss of the polymer film on a fir board after exposure to various blends of the polymer of Example 3 and the urethane and acrylic polymer after exposure to UV340 light for 200 to 1000 hours.

The water dispersible, self-crosslinkable copolymer composition of the present invention comprises a polymerization (e.g., a free radical polymerization) product of a triglyceride oil having (1) a hydroxyl group and (2) containing at least a moiety of a carbonyl group (such as an aldehyde group or a ketone group), (3) a moiety containing at least one vinyl group and/or a substituted vinyl group, and (4) an epoxy group and a water dispersion strengthening group, as the case may be. The monomer derived from an epoxidized triglyceride having a molecular weight of usually more than 300 g/mol is copolymerized with a vinyl or substituted vinyl monomer described below (desirably characterized by a molecular weight of less than 300 g/mole before polymerization). The copolymer is formed. The term vinyl is generally used to define a group having an alpha-beta unsaturation wherein the two carbon atoms of the alpha-beta unsaturation together carry three hydrogen atoms. Applicants define substituted vinyl groups to include groups derived from unsaturated aliphatic anhydrides derived from di- or polycarboxylic acids, such as maleic anhydride or itaconic anhydride and/or C _1-4 -alkyl substituted acrylic acid. . In a specific embodiment, the substituted vinyl group is an unsaturated aliphatic anhydride or a di- or polycarboxylic acid directly attached to a hydroxyl group of a carbon of a triglyceride or an epoxy functional group of a triglyceride. Derived by reacting a hydroxyl group (containing one oxygen atom and two carbon atoms). In this particular embodiment, there is no polyether linkage between the triglyceride oil and the vinyl group. In this regard, Applicants have defined a substituted vinyl group as a free radical copolymerizable with a vinyl monomer such as one or more of three hydrogen atoms which may be C _1-4 -alkyl (eg, Derived from methacrylic acid) and/or carboxyl or C _1-4 -alkyl carboxyl groups (eg derived from maleic anhydride or itaconic anhydride). This prepolymer composition is produced by reacting an epoxidized triglyceride oil with a ketone or aldehyde functionalized carboxylic acid and a vinyl group containing carboxylic acid. This reaction is depicted in Figure 1 and is typically carried out at elevated temperatures (typically in the range of from about 100 ° C to about 150 ° C) in the presence of a catalyst. In most cases, it is preferred that the reaction be carried out at a temperature ranging from 120 ° C to about 135 ° C. Zinc, zirconium, chromium, and iron catalysts can be advantageously used to carry out this reaction. Some additional examples of catalysts that may be used include trialkylamines, phosphines (such as triphenylphosphine), and imidazoles (such as N-methylimidazole) and the like.

The triglyceride oil which can be used as a starting material is an unsaturated vegetable oil, tallow, or a synthetic triglyceride (which is generally considered to be derived from a condensation reaction of various fatty acids with glycerin). Although triglycerides are often referred to as oils, they can be solid at room temperature. Under similar reaction conditions, the higher the amount of unsaturation present, the higher the degree of viable epoxidation. The reaction of these unsaturated oils with strong oxidizing agents converts carbon in the fatty acid to carbon double bonds to epoxides. Peracetic acid is a strong oxidizing agent that can be used for this purpose. Peracetic acid can be obtained from the reaction of acetic acid with hydrogen peroxide. Acetic acid can be obtained from known bacterial fermentation processes.

Epoxidized vegetable oils are commercially available from a number of sources, including companies such as Dow Chemical and Chemtura. Functionalized carboxylic acid with ketone or aldehyde Prior to the reaction, the oxygen content of the ethylene oxide is typically in the range of from about 2 to 14 weight percent, and is generally in the range of from 5 to 12 weight percent. In general, it is preferred to use an epoxidized triglyceride oil having an oxygen content of ethylene oxide in the range of 6 to 10% by weight.

While the amount of various groups in the functionalized epoxidized triglyceride prepolymer (functionalized triglyceride) can vary widely, in one embodiment, the amount of the epoxidized triglyceride is functionalized three. The acid glyceride is about 64 to 96 weight percent, more desirably 68 to 87 weight percent, and preferably 72 to 83 weight percent. In a particular embodiment, the amount of carbonyl-functional carboxylic acid component in the functionalized triglyceride is from about 2 to about 25 weight percent, more desirably from about 8 to 20 weight percent, and preferably about 10 Up to 15 weight percent. In a specific embodiment, the amount of the di- or polycarboxylic acid or anhydride thereof incorporated into the functionalized triglyceride is from about 1 to about 15 weight percent of the functionalized triglyceride, more desirably from about 3 to 10 weight percent, and preferably about 4 to 8 weight percent. In a specific embodiment, the amount of the vinyl-containing and/or substituted vinyl carboxylic acid in the functionalized triglyceride is from about 1 to about 10 weight percent, more desirably from about 2 to 6 weight percent, And preferably from about 2.5 to about 5 weight percent, wherein all weights are by weight of the functionalized triglyceride.

The carboxylic acid used to be functionalized with a carbonyl group such as a ketone or an aldehyde typically has the formula:

Wherein A represents a hydrocarbyl moiety having 1 to 20 carbon atoms, and wherein R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The ketone or aldehyde functionalized carboxylic acid generally has the formula:

Wherein n represents an integer of 1 to 8, and wherein R represents a hydrogen atom or a methyl group. In most cases, n represents an integer from 2 to 4, and n generally represents 2.

Preferred carboxylic acids containing a carbonyl group (for example, a ketone or an aldehyde) are 4-pentanone acid (γ-ketovaleric acid, acetamidine propionate, 4-oxopentanoic acid) or pyruvic acid (α-ketopropionic acid, B).醯carboxylic acid). The proportion of the carbonyl-functional group in the radically polymerized polymer, if any, is preferably from 3 to 200 milliequivalents per 100 grams of polymer (more preferably from 6 to 100 milliequivalents per 100 grams of polymer) . Ketone functionalized diols or polyols derived from synthetic sources as well as from a variety of renewable starting materials can also be used.

In the case where a prepolymer of the present invention is produced using a vinyl group-containing carboxylic acid, it generally has the following structural formula:

Wherein R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Preferred vinyl-containing carboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid and the like.

