MXPA99001643A - Process to improve the appearance of a composition of varnish for pi - Google Patents

Abstract

The appearance of a floor varnish composition can be improved with the use of a divalent copper ion crosslinking agent in an amount of 50 to 5000 ppm, based on the polymer solids in said composition.

Description

Process to Improve the Appearance of a Floor Varnish Composition The present invention relates to a process for improving the appearance of a floor varnish composition, and to a floor varnish composition having an improved appearance. More particularly, although not exclusively, this invention relates to the preparation of a composition that is used as a base for varnishing floors comprising a water-insoluble emulsion copolymer containing acid functional residues, and at least one complexing or cross-linking agent. polyvalent metal ion. The compositions that are used as a base for varnishing floors, ionically crosslinked, are well known in the prior art. A composition that is used as a base for varnishing floors is defined as including a dispersion or suspension in water of a film-forming polymer, insoluble in water, and complexes and metal salts that are soluble or dispersed in water. Floor varnish compositions are defined as comprising compositions which are used as a base for varnishing floors together with one or more other ingredients useful for the varnishing of floors, such as alkali-soluble resins, plasticizers, waxes, preservatives, dispersing agents. , coalescents, leveling agents and optical brighteners. The optical brighteners are added to the floor varnish compositions to improve the appearance or cleanliness of the varnish once it has been applied to a floor. EP-A-0696625 and US-A-4371398 disclose examples of optical brighteners, and include distirylbiphenyl and stilbene derivatives, sold by Ciba-Geigy under the tradename TINOPAL; and 2, 2 '- (2,5-thiophenediyl) bis [5-tert-butylbenzoxazole], available from Ciba-Geigy as UVITEX OB. Also, in US-A-4371398 it is suggested that coumarin derivatives such as coumarin 4-methyl-7-diatylamine can be used as optical brighteners in a varnish composition, but a varnish composition comprising said varnish is not specifically disclosed. derivative. An object of the present invention is to improve the appearance of a floor varnish composition, said composition can already include a conventional optical brightener. A compound that offers a double functionality in a floor varnish composition can be very desired for the expert who formulates varnishes: said compounds can be advantageously used in floor varnish compositions either to complement one or more other components and to obtain varnishes from Higher development or to replace, in whole or in part, one or more other components in a varnish composition without loss of development. Accordingly, another object of the present invention is to identify a composite that can offer not only improved appearance in a floor varnish composition, but also some other property pertinent to a varnish composition. Floor varnish compositions based on aqueous dispersions of water insoluble emulsion polymers, containing acidic functional residues and polyvalent metal complex or crosslinking agents, are well known in the prior art. For example, said compositions are disclosed in US-A-3328325, US-A-3467610, US-A-3554790, US-A-3573239, US-A-3808036, US-A-4150005, US-A-4517330. , US-A-5149745 and US-A-5319018. Although it is known that all transition metals are capable of forming polymeric crosslinks, for years there has been a tendency to avoid the use of certain transition metals due to their color production in the crosslinked film of the varnish and, instead, to use a metal that produces a faint color in the crosslinked film of varnish, such as zinc. Copper dimethylaminoethate is disclosed in Example 11 of US-A-3554790 as a crosslinker in a floor varnish, in an amount equivalent to 108.640 ppm of Cu ++ in polymer solids. In accordance with the present invention, a process for improving the appearance of a floor varnish composition is provided, the process comprising: a) charging a reaction zone with an aqueous dispersion or suspension of a water insoluble polymer, said polymer is prepared from more than an ethylenically unsaturated monomer and containing acid functional residues, and from 10 to 100% of the stoichiometric amount based on said polymer functionality acid of at least one polyvalent metal crosslinking agent, and b) reacting said polymer and said crosslinking agent to form a crosslinked polymer product, wherein said a polyvalent metal complex or poly meric ion crosslinking agent comprises a divalent copper ion in an amount of 50 to less than 5000 ppm, based on the polymer solids. According to another aspect of the present invention, there is provided a composition that is used as a base for varnishing floors that produces floor varnishes with improved appearance, comprising an aqueous dispersion or suspension of a water insoluble polymer, said polymer is prepared to starting from more than one ethylenically unsaturated monomer and containing acidic functional