MXPA96003799A - Polyurethane composition resistant to damage and destroying - Google Patents

Abstract

The present invention relates to the polyurethane composition is an oil-modified urethane polymer, dispersible in stable water. In another embodiment, the present invention provides a conventional wear and rub resistant coating composition, the coating composition comprising a prepolymer having isocyanate groups, acid or amine salt forming groups and ethylenic unsaturation and an active hydrogen containing compound. having an active hydrogen functionality of two or more, wherein a portion of the prepolymer has an extended chain with an active hydrogen-containing compound having an active hydrogen functionality of four or

Description

"COMPOSITION OF POLYURETHANE RESISTANT TO DAFlO AND WEAR" FIELD OF THE INVENTION This invention relates to polyurethane compositions and, in particular, to oil-modified urethane coating compositions, dispersed in water, having improved resistance to usual wear and rubbing.

BACKGROUND OF THE INVENTION Those versed in the coatings industry generally know that polyurethane coatings exhibit excellent abrasion resistance, excellent flexibility, resistance to chemicals and -...durability. These coatings have found important utility for coating hard surfaces, such as hardwood floors that require highly durable coatings that resist the usual wear and tear. The conventional oil-modified urethanes are prepared in organic solvents and applied as clear or pigmented finishes. Once it is applied, the solvent evaporates and the film is cured by oxidation in air of the oil portion _e? polymer. Urethanes carried in conventional solvent have provided high performance floor coverings for many years, but due to government regulations about volatile organic compounds (VOCs) they are now being restricted in certain locations, although versions of these led coatings are known. in solvent, which have a high content of solids and less contaminants, typically there is a compromise between performance, particularly dry regime and hardness. An alternative is to use polyurethanes dispersible in water, carried in water. Applications for this type of "/" include final coatings for wood and vinyl flooring, vinyl upholstery, plastics, base paints and sizing for the automotive industry, leather finishes, Finishes for fiberglass, printing inks and adhesives Water-based urethane coatings are particularly attractive as coatings or varnishes for wood floors, due to their abrasion resistance, fast air drying, low. "* Contained volatile organic (VOC), lack of flammability and ease of cleaning with water. Generally, water-dispersible polyurethanes can be prepared by first reacting polyalcohols and a dihydroxycarboxylic acid with an excess of diisocyanate to form an isocyanate-terminated prepolymer. Said prepolymer is then dispersible in water by neutralization of the acid group with ammonia or tertiary amine to form the corresponding salt group. An alternative jib is to replace the dihydroxycarboxylic acid moiety with a tertiary dihydroxy amine which would be neutralized with an acid such as hydrochloric acid, acetic acid or the like. These polymers are mostly linear, since highly entangled polymers form gels that are not suitable for coating applications. For example, U.S. Patent No. 4,277,380 to Williams and co-inventors, proposes that aqueous polyurethane dispersions can be prepared by reacting an unsaturated ethylenically fatty acid ester, a fatty acid, a semi-dryer, and a urethane prepolymer. terminated with isocyanate of a hydrocarbon diisocyanate and a dihydroxyalkanoic acid. This functional polymer of acid can then be neutralized with ammonia or amines, preferably tertiary amines, and can be dispersed in water. Coating compositions of this type have deficiencies in that they are brittle and do not have the storage stability for a long time necessary for a commercially available lacquer US Patent Nos. 4,066,591 and US Pat. 4,147,679, by Scriven and co-inventors, proposes that polyurethane-polyurea dispersions can be prepared from polyurethane prepolyners containing ethylenic unsaturation, which are extended chain with diamines. These dispersions do not provide adequate performance, particularly with respect to the resistance to conventional wear and rubbing, for such applications as wood floor covering. In general, linear polyurethane dispersions do not provide all the desired key aspects in a floor finish, for example, the usual wear resistance and rubbing. Due to the cost of these polyurethane dispersions, suppliers of the floor finishing industry add acrylic emulsions to reduce the cost. This modification results in floor finishes with -sistance to impact much more deficient. Poly functional aziridines can crosslink these polymers, which significantly improves these properties; However, aziridines can cause serious risks for the health. Carbodiimides have been recommended as crosslinking agents for anionic polyurethane dispersions, but have been shown to be significantly less effective. Thus, there is a need for a dispersion ^ oil-modified polyurethane, stable to storage, which produces rapid drying in air, high purity, good resistance to usual wear, rubbing, abrasion and which produces coatings resistant to stains. and the chemical substances.