In a specific embodiment, the synthesis of the water dispersible, self-crosslinkable prepolymer composition involves the reaction of an epoxidized vegetable oil with a ketone or aldehyde functionalized carboxylic acid, and then, if appropriate, in the presence of a catalyst, Polycarboxylic acid An aqueous anhydride (such as maleic anhydride) is reacted to produce an aqueous self-crosslinkable copolymer dispersion. A diluent such as acetone, methyl ethyl ketone, or preferably a vinyl monomer is usually added to maintain the viscosity within a commercially acceptable range. This reaction is described in Figure 2 and is typically carried out at elevated temperatures in the presence of a catalyst. The catalyst can be a tertiary amine such as a trialkylamine, a hydrazine compound, an inorganic metal salt, a metal alkoxide, or a metal chelating compound. Some representative examples of catalysts that can be used include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tertiary butylamine, pyridine, isoquinoline, quinoline, N,N. - dimethylcyclohexylamine, N-ethylmorpholine, dimethylaniline, dimethylbenzylamine, Al, B, Be, Fe(III), Sb(V), Sn, Ti, Zr, and Zn Alkenes, tongs, or halides, and the like. It is generally preferred to use a trialkylamine such as triethylamine as the catalyst because it acts as a catalyst and a free base.

The anhydride of the di- or polycarboxylic acid which may be used to prepare the water-dispersible prepolymer may be aliphatic or aromatic. Some representative examples of the anhydride include maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride, pyromellitic anhydride, hexaic anhydride, trimellitic anhydride, and the like. Preferred anhydrides for this purpose are maleic anhydride, itaconic anhydride, succinic anhydride, trimellitic anhydride, and phthalic anhydride. The most preferred anhydrides are maleic anhydride and itaconic anhydride. These anhydrides, after the ring opening reaction, as described in Figure 2, act as a dispersing agent for the free water dispersible prepolymer. An alternative embodiment of the invention utilizes an external surfactant as a dispersing agent.

The water dispersible, self-crosslinkable prepolymer composition typically has a number average molecular weight in the range of from about 1,500 to about 19,000. The prepolymer generally has a number average molecular weight in the range of from about 2,000 to about 9,000, and more typically from about 2,500 to about 5,000. The number average molecular weight within the circumference. High molecular weight can be produced by coupling a plurality of epoxidized oils (e.g., via an ester linkage from a carboxylic acid group of maleic anhydride) to a prepolymer.

The moiety containing at least one carbonyl group (eg, aldehyde or keto group) has the formula:

Wherein A represents a hydrocarbyl moiety having 1 to 20 carbon atoms, and wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. In many cases, these parts have the following formula:

Wherein n represents an integer of 1 to 8, and wherein R represents a hydrogen atom or a methyl group. In most cases, n represents an integer from 2 to 4, and n generally represents 2.

The portion containing at least one vinyl group and/or substituted vinyl group has a formula selected from the group consisting of:

Or a mixture of this moiety, wherein n represents an integer from 0 to 8, and wherein R ¹ , R ² , and R ³ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. In most cases, n represents an integer from 0 to 4, and n is typically zero. Typically, from 1 to about 4 functional groups are attached to each triglyceride oil molecule, and more typically 2 or 3 functional groups are attached to each triglyceride oil molecule. In a particular embodiment of the invention, the prepolymer is neutralized by reaction with at least one neutralizing agent and dispersed in an aqueous medium.

Various additional monomers may optionally be copolymerized with the prepolymer. For example, the acrylic polymer or copolymer can be derived from various unsaturated monomers such as acrylates, alkyl (alkyl) acrylates, vinyl chloride, vinyl chloride, vinyl esters (such as vinyl acetate), styrene, dibutyl Alkene, acrylonitrile, and a monomer containing an unsaturated acid.

Copolymerizing a copolymer of functionalized triglyceride with an acrylate and other monomers, in one embodiment, desirably comprising from about 20 to about 65 or 75 weight percent functionalized epoxidation by weight of the copolymer The oil residue is more desirably about 30 to 55 weight percent, and preferably about 35 to 50 weight percent. In one embodiment, the amount of acrylate, alkyl acrylate, and/or vinyl ester (having a total of two or three of the conjunctions "and") is from about 5 to 40 weight percent, more desirably about 10 to 30 weight percent, and preferably about 12 to 25 weight percent. In a particular embodiment, the amount of styrene or C _1-4 alkyl substituted styrene is desirably from about 0 or 5 to 20, 25, or 30 weight percent, more desirably from about 5 to 25 weight percent. In a specific embodiment, the amount of the polyfunctional crosslinking agent (eg, di-, tri- or tetra-acrylate of dihydric alcohol, or divinyl benzene) is from about 0 to about 5 weight percent of the copolymer, and more desirably It is about 0.5 to 3 weight percent. In a specific embodiment, other unsaturated free-radically polymerizable monomers (defined as acrylates, alkyl acrylates, vinyl esters, styrene, and polyfunctional monomers) may be copolymerized from about 0 to about 20 or 30 weight percent is used. Of course, the above composition range of each monomer component can be combined with the range of other monomer components to produce a desired copolymer composition.

Various alkyl acrylates (or esters of acrylic acid) have the following formula:

Wherein R ⁷ is an alkyl group having 1 to about 15 carbon atoms, an alkoxyalkyl group having a total of 1 to about 10 carbon atoms, a cyanoalkyl group having 1 to about 10 carbon atoms, or 1 to 1 A hydroxyalkyl group of about 18 carbon atoms. The alkyl structure may contain a primary, secondary or tertiary carbon configuration and typically contains from 1 to about 10 carbon atoms, and preferably from 2 to 8 carbon atoms. Examples of such acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl 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-ethylhexyl acrylate, and the like.

A variety of alkyl alkyl acrylates (or alkyl acrylates) have the formula:

Wherein R ⁸ is an alkyl group having 1 to about 15 carbon atoms, an alkoxyalkyl group having a total of 1 to about 10 carbon atoms, a cyanoalkyl group having 1 to about 10 carbon atoms, or 1 to 1 A hydroxyalkyl group of about 18 carbon atoms (as described above), and wherein R ⁹ is an alkyl group having 1 to about 4 carbon atoms, desirably 1 or 2 carbon atoms, and particularly preferably a methyl group. Examples of various (alkyl)alkyl acrylates include methyl methacrylate, ethyl methacrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate. , ethoxypropyl acrylate and the like. The derivatives include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like. Mixtures of two or more of the above monomers may also be used.