residues, and from 10 to 100% of the stoichiometric amount based on said polymer functional acid of at least one polyvalent metal crosslinking agent, wherein said complex crosslinking agent or polyvalent metal ion comprises a divalent copper ion in an amount of 50 to less than? 000ppm, based on the polymer solids. In another aspect, the present invention provides the use of an amount of 50 to less than 5000ppm based on the polymer solids in a composition used as a base for varnishing floors, comprising an aqueous dispersion or suspension of a water insoluble polymer. , said polymer is prepared from more than one ethylenically unsaturated monomer and containing acidic functional residues, and from 10 to 100% of the stoichiometric amount based on said acid polymer functionality of at least one polyvalent metal crosslinking agent, for improve the appearance of a floor varnish comprising said composition that is used as a base for varnishing floors. It has been found that floor varnish compositions comprising a divalent copper ion crosslinking agent, in a prescribed amount, have an improved appearance compared to similar varnish compositions that do not comprise said copper ions. It has also been found that the appearance of a varnish composition that already comprises an optical brightener can be improved through the use of a divalent copper ion crosslinking agent, even when the divalent copper ion is present in very low amounts. This finding is particularly surprising because the divalent copper crosslinkers have hitherto only been incorporated into floor varnish compositions in such relatively high amounts (above 5000ppm in US-A-3554790) that these remove the aesthetic appearance of the dry film of varnish. Preferably, the amount of divalent copper ions used is from 100 to 3500ppm, more preferably from 200 to 2000ppm, and more preferably from 250 to 1500ppm, based on the polymer solids. As long as the amount of divalent copper ion used is at the rate of 50 to less than 5000 ppm, based on the polymer solids, the other parameters of the process will easily be derived from known processes for the preparation of floor varnish compositions. For example, said processes are disclosed in US-A-3308078, US-A-3328325, US-A-3467610, US-A-3554790, US-A-3573329, US-A-3711436, US-A-3808036. , US-A-4150005, US-A-4517330, US-A-5149745 and US-A-5319018. Preferably, the water-insoluble copolymer has a Tg of at least 10 ° C, more preferably of at least 40 ° C. (calculated using the Fox equation: 1 / Tg Wñ / gA + WB / g, B, where Tg is the temperature of transition to glass (° K), TgA and gf ß are the temperatures of transition to glass of homopolymers A and B, and W and Wß represent the weight fractions of components A and B of the copolymer, respectively (T.G.Fox, Bulletin of the American Physical Society 1, 123 (1956)). Preferably, the crosslinked polymer product, formed by the reaction of the water-insoluble polymer and the cross-linking agent, has a minimum film-forming temperature on the Tg of the water-insoluble copolymer. The water-insoluble polymer is preferably formed from a monomer mixture comprising 0% or up to 70%, preferably 25% to 50%, by weight of at least one aromatic vinyl monomer; from 3% to 50%, preferably from 5% to 25% by weight, of at least one acid monomer; and not more than 97%, preferably 30% to 97% and more preferably 30% to 70% by weight, of at least one monomer selected from the alkyl (meth) acrylates (C? -C20), Preference is given to the alkyl (meth) acrylates (C? -C12). Preferably, the vinyl aromatic monomer (s) is / are ethylenically unsaturated alpha or beta aromatic monomers, and is preferably selected from the group consisting of styrene (Sty), vinyl toluene, styrene 2 -bromine, o-bromo styrene, p-chloro styrene, o-methoxy styrene, p-methoxy styrene, allyl phenyl ether, allyl tolyl ether, and alpha-methyl styrene. Styrene is the most preferred monomer. Preferably, the acidic monomer (s) is / are the monoethylenically unsaturated acids alpha or beta, and are preferably selected from the group consisting of maleic acid, fumaric acid, aconitic acid, crotonic acid, citraconic acid , acryloxypropionic acid, acrylic acid, methacrylic acid (AMA) and itaconic acid. The AMA is the one that is preferred. Other monoethylenically unsaturated acid monomers which can be copolymerized to form the water-insoluble film-forming polymers are the partial esters of dicarboxylic, aliphatic, unsaturated acids, and the alkyl medium esters of said acids. For example, the alkyl middle esters of itaconic acid, fumaric acid and maleic acid, wherein the alkyl group contains from 1 to 6 carbon atoms such as itaconate of methyl acid, itaconate of butyl acid, ethyl fumarate, butyl acid fumarate and methyl acid maleate. The monomer mixture does not comprise more than 97% by weight of at least one monomer selected from methyl methacrylate (MAM), methyl acrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate (AB), butyl methacrylate. (MAB), iso-butyl methacrylate (MAIB), 2-ethyl hexyl acrylate, n-octyl acrylate, sec-butyl acrylate and cyclopropyl methacrylate. The monomer mixture may also comprise 