BRIEF DESCRIPTION OF THE INVENTION It is an object of the present invention to provide a "stable polyurethane coating apposition having improved resistance to usual wear and rubbing." It is another object of the present invention to provide a stable composition of polyurethane that can be dried in air, which has high hardness and is resistant to abrasions, chemicals and stains These and other objects, aspects and advantages are obtained by the polyurethane composition of the present invention The polyurethane composition is a modified ethane polymer with oil, dispersible in water The urethane polymer comprises a polymer having isocyanate groups, acid or amine salt forming groups and ethylenic unsaturation, and an active hydrogen-containing compound having active hydrogen functionality of two or more; where a portion of the prepolymer has an extended chain with a compound containing active hydrogen that has e active hydrogen functionality of four or more. In another embodiment, the present invention provides a coating composition resistant to normal wear and rubbing. The coating composition comprises a urethane composition dispersed in water and a promoter that promotes entanglement by air oxidation of the ethylenically unsaturated portion of the urethane composition. The urethane composition comprises a prepolymer having isocyanate groups, acid or amine salt-binding groups and ethylenic unsaturation and a hydrogen-containing compound having active hydrogen functionality of two or more; wherein a portion of the prepolymer has its extended chain with a compound containing active hydrogen, having an active hydrogen functionality of four or more. In another embodiment, the present invention provides a method for forming an oil-modified urethane polymer, dispersible in water, resistant to usual wear and rubbing. The method comprises the steps of forming a prepolymer having isocyanate groups, acid-forming or amine-forming groups, and ethylenic unsaturation; neutralizing the acid or amine salt of the prepolymer formed in the preceding step; dispersing the neutralized prepolymer in an aqueous medium and extending the chain of the dispersed prepolymer with an active hydrogen-containing compound, having an active hydrogen functionality, conditional upon a portion of the chain extension being carried out with a compound which contains active hydrogen having an active hydrogen identity of four or more.

DETAILED DESCRIPTION OF THE INVENTION As summarized above, the present invention provides an oil-modified, water-dispersible urethane polymer. The urethane polymer comprises a prepolymer having isocyanate groups, acid or amine salt-forming groups and ethylenic unsaturation; and a tax that contains active hydrogen, which has an active hydrogen functionality of two or more. A portion of the prepolymer has the chain extended with an active hydrogen-containing compound having an active hydrogen functionality of four or more. The urethane polymer is dispersed in an aqueous medium, such as water, to provide a coating composition resistant to normal wear and rubbing. The coating composition is stable, has high hardness and is resistant to abrasions, chemical substances and stains. Particularly suitable polyisocyanates are those corresponding to the formula R (NCO) n, wherein R represents a difunctional aliphatic hydrocarbon radical containing from 4 to 18 carbon atoms, or a difunctional cycloaliphatic hydrocarbon radical containing from 5 to 15 carbon atoms. It is also possible, although not preferred, to use polyisocyanates in which R is a difunctional diffractional aromatic dichloride radical containing from 6 to 40 carbon atoms, or an araliphatic hydrocarbon radical containing from 7 to 40 carbon atoms. Examples of isocyanates include: 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trirnethyl-1,6-diisocyanatohexane, 1,10-decarnethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-methylene (isocyanatocyclohexane), l-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, rn- • "p-phenylene diisocyanate, 2,6- and 2,4-tolylene diisocyanate , xylene diisocyanate, 4-chloro-l, 3-phenylene diisocyanate, 4'-biphenylene diisocyanate, 4,4'-diphenyl isocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate and polymethylene polyisocyanates The polyisocyanates can include various other functional moieties, such as ketones, esters, aldehydes, amides, halogenated hydrocarbon ethers and tertiary amines Examples of polyisocyanates are described, for example, in US Pat. Nos. 4,066,591 and 4,147,679 of Scriven and co-inventors; 4,277,380 of Williams and co-inventors; 4,499,233 from Tetenbaum and co-inventors; and 4,745,151 by Noli and co-inventors, the descriptions of which are hereby incorporated by reference in their entirety. The preferred acid-forming acid groups are introduced into the prepolymer by reacting the isocyanate compounds with those containing both hydrogen and acid groups. Specific examples of compounds containing active hydrogen and acid groups capable of forming salt are hydroxy acids and carbocarboxylic acids, arninocarboxylic acids, indoxycarboxylic acids, syphonic acids, hydroxyalonic acids, sulphonic acids and anionsulonic acids, such as those described in U.S. Patent Nos. 4,147,679 to Scriven and co-inventors and 4,745,151 to Noli and co-inventors. A particularly suitable compound is ^ ethylolpropionic acid. The prepolymers have an acid value of 10 to 50 to 100% solids. Suitable neutralizing agents for these acidic groups include inorganic and organic bases, such as sodium hydroxide, potassium hydroxide, ammonia and tertiary amines, such as triethylamine, dimethylethanolamine and the like. Preferred salt-forming base groups are introduced into the prepolymer by reacting the isocyanate compounds with those containing both hydrogens and basic groups. Specific examples of compounds containing active hydrogens and basic tertiary arnino groups are: the aliphatic, cycloaliphatic, aromatic and heterocyclic aminoalcohols, the corresponding diols and triols. Examples include: N, N-direthylethanolamine, N-methyl-N- (β-hydroxyethyl) aniline, N-hydroxy-ethylpiperidine, methyldiethanol, cyclohexyldiethanolamide, N, N- (bis-hydroxyethyl) aniline, N, N- O'-síhidroxietiD-a-aminopiridina. Other specific examples are amines, diamines, triamines and amides, such as N, N-dimethylhydrazine, N, N-dimethylethylenediamine, alpha-aminopyridine, N-arninopropylethyleneimine and bis (3-aminopropyl) methylamine. The prepolymer have an amine value of 10 to 50 to 100 solids. Suitable neutralizing agents for these basic groups are organic and inorganic acids, such as hydrochloric acid, acetic acid, phosphoric acid, glycolic acid, lactic acid and the like.