Vinyl esters can generally be represented by the formula:

Wherein R ¹⁰ is an alkyl group usually having from 1 to about 10 or 12 carbon atoms, and preferably from about 1 to about 6 carbon atoms. Thus suitable vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate and the like. Vinyl esters having a larger R ¹⁰ group include vinyl versatate monomers such as Veo VA-P, Veo Va-10, and Veo Va-11.

Consider styrenic monomers (such as primary monomers in styrene-butadiene polymers, or comonomers in acrylate polymers), often referred to as vinyl-substituted aromatic compounds (styrene-based And including styrene, alkyl-substituted styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and alkyl, cycloalkyl, aryl, alkaryl, and aralkyl derivatives thereof, The total number of carbon atoms along with the substituent is usually from 8 to about 12. Examples of the compound include 3-methylstyrene (vinyltoluene), α-methylstyrene, 4-n-propylstyrene, 4-tributylbutylene, 4-dodecylbenzene Alkene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, 4-methoxystyrene, 4-dimethylaminostyrene, 3,5-diphenoxystyrene, 4 - p-tolylstyrene, 4-phenylstyrene, 4,5-dimethyl-1-vinylnaphthalene, 3-n-propyl-2-vinylnaphthalene, and the like. Generally preferred is styrene.

The unsaturated acid-containing monomer includes acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl acrylate, and the like. Preferred is acrylic acid. It is also possible to use a half ester of the above dicarboxylic acid as a monomer, wherein the ester moiety is desirably an alkyl group having 1 to about 10 carbon atoms, and specified examples include monomethyl maleate and fumaric acid Methyl ester, monomethyl meconate, and the like.

Other copolymerizable (ethylene unsaturated) monomers can be used to make copolymers, including styrenic monomers (such as comonomers in acrylate latex), vinyl chloride monomers, acrylonitrile monomers, Various vinyl ester monomers, various acrylamide monomers, various alkanol acrylamides, and the like. The vinyl chloride type monomer includes vinyl chloride, vinyl chloride, and the like.

Various vinyl ethers can be represented by the formula: H ₂ C=CH-OR ⁴

Wherein R ^{4 is} desirably an alkyl group having from 1 to about 10 carbon atoms. Designated examples include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, etc., preferably methyl vinyl ether.

Acrylonitrile type monomers which can be used include acrylonitrile, methacrylonitrile, or ethacrylonitrile. The acrylamide monomer which can be polymerized to form a copolymer generally has the formula:

Wherein R ⁵ represents a hydrogen atom or a methyl group, and wherein R ⁶ represents a hydrogen atom or an alkyl group (straight chain or branched) having 1 to about 18 carbon atoms. Designated examples include acrylamide, ethyl acrylamide, butyl acrylamide, tertiary octyl acrylamide, tertiary butyl methacrylate, and the like. Unlike other optional monomers, the one or more acrylamides can be used in large amounts, such as up to about 20 weight percent of the copolymer, and desirably from about 0.5 to about 10 weight percent.

Functionalized acrylamide can also be used. Examples of the acrylamide include AMPS, i.e., 2-acrylamido-2-methylpropanesulfonic acid, DMAPMA, i.e., dimethylaminopropylmethacrylamide, and the like.

The carbonyl group-containing unsaturated comonomer can be copolymerized with the above monomers to produce an acrylic or vinyl polymer. Examples of the carbonyl group-containing monomer which may be mentioned include acrolein, methacrolein, diacetone-acrylamide, crotonaldehyde, 4-vinylbenzaldehyde, vinylalkylketone of 4 to 7 carbon atoms ( Such as vinyl methyl ketone), and the propyleneoxy group of the formula H ₂ C=C(R ³ )-C(O)-OC(R ¹¹ )HC(R ¹² )(R ⁹ )-C(O)H- And methacryloxy-alkylpropanol, wherein R represents a hydrogen atom or a methyl group, R ¹¹ is H or an alkyl group of 1 to 3 carbon atoms, R ¹² is an alkyl group of 1 to 3 carbon atoms, and R ⁹ is an alkyl group of 1 to 4 carbon atoms. Other examples include acrylamido-trimethylacetaldehyde, methacrylamido-trimethylacetaldehyde, 3-acrylamidomethyl-ananiline, diacetone acrylate, acetone acrylate, diacetone Methacrylate, acetamethylene ethacrylate, 2-hydroxypropyl acetate acetate, and butane diol acetate acetate. Further details of the use of these monomers are provided in U.S. Patent No. 4,983,662. For a more detailed description of the use of this monomer, the teachings of U.S. Patent No. 4,983, 662, incorporated herein by reference.

In a specific embodiment, the above vinyl monomer may be used in the formation of a prepolymer or a vinyl polymer using an active hydrogen-containing vinyl monomer, and is intentionally attached to the water-dispersible prepolymer of the present invention. Branch or copolymerization. The active hydrogen-containing vinyl monomer includes 2-hydroxyethyl acrylate (2HEA) and 2-hydroxyethyl methacrylate (2HEMA).

Free radical initiators well known in the art and in the literature can be used to initiate polymerization of various monomers or comonomers described above to form polymers or copolymers. This free radical initiator typically includes persulfates, peroxides, and azo compounds, as well as redox combinations and sources of radiation. Examples of preferred persulfate initiators include potassium persulfate, sodium persulfate, or ammonium persulfate, and the like. The free radical polymerization can be an emulsion, solution, or dispersion polymerization.

Generally any type of peroxide, azo, redox system, or related initiator system can be used. The peroxide system comprises dicumyl peroxide, cumene hydroperoxide, butyl perbenzoate, hydrazine (tertiary butylperoxy) diisopropylbenzene, dihydrogen peroxide Propyl benzene, n-butyl 4,4-anthracene (tertiary butylperoxy)pentanoate, and benzammonium peroxide and tertiary butyl hydroperoxide. Preferred are cumene hydroperoxide, tertiary butyl hydroperoxide, and diisopropylbenzene hydroperoxide. The azo initiator includes 2,2'-arsenazo (isobutyronitrile) (AIBN), and related azo initiators.