0% or up to 40% by weight of at least one hydrophilic, nonionogenic, polar or polarizable monomer, such as acrylonitrile, methacrylonitrile, cis- and trans-crotononitrile, alpha-cyanostyrene, alpha-chloroacrylonitrile, ethyl vinyl ether, isopropyl vinyl ether, isopropyl vinyl ether, isobutyl and butyl vinyl ether, diethylene glycol vinyl ether, decyl vinyl ether, vinyl acetate, isobornyl methacrylate, (methyl) hydroxyalkyl acrylates such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, butanediol acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, -hydroxypropyl and vinyl thiols such as 2-mercaptopropyl methacrylate, 2-sulfoethyl methacrylate, methyl vinyl thiol ether and propyl vinyl thio ether. The monomer mixture may also comprise 0% or up to 10% by weight of at least one monomeric vinyl ester, wherein the acid part of the ester is selected from the aliphatic (Cx-Cxß) and aromatic acids. Such acids include formic, acetic, propionic, n-butyric acids, n-valeric, palmitic, stearic, phenylic, benzoic, chloroacetic, dichloroacetic, gamma-butyric, 4-chlorobenzoic, 2,5-dimethyl benzoic, o-toluic, 2,4,5-trimethoxy benzoic, cyclobutane carboxylic, carboxylic cyclohexane, 1- (p-methoxy phenyl) cydohexane carboxylic, 1- (p-tolyl) -1-cyclopentane carboxylic, hexanoic, myristic and p-toluic. The hydroxy vinyl portion of the monomer, for example, can be selected from hydroxy vinyl compounds such as hydroxyethylene, 3-hydroxy-pent-1-ene, 3,4-dihydroxybut-1-ene and 3-hydroxy-pent. -1-ene, it being understood that said derivation may be purely formal, as in the case of the vinyl acetate monomer in which the compound can be considered to be derived from acetic acid and hydroxyethylene, although the monomer can not in fact be prepared from said precursor compound. The process for the preparation of the water-insoluble, dispersible aqueous polymers of this invention is well known in the art. The practice on emulsion polymerization is discussed in detail in the D.C. Blackley, Emulsion Polymerization (Wiley, 1975). The latex polymers of this invention can also be formulated using emulsions of internally plasticized polymer. The preparation of the internally plasticized polymer emulsions is described in detail in US-A-4150005, and the preparation of the non-plasticized, internally emulsion polymers for polishing the floors is described in US-A-3573239, US-A-3328325, US-A-3554790 and US-A-3467610. Conventional emulsion polymerization techniques, as described above, can be used to prepare the polymer latexes of this invention. In this way, the monomers can be emulsified with anionic or nonionic dispersing agents; preferably, about 0.5% to 10% of these are used over the weight of the total monomers. The acidic monomers are soluble in water and therefore serve as dispersing agents, which helps in the emulsification of other monomers used. A polymerization initiator of the free radical type, such as ammonium or potassium persulfate, can be used alone or in conjunction with an accelerator, such as potassium metabisulfate or sodium thiosulfate. The initiator and accelerator, commonly known as catalysts, can usually be used in proportions of 0.5% to 2%, each based on the weight of the monomers to be copolymerized. The polymerization temperature, for example, can be from room temperature to 90 ° C, or more, as is done regularly. Examples of emulsifiers which are suitable for the polymerization process of the emulsions useful in this invention, include the ammonium and alkali metal salts of the alkyl, aryl, alkaryl and aralkyl sulfonates, polyether sulfates and sulfates, such as sulfonate of sodium vinyl, and sodium methallylsulfonate; the corresponding phosphates and phosphonates, such as phosphoethyl methacrylate; and the alkoxylated fatty acids, esters, alcohols, amines, amides and alkylphenols. Chain transfer agents, including mercaptan, polymercaptan and polyhalogen compounds, are usually desired in the polymerization mixture to control the molecular weight of the polymer. The floor varnish composition preferably comprises the water insoluble polymer, as defined in the above embodiment, from 10 to 100% of the equivalents of the acidic residues in the polymer of at least one polyvalent metal complex or poly meric crosslinking agent. , including from 50 to 5000 ppm of the divalent copper ion, and optionally at least one basic alkali metal salt or hydroxide, as taught in US-A-4517330. The polyvalent metal can be divalent copper alone or a mixture of divalent copper and another polyvalent metal, preferably a transition metal such as zinc. A floor varnish composition is preferred wherein the content of the complex cross-linking agent or total transition metal ion is from 25% to 80% of the equivalent of the acidic residues in the polymer, and / or the molar ratio of the content of the Total transition metal is from 1.0: 0.25 to 1.0: 2.0. Still more preferred is a composition wherein the content of the total transition metal is from 30% to 70% of the equivalent of the acidic residues in the polymer, and / or the molar ratio of the total transition to the alkali metal is 1.0: 0.5 to 1.0: 1.5.