- The ethylenic unsaturation in the prepolymer is introduced by ester polyols prepared by reaction of an aromatic or aliphatic polyol containing at least two hydroxyl groups per molecule and a fatty acid, characterized in that a portion thereof is an unsaturated fatty acid. Fatty acids are sometimes referred to as "drying" or "drying" agents, particularly when they are in the form of an ester. An exemplary reaction is to partially sterilize a polyol with a saturated fatty acid. Suitable polyols include diols, triols and higher alcohols of low molecular weight. Specific polyols include ethylene glycol, propylene glycol ,. 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, bisphenol A, glycerin, trimethylolpropane, pentaerythritol, neopentyl glycol and cyclohexanedimethanol. The ethylenic unsaturation can also be provided by transesterification of a drying or semi-drying oil with an aromatic or aliphatic polyol containing: * at least two hydroxyl groups per molecule. Suitable drying or semi-drying oils include flaxseed oil, soybean oil, safflower oil ,. first distillation oil, sunflower oil, dehydrated castor oil, tunga oil, sardine oil, olive oil, cottonseed oil and the like. Suitable unsaturated fatty acids include linoleic, palmitinoleic, linolenic, eleostearic, arachidonic, ricinoleic acids and the like. The reaction of the polyol and the fatty acid can be carried out by transesterification catalysts, such as calcium naphthenate, lithium neodecanoate, zinc acetate, tin oxide and the like. A color stabilizer, such as trisnonyl phenyl phosphite can also be added. Other polyols may optionally be included. Examples of other polyols include polycarbonate, polyester, polyether and acrylic polyols. The term "active hydrogen-containing compound" refers to a compound having hydrogens which, due to its position in the molecule, exhibits activity according to the Zerewitinoff test. Active hydrogens include hydrogen atoms attached to oxygen, nitrogen or sulfur and, therefore, useful compounds will include those having at least two of those groups (in any combination) -OH, -SH, NH I and -NH2. The portions connected to each group can be aliphatic, aromatic, cycloaliphatic or of a mixed type that does not include carbonyl, phosphonyl or sulfonyl bonds, as described in US Patent No. 4,147,679 to Scriven and co-inventors. Examples of such compounds include amines including polyamines, indole alcohols, mercapto- and alcohol-terminated derivatives, which include polyols which are preferred to the reaction facility they exhibit with the polyisocyanates. Amines generally do not give side reactions, providing higher yields of urethane (or urea) product, no by-products, and the products are hydrolytically stable.Also with respect to polyols there is a wide variety of materials available that can be selected for In addition, the polyols have desired reaction rates with the polyisocyanates, both saturated and unsaturated active hydrogen containing taxes can be used, but saturated materials are preferred because of the superior coating properties. which can be used in the preparation of the urethanes of the invention can be or primary or secondary diamines, wherein the radicals attached to the nitrogen atoms can be aliphatic, alicyclic, aromatic, aliphatic substituted with aromatic, substituted aromatics, "* t > aliphatic or heterocyclic, saturated or unsaturated. Examples of suitable aliphatic and alicyclic diamines are: ethylendiarnine, 1,2-α-pyrrolidiarnine, 1,8-mentanediarin, isophoronediamine, propane-2, 2-cyclohexylamine, ethane-bis- (-cyclohexyllanine), 1,6-diarninohexane, hydrazine, and CH3 H2 N (CH2 -CH-0) x CH2 -CH NH2 I CH3 ^ *? where x = 1 to 10. The aromatic diamines such as phenylenedianes and toluenediamines can be used. Examples of the mentioned amines are: o-phenylenediamine and p-tolylendia ina. The N-alkyl and N-aryl derivatives of the above amines can be used, such as, for example, N, '-dime i1-o-phenylenediamine, N, N'-di-p-tolyl-m-phenylenediarin and p-aminodiphenylamine. The extension of the prepolymer to obtain polymers / high molecular weight is achieved by the reaction of the isocyanate-terminated prepolymer, dispersed in water, neutralized, with an active hydrogen-containing compound, having active hydrogen functionality of two or more. Typically this is provided by a diamine or a triarnine. Suitable dianins include: ethylenediamine, 1,2- and 1,3-diarninopropane, 1,6-diaminohexane, 1,3-diamino-2,2-dirnethylpropane, isophoronodianine, 1,3- and 1,4,4-diarninohexane, i, '-diarninodicyclohexyl ethane, 4,4'-diamino-3,3' -dirnetyldicyclohexyl-methane, 1, -bis (2-aminopro-2-yl) -cyclohexane, 3,3'-dimethyl-4,4'- diaminodicyclohexyl-methane and mixtures of these diamines. Suitable triamines include diethylenetriarnine and dipropylenetriarnine. In order to obtain the desired resistance to usual wear and rubbing, a portion of the prepolymer must have the chain extended with an active hydrogen-containing compound having an active hydrogen functionality of four or more. typically, at least 1 to 100%, preferably more than about 10% and better still more than about 25% of the prepolymer is extended with an active hydrogen-containing compound, having active hydrogen functionality of four or more. Examples of compounds containing active hydrogen, which have functionality of four or more include triethylene tetramine, tripropylene tetra and tetraethylenepentane ina. Generally the prepolymer is prepared in the presence, 3? N solvent for the reactants and the prepolymer product. Usually the solvents are organic and can comprise essentially carbon and hydrogen, with or without other elements, such as oxygen or nitrogen. The solvent used is essentially inert to the reaction and, thus, must not contain active hydrogen, as determined by the Zerewitinoff test. Solvents which may be employed include strongly polar solvents, such as methylformamide, esters, ethers, ketoesters, ketones, for example, methyl ethyl ketone and acetone, ether glycol esters, chlorinated hydrocarbons, aliphatic and alicyclic hydrocarbon pyrrolidones, for example, N-Rethyl-pyrrolidones, hydrogenated furnaces, aromatic hydrocarbons and the like, and mixtures thereof. The amount of solvent used to prepare the prepolymer can vary widely and should be sufficient to provide a prepolymer solution having a sufficiently low viscosity to facilitate the preparation of the polymer used in this invention. It is convenient to minimize the amount of solvent to minimize VOCs. For example, the solids content of the prepolymer solution may be about 30 to 100% by weight, preferably about 60 to 100% by weight, approximately. The prepolymer formation can be carried out by mixing the diisocyanate and other reagents in any suitable manner. To facilitate the reaction, about 0.005 to 1000% by weight of the reactants such as a conventional urethane catalyst can be added. These catalysts are exemplified by catalytically active compounds of bismuth, piorne, tin, titanium, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, vanadium, cerium, as well as magnesium oxide, barium oxide , tertiary amines, pyrones and lactams, the preferred catalyst being dibutyltin dilaurate. The modification reaction with oil introduces -% = > unsaturated fatty acid within the structure of the polymer. The urethane polymers modified with oil, prepared according to this invention, have sufficient acid values for their salt form to be dispersible in the aqueous medium, and said values can frequently be from 10 to 50, on a non-volatile basis. The solids content of the solutions, for example, can be from about 30 to 100% by weight, preferably from 60 to 100% by weight, before the formation of the salt and the dispersion in the water.