The polymer or copolymer can be made using a chain transfer agent/polymer physical property modifier. It can utilize conventional chain transfer agents, such as various mercaptans, such as thioethanol mercaptan, hydroxyethyl mercaptan, alkyl esters of mercaptans and acidic acids or various reaction products with indole acetic acid, etc., wherein the alkyl group has about 2 Up to about 20 carbon atoms. Another suitable chain transfer agent is beta-propionic acid and its esters, such as butyl 3-propionate. Examples of the chain transfer agent may include dithiocarbamate, or di or trithiocarbonate.

Once the prepolymer is formed, it is dispersed in an aqueous medium to form a dispersion. Dispersing the prepolymer in an aqueous medium may be prepolymerized by monolithic or solution polymerization as disclosed in U.S. Patent Application Publication No. 2010/0330375 A1. This is done in the same way that the material is dispersed in water. U.S. Patent Application Publication No. 2010/0330375 A1 is incorporated herein by reference. Usually it is done by mixing the prepolymer blend with water. Where solvent polymerization is used, the solvent and other volatile components may optionally be evaporated from the final dispersion if desired. The oxime functional moiety used to crosslink the ketone group can be added at this stage or later.

The two important components of the present invention are copolymers derived from functionalized triglycerides and second known polymers which are separately produced or dispersed in water and then combined. It is desirable that the polymers be separately dispersed such that the respective polymer compositions are present in the separated particles and then blended together. The conventional polymer dispersion may be an acrylate type polymer dispersion (such as a manufacturer of emulsion polymerization), manufactured by first producing a urethane or prepolymer and then dispersing in water followed by chain extension. A dispersion of a urethane in water or a mixture of an acrylate and a urethane polymer dispersed in water. In a specific embodiment, the second, more conventional polymer dispersion can be crosslinked with an external crosslinking agent that is added just prior to coating, or an internal crosslinking agent that can be added during the formulation of the coating or ink from the polymer. . In a specific embodiment, the acrylate and functionalized triacid Copolymers of glycerides, as well as conventional polymer dispersions, can be crosslinked with internal crosslinking agents (added when the polymer is formulated into the final formulation). In a particular embodiment, the copolymer from the acrylate and the functionalized triglyceride can be crosslinked (with an internal crosslinking agent or an external crosslinking agent). The term internal crosslinking is now used to refer to a crosslinking agent (such as a polyacrylate or ketone and a hydrazine/hydrazine functional group) incorporated into the polymer during polymerization. The term external crosslinker is used for additives (such as polyisocyanates) which can be added to the coating just prior to coating. The external crosslinking agent tends to be too reactive and does not mix with the binder during the adhesive manufacturing or coating formulation stage.

One of the advantages of the present invention is that two separate polymer dispersions can be made and can be stored and then blended in various weight ratios later to provide optimum properties as a coating or ink. In a specific embodiment, the first copolymer of the acrylate monomer and the functionalized triglyceride (dispersed in water) is polymerized at a concentration of from about 10 to about 90 weight percent, more desirably from 20 to 80 weight percent. The amount is used (based on the total polymer in the blend). In a more desirable embodiment, the copolymer of the acrylate and the functionalized triglyceride is from about 30 to about 60, 65, or 70 weight percent polymer, and more preferably from about 35 to about 55. Used in an amount of 60, or 65 weight percent. In a related embodiment, the conventional polymer (dispersed in water) is used in an amount of from about 10 to about 90 weight percent (more desirably from about 20 to 80 weight percent) of the polymer in the blend of the two dispersions. And in a more desirable embodiment, about 30, 35, or 40 to about 70 weight percent, and preferably about 40 or 45 to about 65 weight percent of the polymer blend (by polymer plus any The combined amount of the polymer is added as appropriate).

The conventional polymer of the aqueous dispersion may be any polymer, but is preferably an acrylate polymer, a urethane polymer, or an acrylate-urethane hybrid polymer. The acrylate polymer is usually produced by polymerizing an acrylate monomer by an emulsion polymerization method, or may be produced by other methods (methods other than emulsion polymerization), and then dispersed in water like a urethane dispersion forming method. Urethane polymers are known in the art and are generally mixed and reacted by various urethane forming monomers (polyisocyanates, polyols, optionally polyamines, etc.) (as appropriate) The catalyst is produced by a method of forming a prepolymer or a polyurethane. These prepolymers or polyurethanes are functionalized to be water dispersible and then dispersed in water. After dispersion in water, the prepolymer can be extended with a polyol or polyamine to form a higher molecular weight polyurethane. Mixtures of acrylates and urethane polymers are also known in the art and are similar to polyurethane dispersions, but increase some during or after the preparation of the urethane dispersion. It is formed by the step of adding an acrylate monomer and then polymerizing the acrylate monomer into a polyacrylate.

This conventional polymer is often formulated into a coating. In the coating formulation method, a solvent or a plasticizer is usually added to lower the minimum film formation temperature of the coating. These solvents and/or plasticizers are considered volatile organic compounds by regulatory agencies, such as the US Environmental Protection Agency (EPA). The definitions of volatile organic compounds (VOCs) are usually slightly different for different government and regulatory agencies, depending on the perceived toxicity associated with the volatile organic compounds intended for use in coatings. For regulatory purposes, US EPA defines volatile organic compounds as any carbon compound involved in atmospheric photochemical reactions (except for oxygen). Carbon, carbon dioxide, carbonic acid, etc., and designated compounds with low environmental risks and high commercial interests). Other country/region pairs (VOCs) have different definitions, but increase or decrease the compounds from the same volatile and organic definitions for specific country/regional approval reasons. For the purposes of this specification, the US EPA's VOC definition is used herein, and it should be understood that the exact VOC value for any particular country will vary depending on which compound is included or excluded in the country's / region's VOC regulations. VOC determination in US EPA Method 24 coatings is a generally accepted method of quantifying VOCs in the United States.