The alkali and polyvalent metal ion complex and crosslinking agents useful in the present invention are well known in the art. For example, these are described in US-A-3328325, US-A-3467610, US-A-3554790, US-A-3573329, US-A-3711436, US-A-3808036, US-A-4150005, US-A-4517330, US-A-5149745, US-A-5319018 and US-A-5319018. Preferred polyvalent metal complexes include zinc (II) ions of diammonium and zinc (II) of tetraammonium, cadmium glycinate, nickel glycinate, zinc glycinate, zirconium glycinate, zinc alanate, copper beta-alanate. , zinc beta-alanate, zinc valanate, copper bis-dimethylamino acetate. The alkali and polyvalent metal ion complex and crosslinking compounds are readily soluble in the aqueous medium of the lacquer composition, especially at a pH at the rate of 6.5 to 10.5. However, the varnish composition containing these compounds is dried to form a varnish deposit which is essentially insoluble in water but still capable of being removed. The polyvalent metal complex can also be added as a solution to the water-insoluble film-forming polymer latex. This can be completed by solubilizing the metal complex in an alkaline solution such as diluted ammonia. Because the ammonia can be complex with the polyvalent metal compound, a compound such as cadmium glycinate, when solubilized in an aqueous ammonia solution, can be called cadmium ammonia glycinate. Other polyvalent metal complexes described can be similarly named. Although to be suitable, the polyvalent metal complex must be stable in an alkaline solution, a complex which is too stable is undesirable because the dissociation of the metal ion would then be retarded during the film formation of the varnish coating. The floor varnish composition should preferably have a minimum film-forming temperature (TMF) less than 100 ° C, and more preferably less than 80 ° C. The crosslinking agent of polyvalent metal complex and ion can be incorporated into the varnish composition during any stage of its formulation. Similarly, the basic salt of the alkali metal can be incorporated with the complex crosslinking agent and polyvalent metal ion during any stage of the varnish formulation. In general, the floor varnish compositions of the present invention will comprise the following essential components: a) from 10 to 100 parts by weight of solids of the water insoluble polymer, which has been previously or subsequently crosslinked with a complex of polyvalent metal and / or basic alkali metal salt; b) from 0 to 90 parts by weight of solids of the wax emulsion; c) from 0 to 90 parts by weight of solids of the alkali soluble resin (RSA) d) from 0.01 to 20 parts by weight of wetting agents, emulsifiers and dispersion of polymer solids, defoamers, leveling agent; optical brighteners, coalescing solvents and plasticizers, sufficient for the formation of the varnish film at the application temperature; e) enough water to make the total solids of the varnish 0.5% to 45%, preferably 5% to 30%. The total of a), b) and c) must be 100. The amount of c), when present, can be up to 100% of a), and 3% to 25% of the weight of a) is preferred. Satisfactory formulations for the varnishing of floors have been prepared without the inclusion of an RSA. Therefore, an RSA is not an essential component of a durable floor varnish composition. Depending on the inherent properties of the composition used as varnish base and other ingredients (d) of the formulation, the RSA can optionally be used to moderately reduce the total costs of the formulation, improve the level and properties of brilliance , and increase the sensitivity of the varnish to the alkaline spoilage, depending on the final balance of the properties desired by the expert who formulates the varnish and the qualities of the RSA.