The oil-modified urethane polymers of this invention are advantageously employed as aqueous coating compositions, ie, the prepolymers are dispersed in an aqueous medium, such as water. The chain of the dispersed prepolymer is then extended with an active hydrogen-containing compound having an active hydrogen functionality conditional on a portion of the chain extension being carried out with an active hydrogen-containing compound having a hydrogen functionality Four or more. Frequently, the aqueous compositions have a relatively neutral pH, for example, from 6 to 11, preferably from 6.5 to 9.9 approximately. It should be noted that the neutralization of the acid or the amine salt of the prepolymer and the chain extension can occur substantially simultaneously. The urethane composition includes a promoter for promoting the entanglement by oxidation with air of the unsaturated ethylenically unsaturated polymer of the urethane polymer, after application. Suitable promoters include cobalt, calcium, manganese or zirconium neodecanoate; 1,10-phenanthroline and 2,2-bipyridyl. The composition may contain other ingredients for the coating compositions, in order to modify the properties of the resulting oil-modified urethane, such as plasticizers, pigments, colorants, dyes, surfactants, thickeners, heat stabilizers, anti-caking agents, anti-aging agents -provisioning, fillers, sedimentation inhibitors, ultraviolet light absorbers and the like. The additives, such as promoters, heat stabilizers, ultraviolet light absorbers, etc., can be intimately dispersed in the reaction mixture and apparently become an integral part of the urethane polymer. Alternatively, the additive may be introduced after the urethane polymer has been formed, in which case the additive may be incorporated onto the surface of the polymer may be dispersed in the aqueous medium. The urethane coating composition has improved properties of resistance to usual wear and rubbing and is air-dried, has high hardness and is resistant to abrasions, chemicals and stains.