In the United States, coatings (binder polymers, continuous phases, pigments, optional fillers, etc.) are typically formulated to have a coating of less than 300 grams per liter according to US EPA Method 24, more desirably less than 150 grams per liter of coating, and Preferably, the volatile organic content (VOC) of the coating is less than 50 or 25 grams per liter to meet current regulatory requirements or to meet future regulatory requirements beyond expectations. Meeting these VOC limits often means using less solvent or plasticizer, using solvents or plasticizers that are not defined in the VOC regulations, or modifying the formulation or polymer to meet VOC requirements. One of the descriptions is intended to teach how the copolymer of acrylate monomer and functionalized triglyceride (dispersed in water) acts to help meet the minimum film formation temperature requirements of the coating (to apply the coating to the substrate) The desired temperature (eg, 20-25 ° C) forms a continuous film), and the VOC calculation of the coating is maintained at less than 300 grams per liter, more preferably less than 150, as measured by US EPA Method 24 The gram per liter, and preferably less than 50 or 25 grams per liter, meets the various other performance requirements of the coating.

In a specific embodiment where both the copolymer of acrylate and functionalized triglyceride and the conventional polymer dispersion are crosslinkable, both polymers use the same crosslinking mechanism of the chemical form. In another embodiment, the copolymer and the conventional polymer use different types of crosslinking mechanisms.

The prior art has taught the crosslinking mechanism of the dispersion of the polymer in water. Ketone-oxime cross-linking (also known as azomethine cross-linking) uses a combination of a reactive carbonyl group (aldehyde or ketone group) with a ruthenium or osmium group to form a covalent chemical bond. This type of crosslinking is often used in copolymers of acrylates and functionalized triglycerides. Another crosslinking mechanism is a urethane or urea linkage which can be formed from a reactive isocyanate group with a hydroxyl group or a primary or secondary amine group. The isocyanate-containing species may be added just prior to use, or the isocyanate groups may be blocked with isocyanate blocks. If the isocyanate groups are blocked, the isocyanate-containing species can be added prior to use. It is also possible to use a ketoxime type cross-linking in which a ketoximino group is reacted with a hydroxyl group on a polymer to form a covalent bond. Conjugated unsaturated groups can be incorporated into the composition if desired, and these conjugated unsaturated groups can be crosslinked by oxidative crosslinking (often accelerated by a metal drying agent). All of these crosslinking systems can be used for copolymers of this composition and conventional polymers.

Preferred oxime functional moieties are low molecular weight molecules or oligomers having one or more ruthenium or osmium groups. The hydrazine functional group represents a functional group of the formula -NHNH ₂ . In the practice of the present invention, the oxime functional group is derived from a group which reacts with a monoketone or a monoaldehyde having at least 2 carbon atoms and a thiol group. Hydrazine functional moiety may also be two other multi-acyl hydrazine and hydrazine acyl, as represented below, because these molecules have the specified group -NHNH _2.

Although ruthenium itself (H ₂ N-NH ₂ ) raises concerns about operator exposure at high concentrations, molecules containing ruthenium (-NHNH ₂ ) are less exposed and provide polyurethane at or near room temperature. The opportunity to construct molecular weight and/or crosslink molecules/oligomers/polymers after coagulation/film formation of the ester dispersion. Volatile amines can play an important role in the reaction using a hydrazine functional moiety because the amine is/can be used in the polyurethane dispersion to adjust the pH to the alkaline side prior to coalescence, and can be used in water and volatilization. When the amine is evaporated, the pH is biased toward the acid side. This pH shift and water evaporation promotes the reaction of the hydrazine or sulfhydryl group with available ketone or aldehyde groups (while providing molecular weight construction and/or crosslinking).

In a specific embodiment of the invention in which it is not necessary to add an emulsifier (surfactant), the prepolymer comprising a water-dispersion strengthening compound sufficient to form a stable dispersion, the dispersion can be produced without the need of such a compound, if desired. That is, there is substantially no surfactant. Surfactants such as sulfates or phosphates may advantageously be included in the prepolymer composition in a particular embodiment of the invention.

In the case where the prepolymer comprises a water-dispersion-strengthening compound which is produced by flanking a carboxyl group, these carboxyl groups can be converted into a carboxylate anion to further enhance the water dispersibility of the prepolymer. A typical manner of making the dispersion of the present invention is to form a prepolymer blend substantially free of water, which is then mixed to disperse in an aqueous medium. The dispersion of the present invention can also be produced by other methods of producing an aqueous dispersion, including shear mixing, acetone, continuous polymerization, and reverse feed.

It is often desirable to include bisulfite or sulfite to improve the stability of the dispersion. For example, sodium sulfite, potassium sulfite, ammonium sulfite, calcium sulfite, magnesium sulfite, zinc sulfite, sodium hydrogen sulfite, sulfurous acid Potassium hydrogen, ammonium hydrogen sulfite, calcium hydrogen sulfite, magnesium hydrogen sulfite, or zinc hydrogen sulfite may be included in the dispersion. Sulfite or bisulfite is typically added to the dispersion in a post polymerization step because it acts as a chain transfer agent to interfere with the polymerization. In any event, the sulfite or bisulfite is typically added in an amount not exceeding the stoichiometric amount based on the amount of ketone groups in the polymer. The sulfite or bisulfite is generally added to the extent of from 0.1% by weight to 0.5% by weight based on the solid content of the dispersion.

When shear mixing, the prepolymer acts as a polymer backbone by shearing with an emulsifier (external emulsifier such as a surfactant, or having a nonionic, anionic, cationic and/or zwitterionic group) A portion or side portion, and/or an internal emulsifier that becomes the end group of the polymer backbone, is dispersed.

In the acetone process, the prepolymer is formed with or without acetone, MEK, and/or other polar solvents that are non-reactive and readily distillable. The prepolymer is further diluted in the solvent as desired, and the chain is extended with an active hydrogen-containing compound as appropriate. Water was added and the solvent was evaporated.

In the continuous polymerization step, the prepolymer is formed and then pumped through a high shear mixing head and dispersed in water. This is accomplished by multiple streams of prepolymer (or neutralized prepolymer), optionally, and water, and/or surfactant.