For a varnish composition with high coating speeds, the wax level preferably must be greater than 6% by weight of the total solids of a), b) and e). In addition to the divalent copper ions, the varnish composition may contain other crosslinking agents and optical brighteners which may be used in conventional or smaller amounts, depending on the balance of the properties desired by the expert formulating. The coalescing solvents and plasticizers, defoamers, dispersing agents and conventional wetting agents can be used in conventional amounts, depending on the balance of the development properties desired by the expert formulating. Optionally, the expert formulating may include other ingredients of the formulation, such as perfumes or agents that cover odors, dyes or dyes, bacteriocides and bacteriostats. Now, the invention will be described more specifically in terms of the following examples of some preferred embodiments, which are provided for purposes of illustration only, and may be contrasted with the comparative tests that are also provided below.

Floor tests, for the development of the appearance.

To the floor test areas, the residual varnish was scraped and re-varnished with the typical procedure, as follows: Dust was removed from the floors to remove dirt. A 1: 1 aqueous solution of commercial cleaning solution ("SSS Easy Strip", Standardized Sanitation Systems, Inc., Burlington, Massachusetts 01803) was applied with tow, at an index of 1000 square feet per gallon (25m2l_1), after a Soaking period of five minutes, the floors were scrubbed with a black floor fiber with a diameter of 16 inches (40cm.) (3M Company, St. Paul, Minnesota 55101; "Scotch Brite" fine-line floor fiber) in a 175rpm floor machine. (Howell Electric Motors, Plainfield, New Jersey, model 88400-026); the scraped floors were rinsed very well twice wet cleaning with clean water, and allowed to dry. Scraped floors were divided into sections of 20 square feet (2m2) perpendicular to the normal direction of traffic flow on the floor. Four layers of the varnish that was going to be tested were applied to each of the sections, with a small tow no. 37627 of cotton / rayon, of wide width of SSS finish, in an index of ca. 2,000 square feet / gallon (SOm2! "1). Each layer was allowed to dry for one hour before applying the next coat.