EXAMPLES EXAMPLE 1 An oil ester polyol was prepared in a dry flask, equipped with stirrer, thermometer, nitrogen inlet and condenser, where 2500 parts of linseed oil and 203.5 parts of pentaerythritol are reacted in the presence of 3.2 parts of lithium ( 2%) Ten Cem, obtainable from 0P1G, Inc., Cleveland, Ohio. Upon completion of alcoholysis, 3.5 parts of trisnonyl phenyl phosphite stabilizer is added.

The resulting ester oil polyol had a hydroxyl value of 123.6. 120 parts of the ester polyol are added 18.2 parts of dimethylolpropionic acid, 24 parts of neopentyl glycol, 6-hexane diol polyol of adipic acid having a hydroxyl value of 120, 96.4 parts of 4,4'-methylenebis-isocyanatocyclohexane. , 43.2 parts of N-methylpi rolidi ona and 0.08 parts of dibutyltin dilaurate, obtainable as Metacure T-12 from Air Products and Chemicals, Inc., Allentown, Penneylvania. The reaction is heated to 85 ° C until the isocyanate content is constant. The resulting content is then added to 13.7 parts of triethylamine, 2.7 parts of ethylenediamine, 1.6 parts of triethylene tetra as a chain extender, and 502.2 parts of water. 500 parts of this dispersion are added to 1.14 cobalt (5%) cobalt neodecanoate promoter Hydro Cure TI and 0.34 part of Dri-RX, 2, 2-bipyridyl obtainable from llooney - 'rnicals, Inc., Cleveland, Ohio .

EXAMPLE 2 Example 1 is repeated, except that 1.6 parts of tetraethylenepentane ina is used as a chain extender, instead of triethylenetene.

COMPARATIVE EXAMPLE 1 Example 1 is repeated, except that only ethylene diamine is used as a chain extender.

TABLE 1 Example Example 1 Example 2 Comparative 1 Properties in Wet:% of NV 32 33 34 PH 8.1 7.8 7.8 Viscosity, cps at 25 ° C 99 33 39 Properties of Film: Hardness to harden, hours 1.0 1.0 2.0 Resistance to rubbing 4 4 3.5 nsistence al nesgaste usual Good Good Regular Sward hardness 40 40 40 Resistance to chemical substances Good Good Regular Impact, D / R 160/160 160/160 160/160 Table 1 summarizes the wet and film properties of the examples. The drying time is measured in a wet film of 76.2 microns thick, using a Gardner circular dry time recorder. The rub resistance is measured on a wet coating of 76.2 microns thick, cured for seven days at 25 ° C and 50% relative humidity; placing the cured panel on the floor and holding it down with one foot; vigorously kicking the panel five times with a shoe that has a soft rubber sole; Immediately the rubbing that kicks off with mineral spirits (7% aromatics) is cleaned and left to dry perfectly; the rubbing is classified from 0 to 5, with 0 being worse and 5 being the best. The usual wear resistance is measured in a wet coating of 76.2 microns thick cured for 20 days at 25 ° C and 50% relative humidity; applying sustained pressure to the cured film with the fingernail and moving the finger from left to right and back several times; and the usual wear resistance is classified as good if no scratch is observed in the film and as bad if scratches or marks are present. The hardness is measured - "Dried on a wet film of 76.2 microns thick in a cured coating for seven days at 25 ° C and 50% relative humidity, using ASTM D 2134. The resistance to chemicals in a coating is measured. wet film, 76.2 microns thick, cured for seven days at 25 ° C and 50% relative humidity using ASTM D .1308-87. Impact resistance was determined in a wet film coating of 76.2 microns thick, cured for seven days at 25 ° C and 50% relative humidity, using ASTM D 2794-69.