In the reverse feed process, water and optionally neutralizer and/or extender amine are added to the prepolymer under agitation. The prepolymer can be neutralized prior to the addition of water.

The aqueous self-crosslinking copolymer dispersion can then optionally be diluted with additional water to any desired concentration (solids content). The aqueous self-crosslinkable copolymer dispersion can then be used to prepare aqueous coatings and inks, such as paints, varnishes, clearcoats, inkjet inks, and paper coatings, using techniques known to those skilled in the art. Desirable pigments, plasticizers, coalescing solvents, fillers, wetting agents, stabilizers, defoamers, desiccants, fungicides, fungicides, insecticides, antifouling agents, and anticorrosive agents can be directly Mix into an aqueous self-crosslinkable copolymer dispersion.

Pigments are typically added to the paint formulation to impart color and hiding power to the paint. Titanium dioxide is an example of a widely used pigment that imparts hiding power and whiteness. Mineral pigments (such as iron and chromium oxides), organic pigments (such as indigo), and reactive anti-corrosive pigments (such as zinc phosphate) are representative examples of other widely used pigments.

The filler used to make the aqueous coating formulation is typically an inexpensive material that is added to achieve the desired consistency and non-settling characteristics. Fillers can also improve the physical properties of the coating, such as resistance to cracking and abrasion. Some representative examples of widely used fillers include chalk, clay, mica, barite, talc, and vermiculite.

Fungicides and algaecides are often added to indoor and outdoor household paints and are particularly valuable for coating formulations used in warm climates. Antifouling compounds are often added to marine paints to inhibit the growth of marine life.

The film-forming aqueous composition can be prepared by using the aqueous self-crosslinking copolymer dispersion, optionally with a mixture of a suitable coalescing solvent and a plasticizer. The coalescing solvent is preferably at least not miscible with water, and even more preferably water insoluble. A variety of usable solvents are generally preferred as 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. It should be noted that the solvent and plasticizer can be directly mixed with the resin in its aqueous emulsion.

Plasticizers are used to control the hardness of the coating and/or impart flexibility. When a water-based paint is applied to some substrates, it suffers from poor adhesion. Adhesion can often be improved by adding one or more plasticizers to the aqueous coating formulation.

The various plasticizers are desirably selected to be liquid at room temperature (e.g., 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 are not coated when applied to a substrate. The coating composition evaporates. The plasticizer should enhance the water insolubility of the dried coating of the coalesced resin. It is important that the plasticizer or plasticizer mixture is compatible with the resin itself.

A wide variety of plasticizers can be used in the practice of the present invention. It may be, for example, the type listed in the Federation Series on Coatings Technology, Division 22, 1974, entitled "Plasticizers", as long as it satisfies the melting point, boiling point, and compatibility requirements. Some representative examples of 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 group. 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 Alcohol ethyl ether, diethylene glycol methyl ether, diethylene glycol n-butyl ether, diethylene glycol hexyl ether, diethylene glycol n-butyl ether Acid ester, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate, triethylene glycol methyl ether, triethylene glycol ethyl ether, three Ethylene glycol n-butyl ether, ethylene glycol phenyl ether, ethylene glycol n-butyl ether mixture, polyethylene glycol dibenzoate, o- and/or p-toluenesulfonamide, trimethylpentanediol diphenyl Formate, and trimethyl pentanediol monoisobutyrate monobenzoate.

It is desirable to delay the reaction between the ketone group of the prepolymer and the oxime functional moiety until after the particles have coagulated and coalesced, but the technique is not limited thereto. The ketone group is expected to react with the oxime functional moiety to form an azomethine linkage, as taught in U.S. Patent No. 4,210,565, the disclosure of which is incorporated herein by reference. It is desirable that the reaction between the ketone group and the oxime functional portion of the prepolymer be carried out at a suitable rate at 20 ° C to 25 ° C such that the low molecular weight species bearing these portions are at 20 ° C to 25 ° C (ambient drying temperature) Conversion to high molecular weight and/or cross-linked species that contribute to, but not detract from, polymer hardness, strength, solvent resistance, and wear-related properties.

The invention is described by the following examples, which are merely for the purpose of description, and are not intended to limit the scope of the invention. Parts and percentages are by weight unless otherwise indicated.

[Example 1: Ketone/methacrylate functionalized epoxidized soybean oil polyol (functionalized triglyceride)]

The polyketone-functionalized triglyceride was prepared by combining the following components 1-5 in a four-necked flask equipped with a thermometer, a head-type stirrer, and an air inlet. Epoxidized soybean oil (ESO) may be derived from the Jenkinol ^TM 680 Acme Hardesty, or Hallstar of Plasthall ^TM ESO. The temperature of the reaction mixture was raised to 110 to 114 ° C under nitrogen blanket and maintained at this temperature for 1 hour. The temperature is then raised to 121-125 ° C and maintained at this temperature for 2 hours, or until the acid number is < 1.0 (mg/g). The final material was amber in color with a viscosity of ~1,510 cps at 70 ° C and an acid number of 0.9 mg/g.

[Example 2: Functionalization of a ketone/acrylate functionalized triglyceride with an ionic dispersing group]

First, by heating to 60-70 ° C until the solid maleic anhydride is homogenized (melted), maleic anhydride and methyl methacrylate (MMA) (items 1-3), will be implemented as above The ketone/acrylate functional triglyceride (Item 1) prepared as described in the Examples was homogenized to prepare a dispersible functional triglyceride. Triethanolamine (TEA) (item 4) was then added and the mixture was held at 70 ° C for 60 minutes. At this point, most, if not all, of the anhydride has been consumed, as evidenced by the fact that the FTIR spectrum does not show any significant peaks at 1779 and 1849 cm-1 (however, some anhydride peaks are trapped below other absorption peaks such as ester groups). . The mixture was then cooled to 25-30 ° C and item 5 was added and homogenized therein. Thus, a dark amber medium viscosity prepolymer was formed at a prepolymer dispersion temperature of 25-30 °C.