The layers were applied to white vinyl slab composite floors, and cured at ambient conditions. After the layers had dried, they were exposed to pedestrian traffic for a month, without maintenance. They were visually examined to determine the appearance of the layers. The appearance of the layer was determined by evaluating the overall appearance of the film compared to a comparative varnish. This test was designed to distinguish relative differences. Appearance is a property that is difficult to measure quantitatively. Therefore, "the perception of cleanliness" or "clean representation" are the actual criteria of appearance and visual observation, as with other qualitative measures used in the evaluation of floor coverings, it is completely acceptable to those experts in the field. . Appearance was evaluated in the following scale: 5 - much better than comparative 4 - better than comparative 3 - equivalent to comparative 2 - worse than comparative 1 - much worse than comparative Drag resistance of the feet and black heel marks. The method to determine the resistance to deterioration and the black heel, described in the Bulletin of the Association of Manufacturers of Chemical Specialty no. 9-73, except that commercially available shoe rubber heels were used instead of the recommended 2-inch (5.08cm) rubber buckets. In addition, instead of sub-efficiently evaluating the covered substrate, the percentage of the substrate area covered with trailing and black-heeled markings was determined.; this is developed conventionally with transparent graph paper. A black heel mark is a very deposition of the rubber on or inside the layer, where a trailing mark is the result of the physical displacement of the layer, which appears as an area of reduced brilliance. The black heel and drag marks can occur independently or simultaneously at the point where the heel hits the substrate, that is, after removing a black heel mark, deterioration can occur.

Brilliance The method for determining the brightness development of the varnish compositions is described in the "Annual Book of ASTM Standards" section 15, volume 15.04, ASTM D 1455 Test Procedure. Gardner Micro-tri-brilliance meter, no. of catalog 4520, to register a brightness of 60 ° and 20 °.

Coating capacity The method for determining the coating capacity of water-based emulsion floor coatings is described in the "Annual Book of ASTM Standards", section 15, volume 15.04, ASTM Test Procedure D 3153 Waterproof. The method for determining the water resistance of the varnish compositions is described in the "Annual Book of ASTM Standards", section 15, volume 15.04, Test Procedure ASTM D 1793, and was used the following scale for evaluating the water resistance of the coating compositions: Excellent - no watermark or noticeable damage to the coat Very well - thin line of water Well - light grade of whitish film Regular - whitish film with bubbles and rising Poor - complete failure of the film with general bleaching and loss of adhesion.

Resistance to detergent. The method for determining detergent resistance is described in the "Annual Book of ASTM Standards", section 15, volume 15.04, Test Procedure ASTM D 3207, except that a diluted Forward was used ® (SC Johnson and Sons, Inc., Racine, WI) in water, as a test detergent solution.

Removal capacity. The method for determining the removal capacity is described in the "Annual Book of ASTM Standards", section 15, volume 15.04, Test procedure ASTM D 1792, except that 1/20 of diluted from Forward® (SC Johnson and Sons, Inc., Racine, WI) in water with 1% NH3, as a scraping solution.

Film formation. An extract containing 0.4ml was applied. of the coating composition by means of a two inch (5.08 cm.) wide blade applicator (as specified in ASTM D 1436), with a height of 0.008 inches (0.2 cm.), for a length of 4 inches ( 10.16cm.), On a vinyl slab. Immediately after the application of the varnish, the slab was placed on a level surface in a refrigerator at 10 ° C. The dried film was evaluated as follows: Excellent - without cracking Very good - light edge cracking Good - defined edge cracking Regular - defined edge cracking with very light cracking at the center Poor - full edge and center cracking.

EXAMPLES The following examples are presented to illustrate the invention. These are not intended to limit the invention.

