MXPA00011524A - Polymeric compositions for soil release on fabrics - Google Patents

Abstract

A copolymer composition and its use as a soil release agent for fabrics comprising monomers copolymerized in the following percentages by weight:(a) from about 30%to about 49%of at least one monomer of formula (I):Rf-Q-A-C(O)-C(R)=CH2, wherein Rf is a straight or branched-chain perfluoroalkyl group of from 2 to about 20 carbon atoms, R is H or CH3, A is O, S or N(R'), wherein R'is H or an alkyl from 1 to about 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, -(CnH2n)(OCqH2q)m-, -SO2-NR'(CnH2n)-, or -CONR'(CnH2n)-, wherein R'is H or an alkyl of from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;(b) from about 10%to about 70%of at least one monomer or a mixture of monomers selected from the formulae (IIA):(R1)2N-(CH2)r-Z-C(O)-C(R2)=CH2, (IIB):(O)(R3)(R4)N-(CH2)r-Z-C(O)-C(R2)=CH2, (IIC):X-(R5)(R4)(R3)N+-(CH2)r-Z-C(O)-C(R2)=CH2, wherein Z is -O- or -NR5-;R1 is an alkyl group of from 1 to about 3 carbon atoms;R2 is H or an alkyl radical of 1 to about 4 carbon atoms;R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a morpholine, pyrrolidine, or piperadine ring;R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring;r is 2 to 4;and wherein for formula (IIA) the nitrogen is from about 40%to 100%salinized;and (c) eventually other monomers.

Description

POLYMERIC COMPOSITIONS FOR THE RELEASE OF DIRT IN CLOTHES FIELD OF THE INVENTION This invention relates to fluorochemical copolymers and their application to fabrics and fabric mixtures for transmitting dirt release properties.

BACKGROUND OF THE INVENTION The fouling of the fabrics, always a problem with the textile products, came to be even more than a problem with the appearance of fabrics with permanent impressions composed of mixtures of cotton-synthetic fibers. These were treated with various additives, which often make them more difficult to clean. In addition, fabrics with permanent impressions are better washed at low temperatures and with gentle agitation, while fouling is better removed at higher temperatures and with vigorous agitation. For these reasons, the various agents for the release of dirt are frequently applied to these fabrics to aid in the REF: 124451 removal of dirt during washing. Preferably, these soil release agents do not remove themselves during washing (ie, are durable), and either improve or do not damage other properties of the fabric. Fluorochemical products, despite their comparatively high cost, are probably the most widely used dirt release agents in cellulosic fabrics due to their performance in low concentrations, their compatibility with permanent printing finishes, and their exemption from most of undesirable side effects. Without. However, these agents also tend to affect the hydrophilicity and oleophobicity (i.e., water and oil repellency) of the fabrics in ways that may be desirable for some applications but undesirable for others. For example, hydrophilic soil release agents are useful for maintaining the desired capillary absorbency of skin moisture provided by the fabrics, but such hydrophilicity may not be desirable for some other applications such as outer clothing. The balance of these characteristics to achieve the desired properties for certain applications while maintaining good dirt release properties is often difficult. A widely used class of fluorochemical products for the release of dirt is composed of perfluorinated urethanes containing portions of polyethylene oxide. Such urethanes and their intermediate isocyanates are expensive and potentially dangerous for their manufacture. Urethane-type products are often repellent as well as dirt-releasing, and thus reduce the comfort of the use of cotton or similar garments. These existing products are difficult to modify when it is desired to increase the degree of hydrophilicity of the fabric for a particular application. Fluorochemical products which are not based on urethane have been used for oil and water repellency in the paper industry. U.S. Patent No. 5,674,961 to Fitzgerald discloses a class of fluorochemical copolymers useful for improving the paper's resistance to water, oil and grease. No information in this patent suggests that this copolymer could be useful as an agent for the release of dirt, a completely different type of application than greaseproof paper. U.S. Patent No. 4,147.85]. from Raynolds teaches fluorochemical copolymers useful for oil and water repellency applications for paper and fabrics. Again, there is no suggestion that these copolymers are useful as an agent for the release of dirt. Fluorochemical products for the release of dirt which are as effective as perfluorinated urethanes, but which do not involve expensive and potentially hazardous isocyanate / urethane chemical manufacturing processes are highly desirable and would have extended applications. Even more desirably, this agent for the release of dirt would be made by a process, which makes it easier to modify the degree of hydrophilicity of the agent and the treated fabric over a wide range to favor various applications. The present invention provides such fluorochemical products for the release of dirt.