[Example 3: Copolymerization of acrylate with ionic/ketone/acrylate functionalized triglyceride]

The ionic/ketone/acrylate functional triglyceride (180 parts) formed at ~25 ° C was dispersed in 373 parts of water having an initial temperature of ~20 ° C, thus providing a low-grain dispersion with a translucent appearance. liquid. Adding 58.6 parts of styrene, 12.3 parts of methyl methacrylate, and 5.8 parts of divinylbenzene (DVB 80) to the resulting dispersion, and homogenizing them into a dispersion; thus causing an increase in particle size, such as a dispersion having The opaque appearance is evidenced. 0.03 parts of 1% Fe-EDTA, and 8.0 parts of 3.5% tributyl butyl hydroperoxide (which can be mixed into the dispersion before slowly adding 10.0 parts of 2.0% isoascorbic acid having an initial temperature of 21 ° C), The resulting dispersion is subjected to radical polymerization. The vinyl functional monomer was initiated and polymerized as such, and an exotherm of 21 to 42 ° C was observed. A decrease in particle size and an increase in viscosity were observed with vinyl polymerization. After the vinyl polymerization, 1.6 parts of sodium hydrogen sulfite per 100 parts of the polymer solid was slowly added to obtain a weight percentage aqueous solution. Then 7.7 parts of dioxane adipate is added to the dispersion to provide a polymer which may self-crosslink via condensation of hydrazine with the ketone on the polymer; its effect on the dried coating is observed to be a significant increase in hardness, and Damage and heel black spot resistance is very good. Final dispersion (acrylate and official) The copolymer of the triglyceride dispersion has a deposition content of <0.1%, a solid content of 40.2% by weight, a viscosity of 38 cps (at 25 ° C and pH 7.0), and a particle size of 52.3 nm.

Commercially available aqueous polymer dispersions, Example 3, and blends of the dispersions and Example 3 were tested for minimum film formation temperature, chemical resistance, drying time using a recorder, chemical resistance ASTM D1308, sandability, 1000 hour QUV exposure, and dynamic mechanical analysis.

The conventional polymer dispersion is selected from the group consisting of: Carboset® 2968 (CST 2968), an acrylate copolymer emulsion having 42 weight percent solids, pH 8.1, and 57 ° C MWT; Turboset® 2027 (TST 2027), one having A melamine-acrylic hybrid dispersion of MffT at about 2 °C; Turboset® Ultra Eco (TSTULECO), a self-crosslinking of MffT with about 36 weight percent solids, pH 8-9, and 4 °C polyurethane - acrylic hybrid ^{dispersion; Santocure TM 970 (SCR 970)} , a thermoplastic polyurethane dispersion; and Carboset® CR-765 (CR-765 ), having 42 weight percent of Solid, pH 8.2, and a styrene-acrylic copolymer of MffT at 34 °C.

The minimum film formation temperature (MWT) test was performed on pure resin and resin blends, rather than on finished finishes. For the blend of CST 2968 and Example 3, and the blend of SCR 970 and Example 3, the measured MffT was lower than the theoretical MffT.

The data in Table 4 illustrates the incorporation of a high MffT polymer from the copolymer of Example 3 from an acrylate to a functionalized triglyceride, providing a MffT closer to room temperature without the need for a large amount of plasticizer or coalescent.

Low Temperature Film Formation (4.4 ° C / 50% Relative Humidity) and Weekly Temperature Film Formation: Blending Example 3 with TSTULECO produced a lower temperature film formation than either resin itself. The coating was applied to unsealed chart paper, sealed chart paper, and sealed black chart paper.

In Table 5, some polymers (TSTULECO and Example 3) were difficult to form a film on both unsealed and sealed chart paper. Blending TSTULECO with Example 3 resulted in better film formation on the chart paper.

Chemical resistance - 1 hour exposure, 1 hour recovery time: The chemical resistance test was 1 hour exposure and 1 hour recovery according to ASTM D1308. The response score is as follows.

The second blend shows an improvement in resistance to the specified chemical, which in turn improves the total score of the resistant properties. The score is 0 to 20, and 20 is the best chemical resistance. TSTULECO is self-crosslinking and benefits from the addition of Example 3. The Example 3 blend with acrylic emulsion CST29688 showed a complete negative impact on performance and reduced the chemical resistance properties of CST29688.

Sanding resistance: The blending formulation shows an improvement in the powder during sanding, and the sandpaper is not sticky (the agglomerate is a measure of sandpaper sticking). Wood finish sanders are happy to see dust generation - proving that a small amount of surface is actually removed and smoothed. In Example 3, the development of the powder of the topcoat having a poor powder production was excellent. None of the topcoats caused sticking on the sandpaper - when more dust/powder was produced, sometimes the dust stuck on the surface of the sandpaper and stuck it - the sticky ball was called a block.

Drying time using the recorder: The recorder measures different drying stages, which are interpreted as dry touch, dry surface, and dry out. The wet film was cast on glass and the recorder was placed in the film to determine the amount of time the film reached each stage according to the drying method of ASTM D5895.

The blend of CST2968 and TSTULECO shows a better open time without significantly changing the dry-through properties - it is desirable because the topcoat has more time to flow or manipulate during coating, but does not increase the desire The time required to trim the item for the next step. The next step may be to sand the seal, coat other lacquer coatings, or encapsulate the final product.

QUV: Exposure to UV340 light for 1000 hours - completed in a 4 hour cycle (4 hours light and 4 hours dark room with moisture). Glossy readings were performed on a Byk-Gardner three-angle gloss meter according to the supplier's instructions. The result of Fig. 3 was obtained using solid fir as a substrate.

The results in Figure 3 show that the polyurethane dispersion and the blend of Example 3 resulted in higher gloss retention than the individual polyurethane itself. SCR970 is thermoplastic, and TSTULECO and TST2027 are self-crosslinking polyurethane dispersions - both types show improved gloss retention. This study also tested the blend-thermoplastic and self-crosslinking acrylic emulsions, but the gloss retention did not exhibit the same improvement. Make The same exposure with mahogany as the substrate shows results similar to those in the above chart.

The present invention has been described with respect to the specific embodiments and details of the present invention, and various changes and modifications may be made without departing from the scope of the invention.