Claims (43)

1. NOVELTY OF THE INVENTION CLAIMS 1. - An oil-modified urethane polymer dispersible in water, characterized in that it comprises: (a) a prepolymer containing: (i) isocyanate groups; (ii) acid or amine salt forming groups; and (iii) ethylenic unsaturation, which is the result of the reaction of the prepolymer with an unsaturated ester polyol; (b) a compound containing active hydrogen, having active hydrogen functionality of two or more; wherein at least 20% of the prepolymer has the chain extended with a compound containing active hydrogen having active hydrogen functionality of four or more. 2.- The oil-modified urethane polymer, Water-insensitive according to claim 1, further characterized in that the active hydrogen-containing compound having active hydrogen functionality of four or more is triethylenetetramine, tripropylenetetramine or tetraethylenepentanine. 3. The water-dispersible oil-modified urethane polymer according to claim 1, further characterized in that the isocyanate group is provided by the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene isocyanate , 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylene di-isocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-ethylenebis (isocyanatocyclohexane), l-isocyanato-3-isocyanatomethyl-3 , 5,5-trimethyl-cyclohexane, my p-phenylene diisocyanate, 2,6- and 2,4-tolylene diisocyanate, xylene diisocyanate, 4-chloro-l, 3-phenylene diisocyanate, 4,4-diisocyanate '-biphenylene, diphenylisocyanate of 4,' -methylene, 1,5-naphthylene diisocyanate, 1,5- "dihydrazethane dihydrazethane and polymethylene polyphenylisocyanates 4.- The water-dispersible, oil-dispersed urethane polymer in accordance with with claim 1, further characterized in that the acid salt forming group is introduced into the prepolyme by a compound containing active hydrogen and active acid groups neutralized by a neutralizing base. 5.- The urethane polymer modified with oil, "water-removably, according to claim 4, further characterized in that the active hydrogen-containing compound and the acid-active groups is selected from the group consisting of hydroxy- and mercapto-carboxylic acids, aminocarboxylic acids, aminohydroxycarboxylic acids, sulfonic acids, hydroxysulphonic acids and arninosulonic acids 6. The oil-modified urethane polymer, water-dispersible, according to claim 4, further characterized in that the compound having the hydrogen and the acid-active groups is dimethylolpropionic acid. and the neutralizing base is a base selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide and tertiary amines 7. The water-dispersible, oil-modified urethane polymer according to claim 1, further characterized in that the amine salt-forming group is introduced into the prep It is smeared by a compound containing active hydrogens and active basic groups, which are rutralized by means of a neutralizing acid. 8. The water-dispersible oil-modified urethane polymer according to claim 7, further characterized in that the amine salt-forming group is selected from the group consisting of aliphatic, cycloaliphatic, aminoalcohols, diols and triols. aromatic and heterocyclic; amines, diamines, triamines and amides. 9.- The urethane polymer modified with oil, The composition according to claim 7, further characterized in that the neutralizing acid is selected from the group consisting of hydrochloric acid, acetic acid, phosphoric acid, glycolic acid and lactic acid. 10. The water-dispersible, oil-modified urethane polymer according to claim 1, further characterized in that ethylenic unsaturation is provided by means of an ester polyol prepared by reaction of aromatic or aliphatic '/' polyol containing at least two hydroxyl groups per molecule, with a fatty acid wherein a portion of the fatty acid is unsaturated 11.- The oil-modified urethane polymer, water-dispersible, according to claim 10, further characterized in that the polyol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, Bisphenol fl, trimethylolpropane, pentaerythritol, glycerin, neopentyl glycol and Iclohexanedimethanol, and mixtures thereof. 12. The water-dispersible, oil-modified urethane polymer according to claim 1, further characterized in that ethylenic unsaturation is provided by means of an ester polyol formed by the transesterification of a drying or semi-drying oil with a Aromatic or aliphatic polyol containing at least two hydroxyl groups per molecule. 13. The water-dispersible, oil-modified urethane polymer according to claim 12, further characterized in that the polyol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3 -butylene glycol, 1,4-butanediol, bisphenol fl, trimethylolpropane, pentaerythritol, glycerin, neopentyl glycol and cyclohexanedirithanol, as well as their mixtures. 