Formulation of coatings based on copper-modified emulsions. In order to properly evaluate the development of an emulsion polymer for use in a varnish base, it is necessary that the polymer be formulated as a varnish. The formulation of the emulsion polymers of this invention is common to the practice of floor varnish formulations. The ingredients used and their proportions and manner of addition are the same as commonly practiced in emulsion polymers of conventional technology. ÍA. Aqueous varnish formulation for floors for examples 1 to 4 (Order of addition shown) Material Function Quantity (parts by weight) Diluent water 43.2 FC-120 (1%) L wetting agent 1.00 Kathon CG / ICP (1.5%) "biocide 0.03 SE-21J defoaming 0.02 Diethylene glycol ethyl ether coalescer 2.63 Dipropylene glycol -methyl ether coalescer 3.68 Plasticizer dibutyl phthalate 1.10 Tributoxyethyl Phosphate Auxiliary Leveling 1.58 Emulsion (38%) used as base 40.31 ASR-Plus (35%) "resin that is inflated / 2.35 soluble in alkali AC-540N (30%) 4 wax emulsion 4.10 polyethylene Formulation constants: Polymer / RSA / Wax index 88/7/5 Theoretical non-volatile solids 20% 1 3M Co. (Minneapolis, MN) 2 Rohm and Haas Co. (Philadelphia, PA) 3 Acker Silicones Corp. (Adrián, MI) 4 Allied-Signal Corp. (Morristown, NJ) ÍA. Aqueous varnish formulation for floors for examples 5 to 6. (Order of addition shown) Material Function Quantity (parts by weight) Water thinner 44.61 FC-120 (1%) 1 wetting agent 0.45 Kathon CG / ICP (1.5%) "biocide 0.03 SE-21J defoaming 0.02 Diethylene glycol ethyl ether coalescer 2.64 Dipropylene glycol methyl ether coalescer 1.64 Dibutyl plasticizer phthalate 0.73 Tributoxyethyl phosphate auxiliary leveler 0.73 Emulsion (38%) vehicle 36.57 ASR-Plus (35%) "resin that is inflated / alkaline-soluble 2.65 E-43N (40% r emulsion of wax 4.64 of polypropylene AC-325N (35%) 5 wax emulsion 5.29 polyethylene Formulation constants: Polymer / RSA / wax index 75/5/20 Theoretical non-volatile solids 20% 1 3M Co. (Minneapolis, MN) 2 Rohm and Haas Co. (Philadelphia, PA) 3 Acker Silicones Corp. (Adrián, MI) 4 Eastman Chemical Corp. (Easport, TN) 5 Allied-Signal Corp. (Morristown, NJ) Examples 1 to 4 demonstrate the improvement in the appearance properties of the invention, using a conventional water-based polymer according to the technology taught in US-A-4517330.

Example 1 A polymer latex was prepared with a monomer composition of 35AB / 9MAM / 40ST / 16AMA. The latex composition also contained 3.6% Zn ++ in latex solids, added as Zn (NH3) 4 (HCO) 3) 2, and 0.7% K + in the latex solids, added as KOH. Example 1 is a comparative that does not contain copper. Example 1 was formulated in the test composition, as described in formulation IA.

Examples 2 to 4 The coating composition of example 2 contains 500ppm Cu (II), added as Cu (OH) 2, but otherwise has the same composition as described in Example 1.

Example 2 was formulated in the test composition, as described in formulation IA. The coating composition of Example 3 contains lOOOppm of Cu (II), added as Cu (OH) 2, but otherwise has the same composition as described in Example 1.

Example 3 was formulated in the test composition, as described in formulation IA. The coating composition of Example 4 contains 5000ppm Cu (II), added as Cu (0H) 2, but otherwise has the same composition as described in Example 1.

Example 4 was formulated in the test composition, as described in formulation IA. The compositions of Examples 1 to 4 were tested for the appearance and other development properties of the floor varnish. The results, listed in Table 1, show that the coating composition having copper improves the appearance characteristic of a coating without affecting the key properties of the floor varnish development.