Claims (19)

A blend of two compositionally different polymer dispersions comprising: a) from 10 to 90 weight percent of a colloidally dispersed self-crosslinkable copolymer in water comprising from 25 to 80 weight percent of polymeric unsaturation a monomer (desirably characterized by a molecular weight of less than 300 g/mole before polymerization), and 20 to 75 weight percent of a monomer characterized by an acrylate and ketone functionalized epoxidized triglyceride oil, wherein the functional group is More than one carboxylic acid-containing component having a carboxylic acid function or a carbonyl function, and imparting crosslinking power to the acrylate polymer; b) 10-90 weight percent of water in a gel-like dispersion of acrylate, urethane An ester, or urethane-acrylate hybrid polymer, wherein the weight percentages of a) and b) are based on the combined weight of the dispersed solids in a) and b), and any optional additional dispersed solid polymer dispersion. . A blend of two differently different polymer dispersions as claimed in claim 1, wherein a) is from 20 to 80% by weight, and b) is from 20 to 80% by weight. A blend of two differently different polymer dispersions according to claim 1 or 2, which further comprises a crosslinkable aqueous dispersion of the acrylate and/or urethane polymer in the water or External crosslinker. A blend of two compositionally different polymer dispersions according to any of the preceding claims, wherein a) is from 30 to 70 weight percent, and b) is from 30 to 70 weight percent. A blend of two compositionally different polymer dispersions according to any one of the preceding claims, wherein b) the gel-like dispersed acrylate and/or urethane polymer in the water comprises a ketone or an aldehyde group, respectively. The form of the reactive carbonyl group is such that it can be crosslinked via a ketone-oxime or ketone-oxime type crosslinking reaction. A blend of two differently different polymer dispersions according to any one of the preceding claims, wherein b) the respective gel-like dispersed acrylate and/or urethane polymer in the water comprises an acrylate polymer . A blend of two differently different polymer dispersions according to any one of claims 1 to 5, wherein the water is separately dispersed in a gel form, such as an acrylate, a urethane or an acrylate-amine group. The acid ester blend polymer comprises a urethane polymer dispersed in water. A blend of two compositionally different polymer dispersions according to any one of claims 1 to 5, wherein the respective colloidally dispersed acrylate, urethane or acrylate dispersed in water - The urethane hybrid polymer comprises an acrylate-urethane hybrid polymer. The blend of two differently different polymer dispersions according to any one of claims 1-8, wherein the blend further comprises at least one selected from the group consisting of sodium sulfite, potassium sulfite, ammonium sulfite, sulfurous acid Calcium, magnesium sulfite, zinc sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, calcium hydrogen sulfite, magnesium hydrogen sulfite, sulfites of the group consisting of zinc hydrogen sulfite or A salt of bisulfite. A blend of two differently different polymer dispersions according to claim 9, wherein the sulfite or bisulfite salt is from 0.1 weight percent to 5.0 based on the polymer solids content of the dispersion. The content within the range of weight percentages is present. A method for modifying a film formation procedure of a conventional polymer dispersion in water, which comprises providing an acrylate, urethane or acrylate-urethane hybrid polymer dispersion, and the conventional polymer The dispersion is diluted with a first polymer dispersion derived from crosslinking the acrylate- and carbonyl-functionalized triglyceride oil with a dispersing group, an unsaturated polymerizable group, and a carbonyl group. The carboxylic acid functional group molecule is polymerized, wherein the carboxylic acid functional group molecule further comprises at least one selected from the group consisting of an ionic water-dispersing group, an unsaturated polymerizable group, and a carbonyl crosslinking group to form a ketone-oxime type crosslinking. Functional group. A method of modifying a film forming procedure of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion according to claim 11, wherein the acrylate, urethane or acrylic acid The ester-urethane hybrid polymer dispersion comprises an acrylate emulsion. A method of modifying a film forming procedure of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion according to claim 11, wherein the acrylate, urethane or acrylic acid The ester-urethane hybrid polymer dispersion contains a urethane dispersion or an acrylate-urethane mixed dispersion. A method of modifying a film forming procedure of the acrylate, urethane, or acrylate-urethane hybrid polymer dispersion as claimed in claim 11, 12, or 13, wherein the first polymer is passed The dispersion modified acrylate, urethane, or acrylate-urethane hybrid polymer dispersion is formulated to have a volatile organic content of less than 300 grams per liter of paint or as measured in accordance with USA EPA Method 24 A coating or ink composition of ink. A method of modifying a film forming procedure of the acrylate, urethane, or acrylate-urethane hybrid polymer dispersion as claimed in claim 11, 12, or 13, wherein the first polymer is passed The dispersion modified acrylate, urethane, or acrylate-urethane hybrid polymer dispersion is formulated to have a volatile organic content of less than 150 grams per liter of paint or as measured in accordance with USA EPA Method 24 A coating or ink composition of ink. A method of modifying a film forming procedure of the acrylate, urethane, or acrylate-urethane hybrid polymer dispersion as claimed in claim 11, 12, or 13, wherein the first polymer is passed The dispersion modified acrylate, urethane, or acrylate-urethane hybrid polymer dispersion is formulated to have a volatile organic content of less than 50 grams per liter of paint as measured according to USA EPA Method 24 A coating or ink composition of ink (more desirably less than 25 grams per liter). A method of modifying a film forming procedure of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion according to any one of claims 11-16, wherein the first polymer is dispersed The solids of the liquid comprise from about 10 to about 90% by weight of the solids of the modified polymer dispersion, and the solids of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion comprise From about 10 to about 90% by weight of the solids of the modified polymer dispersion. A method of modifying a film forming procedure of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion according to any one of claims 11-16, wherein the first polymer is dispersed The solids of the liquid comprise from about 20 to about 80% by weight of the solids of the modified polymer dispersion The solid, and the solid of the acrylate, urethane, or acrylate-urethane hybrid polymer dispersion comprises from about 20 to about 80 weight percent of the solids of the modified polymer dispersion. A method of modifying a film forming procedure of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion according to any one of claims 11-16, wherein the first polymer is dispersed The solids of the liquid comprise from about 30 to about 70% by weight of the solids of the modified polymer dispersion, and the solids of the acrylate, urethane or acrylate-urethane hybrid polymer dispersion comprise From about 30 to about 70% by weight of the solids of the modified polymer dispersion.