14. The water-dispersible, oil-modified urea-retained polymer according to claim 12, further characterized in that the oil is selected from the group consisting of linseed oil, soybean oil, safflower oil, first grade oil, and distillation, sunflower oil, dehydrated castor oil, tunga oil, sardine oil, olive oil and cottonseed oil. 15. The oil-modified urethane polymer, water-dispersible, according to claim 10, further characterized in that the saturated fatty acid is selected from the group consisting of linoleic, imitoleic, linolenic, eleostearic, arachidonic and ricinoleic acids. 16. The water-dispersible, oil-modified urethane polymer according to claim 1, further characterized in that the prepolymer includes an additional polyol selected from the group consisting of polycarbonate, polyether and acrylic polyester polyols. 17. The urethane polymer modified with oil, water soluble, according to claim 16, further characterized in that the additional polyol is a polyol of neopentyl glycol-l, 6-hexane-diol-adipic acid which has a hydroxyl value of 120. 18.- A usual wear and rub resistant composition, characterized in that it comprises a urethane composition dispersed in an aqueous medium containing a prepolymer containing an organic polyisocyanate, acid or amine salt forming groups. , ethylenic unsaturation, v '^ e results from the reaction of the prepolymer with an unsaturated ester polyol and an active hydrogen-containing compound having an active hydrogen functionality of two or more; wherein at least 20% of the prepolymer has its extended chain with an active hydrogen-containing compound having active hydrogen functionality of four or more; and a promoter that promotes entanglement by air oxidation of the ethylenic unsaturation of the urethane composition. 19.- The usual sega-resistant and rub-resistant coating composition according to claim 18, further characterized in that the compound containing the active hydrogen, having active hydrogen functionality of four or more, is triethylenetetranoline, tripropylenetetramine or tetraethylenepentanine. . 20. ~ The usual wear and rub resistant coating composition according to claim 18, further characterized in that the acid salt setter is introduced into the prepolymer by a compound containing active hydrogen and neutralized active acid groups by medium of a neutralizing base. 21. The usual wear-resistant and rubbing coating composition according to claim 20, further characterized in that the compound containing active hydrogen and active acid groups is selected from the group consisting of hydroxy- and mercapto-acidic acids. aminocarboxylic acids, arninohydroxycarboxylic acids, sulfonic acids, hydroxysulphonic acids and aminosulphonic acids. 22. The usual and rubbing resistant coating composition according to claim 20, further characterized in that the compound having active hydrogen and active acid groups is dirnethylolpropionic acid and the neutralizing base is a base selected from the group consisting of of sodium hydroxide, potassium dioxide, ammonium hydroxide and tertiary amines. 23. The usual and rubbing resistant coating composition according to claim 18, further characterized in that the amine salt-forming group is introduced into the prepolymer by a compound containing active hydrogens and active basic groups neutralized by medium of a neutralizing acid. 24. The coating composition resistant to the usual rubbing and rubbing, in accordance with claim 23, further characterized in that the amine salt-forming group is selected from the group consisting of aliphatic, cycloaliphatic aminoalcohols, diols and triols. , aromatic and heterocyclic, amines, diarrins, triaminae and amides 25.- The usual wear-resistant and rubbing coating composition, according to claim 23, further characterized in that the neutralizing group is selected from the group consisting of hydrochloric acid, acetic acid, phosphoric acid, glycolic acid and lactic acid 26.- The usual wear-resistant and rubbing coating composition, according to claim 18, further characterized in that ethylenic unsaturation is provided by means of a polyol of ester prepared by the reaction of an aromatic or aliphatic polyol containing at least two hydroxyl groups per .alpha., with a fatty acid wherein a portion of the fatty acid is unsaturated. 27. The usual wear-resistant and rubbing coating composition according to claim 26, further characterized in that the polyol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, bisphenol fl, trimethylolpropane, pentaerythritol, glycerin, neopentyl glycol, and .clohexanedimethanol, and mixtures thereof. 28. The usual wear-resistant and rubbing coating composition according to claim 18, further characterized in that ethylenic unsaturation is provided by transesterification of a drying or semi-drying oil with an aromatic or aliphatic polyol containing at least two hydroxyl groups per molecule. 29.