Table 1 Example 1 Example 2 Example 3 Ex. 4 (comparative) without copper 500ppm lOOOppm SOOOppm copper copper copper Appearance 3 4 4 2 Resistance to black heel marks (% coverage) 4.1 4.0 4.0 4.3 Resistance to drag marks (% coverage) 2.5 2.5 2.5 2.5 Brilliance 60 °, 20 ° 75 °, 25 ° 77 °, 22 ° 75 °, 22 ° 70 °, 20 ° Good coating capacity good good good Water resistance very good - very good - very good - very excellent excellent excellent good - Excellent Excellent detergent resistance excellent excellent excellent Excellent removal capacity excellent excellent excellent Excellent excellent excellent film formation excellent examples 5 to 6 demonstrate the improvement in appearance of the invention using a conventional water-based polymer formulated within the coating composition.

Example 5 A latex polymer was prepared according to the technology taught in US 4,150,005 to Gehman et. al., obtaining a composition of 30AB / 10.5MAM / 5 HEMA / .5 AMA // 40 STY / 5 MAM / 5 AA. Example 5 is a comparative that does not contain copper. Example 5 was formulated within the coating composition, as described in formulation IB.

Example 6 The coating composition of Example 6 contains lOOOppm of Cu (II), added as Cu (OH) 2, but otherwise has the same composition as described in Example 5. Example 6 was formulated into the composition of test, as described in example 5. The compositions of examples 5 and 6 were tested for the development properties of the floor varnish and the appearance. The results, which are listed in Table 2, show that the coating composition having copper improves the cleaning characteristic of a layer without affecting the key properties of the floor varnish development. Table 2 Example 5 Example 6 (comparative) without copper 100 Oppm of leveling copper 3 4 Brand resistance of 2.6 2.5 black heel (% coverage) Brand resistance of 4.0 4.3 drag (% coverage) Brilliance 60 °, 20 83 °, 30 ° 85 °, 33 ° Good coating ability good Very good water resistance very good - excellent excellent Excellent excellent detergent resistance Excellent excellent removal capacity Excellent excellent film formation

Claims (4)

1. Claims 1. A process for improving the appearance of a floor varnish composition, the process comprises: a) charging a reaction zone with an aqueous dispersion or suspension of a water insoluble polymer, said polymer is prepared from more than an ethylenically unsaturated monomer and containing acid functional residues, and from 10 to 100% of the stoichiometric amount based on said polymer functionality acid of at least one polyvalent metal crosslinking agent, and b) reacting said polymer and said crosslinking agent to form a crosslinked polymer product, wherein said at least one polyvalent metal complex or poly meric ionic crosslinking agent comprises a divalent copper ion in an amount of 50 to less than SOOO ppm, based on the polymer solids.
2. 2. A process according to claim 1, wherein the amount of the divalent copper ions used is from 100 to 3500ppm, more preferably from 200 to 2000ppm, and more preferably from 250 to 1500ppm, based on the solids of polymer
3. 3. A composition that is used as a base for varnishing floors that produces floor varnishes with improved appearance, comprising an aqueous dispersion or suspension of a water insoluble polymer, said polymer is prepared from more than one ethylenically unsaturated monomer and which contains acid functional residues, and from 10 to 100% of the stoichiometric amount based on said acid polymer functionality of at least one polyvalent metal crosslinking agent, wherein said at least one polyvalent metal complex or crosslinking agent comprises a divalent copper ion in an amount of 50 to less than 5000ppm, based on polymer solids.
4. 4. The use of a divalent copper ion in an amount of 50 to less than 5000ppm based on the polymer solids in a composition used as a base for varnishing floors, comprising an aqueous dispersion or suspension of a water insoluble polymer , said polymer is prepared from more than one ethylenically unsaturated monomer and containing acid functional residues, and from 10 to 100% of the stoichiometric amount based on said acid polymer functionality of at least one polyvalent metal crosslinking agent containing said copper, to improve the appearance of a floor varnish comprising said composition that is used as a base for varnishing floors.