- The coating composition resistant to tí ** "usual wear and rubbing, according to claim 28, further characterized in that the polyol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-pro-anodiol, 1,3-butylene glycol, 1,4-butanediol, bisphenol 0, trimethylolpropane, pentaerythritol, glycerin, neopentyl, licol and cyclohexanedimethanol, as well as their mixtures. 30.- The usual wear-resistant and rubbing coating composition, according to claim 26, further characterized in that the fatty part of the group consisting of linoleic, palrnitoleic, linolenic, eleostearic, arachidonic and ricinoleic acids is selected. . 31.- The usual wear-resistant and rubbing coating composition according to claim 28, further characterized in that the oil is selected from the group consisting of linseed oil, soybean oil, safflower oil, first distillation oil , sunflower oil, dehydrated castor oil, tunga oil, sardine oil, olive oil and cottonseed oil. 32. The usual wear-resistant and rubbing coating composition according to claim 18, further characterized in that the prepolymer includes an additional polyol selected from the group consisting of polyester, polycarbonate, polyether and acrylic polyols. 33. - The usual wear-resistant and rubbing coating composition according to claim 32, further characterized in that the additional polyol is a polyol of neopentyl glycol-6-hexanediol-adipic acid having a hydroxyl value of 120. 34. - A method for forming an oil-modified urethane polymer, dispersible with water, resistant to usual wear and rubbing, characterized in that said method comprises the steps of: (a) forming a prepolymer having isocyanate groups, salt forming groups of acid or amine and ethylenic unsaturation resulting from the reaction of the prepolymer with an unsaturated ester polyol; (b) neutralizing the acid or amine salt of the prepolymer formed in step (a); (c) dispersing the neutralized prepolymer in an aqueous medium; and (d) extending the chain of the dispersed prepolymer with an active hydrogen-containing compound, having an active hydrogen functionality with the proviso that at least 20% of the chain extension is carried out with a compound containing active hydrogen having an active hydrogen functionality of four or more. 35. The method according to claim 34, further characterized in that the active hydrogen-containing compound having a hydrogen functionality of four or more is tpetilentetran, tripropylenetetramine or tetraethylenepentaarnine. 36.- The method of compliance with the claim 34, further characterized in that the isocyanate group is derived from the group consisting of 1,4-tetrarnetylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylene diisocyanate. , 1,4-cyclohexylene diisocyanate, 4,4'-methylenebis (isocyanatocyclohexane), l-oocyanato-3-ocyanatomethyl-3,5,5-trimethyl-cyclohexane, rn ~ diisocyanate and p-phenylene, diisocyanate of 2, 6- and 2,4-tolylene, xylene diisocyanate, 4-chloro-l, 3-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-methylene diphenylisocyanate, 1,5-naphthylene diisocyanate , 1,5-tetrahydronaphthylene diisocyanate and polymethylene polyphenylisocyanates. 37.- The method according to the claim 34, further characterized in that the salt forming group of , "" "" "is then introduced into the prepolymer by a compound containing active hydrogen and active acid groups neutralized by a neutralizing base. 38. The method according to claim 37, further characterized in that the compound containing active hydrogen and acidic active groups is selected from the group consisting of hydroxy- and rcaptocarboxylic acids, arninocarboxylic acids, aminohydroxycarboxylic acids, sulfonic acids, acids hydroxysulfonic and aminosulphonic acids. 39. The method according to claim 37, further characterized in that the compound having active hydrogen and active acid groups is dirnethylolpropionic acid and the neutralizing base is a base selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide and tertiary amines. 40.- The method of compliance with the claim 34, further characterized in that the amine salt-forming group is introduced into the prepolymer by a compound .e contains active hydrogens and active basic groups neutralized by means of a neutralizing acid. 41. ™ The method according to the claim 40, further characterized in that the amine salt-forming group is selected from the group consisting of alcohols, diols and triols, aliphatic, cycloaliphatic, aromatic and heterocyclic; amines, diamines, triamines and amides. 42. ™ The method according to the claim Also characterized in that the neutralizing acid is selected from the group consisting of hydrochloric acid, acetic acid, phosphoric acid, glycolic acid and lactic acid. 43. ™ The method according to claim 32, further characterized in that steps (b) and (d) are effected substantially simultaneously.