BRIEF DESCRIPTION OF THE INVENTION The present invention comprises a copolymer composition, which transmits dirt release properties to fabrics and mixtures of; fabrics comprising copolymerized monomers in the following percentages by weight: (a) from about 30% to about 49% of at least one monomer of the formula I: Rf-Q-A-C (0) -C (R) = CH2 I wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH3, A is O, S or N (R '), wherein R' is H or an alkyl of 1 to about 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 5 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR '(CpH2n) -, where R' is H or an alkyl of 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15; (b) from about 10% to about 70% of at least one monomer or mixture of selected monomers of formula IIA, formula IIB and formula IIC: (Ri) 2N- (CH2) rZC (0) -C (R2) = CH2 HA (0) (R3) (R4) N- (CH2) rZC (0) -C (R2) = CH2 IIB X "(Rs) ) (R) (R3) N + - (CH2) rZC (0) -C (R2) = CH2 IIC wherein Z is -0- or -NR5-; Ri is an alkyl group of 1 to about 3 carbon atoms; R2 is H or an alkyl radical of 1 to about 4 carbon atoms; R3 and R are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a ring of morpholine, pyrrolidine, or piperadine; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for the formula HA the nitrogen is from about 40% to 100% salinized; Y, (c) from 0% to about 7% of a monomer of formula III, IV, V or VI or a mixture thereof: o / \ CH2-CH-CH2-stC (O) - (R2) = CH2 III Cl-CH2-CH (OH) CH2-0-C (0) -C (R2) = CH2 IV; (R6) OC (0) C (R6) = C -2 V; or CH2 = CC12 VI wherein each R2 is independently H or a radical of; alkyl of 1 to about 4 carbon atoms and each Re is independently H or an alkyl of 1 to about 8 carbon atoms. The present invention further comprises a method for treating fabrics and fabric blends for transmitting dirt release properties comprising applying to the surface of the mixed fabric or fabric an effective amount of the copolymer composition comprising copolymerized monomers in the following Percentages by weight: (a) from approximately 30% to approximately 90% of at least one monomer of formula I: Rf-Q-A-C (0) -C (R) = CH2 I wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH3, A is O, S or N (R '), wherein R' is H or an alkyl of 1 to about 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR '(CnH2n) -, where R' is H or an alkyl of 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15; (b) from about 10% to about 70% of at least one monomer or mixture of monomers selected from the formula HA, formula IIB and formula IIC: (R?) 2N- (CH2) rZC (O) -C (R2) = CH2 HA (O) (R3) (R4) N- (CH2) rZC (0) -C (R2) = CH2 HB X "( R5) (R4) (R3) N + - (CH2) rZC (0) -C (R2) = CH2 IIC wherein Z is -O- or -NR5-; Ri is an alkyl group of 1 to about 3 carbon atoms; R2 is H or an alkyl radical of 1 to about 4 carbon atoms; R3 and R are each an alkyl of 1 to 4 atom: carbon, hydroxyethyl, benzyl, or R3 and R3 together with the nitrogen atom form a ring of morpholine, pyrrolidine, or piperadine; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R1, together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for the formula HA the nitrogen is from about 40% to 100% salinized; Y, (c) from 0% to about 7% of a monomer of formula III, IV or a mixture thereof: O / \ CH2-CH-CH2-0-C (O) - (R2) = CH2 III Cl-CH2-CH (OH ') CH2-0-C (0) -C (R2) = CH2 IV; (R6) OC (0) C (R6) = CH2 V; CH2 = CC12 VI wherein each R2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R6 is independently H or an alkyl of 1 to about 8 carbon atoms. The present invention further comprises a fabric or a mixture of fabrics which has been treated according to the method of the present invention as described above. The treated fabric or mixture of fabrics has a fluorine content of from about 0.05% to about 0.5% by weight.

DETAILED DESCRIPTION OF THE INVENTION This invention comprises copolymers. fluorochemicals, improved useful for transmitting dirt release properties to fabrics or blends. By "fabrics" is meant natural or synthetic fabrics composed of fibers of cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon and aramides such as "NOMEX" and "KEVLAR". By "fabric blends" is meant a fabric made of two or more types of fibers. Typically, these blends are a combination of a natural fiber and a synthetic fiber, but may also include a mixture of two natural fibers or two synthetic fibers. Trademarks and trade names are indicated herein by the use of capital letters. The superior dirt release properties, together with the desirable properties of repellency and wicking absorbency can be transmitted to fabrics and fabric blends by the addition of certain fluorochemical copolymers. These can be applied to the fabric in the form of a self-dispersed emulsion or dispersion in water or another solvent either before, after or during the application of other chemical products for the treatment of fabrics. Highly efficient copolymers, useful for this purpose, are characterized in that they contain copolymerized comonomers in the following percentages by weight, relative to the total weight of the copolymers: (a) from about 30% to about 90% of at least one monomer of formula I: Rf-QAC (O) -C (R) = CH2 I wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH3, A is O, S or N (R '), wherein R' is H or an alkyl of 1 to about 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, - (CnH2n) (OCqH2q) p-, -S02-NR '(CnH2n) -, or -CONR' (CnH2n) -, where R 'is H or an alkyl: from 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15; (b) from about 10% to about 70% of at least one monomer or mixture of monomers selected from the formula HA, the formula HB and the formula HC: (R?) 2N- (CH2) rZC (O) -C (R2) = CH2 HA (O) (R3) (R4) N- (CH2) rZC (0) -C (R2) = CH2 IIB X "( R) (R ") (R3) N + - (CH2) rZC (O) -C (R2) = CH2 IIC wherein Z is -0- or -NR5-; Ri is an alkyl group of 1 to about 3 carbon atoms; carbon, R2 is H or an alkyl radical of 1 to about 4 carbon atoms, R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a ring of morpholine, pyrrolidine, or piperadine, R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R and R5 together with the nitrogen atom form a pyridine ring, r is 2 to 4; where for the formula HA the nitrogen is about 40% to 100% salinized; (c) from 0% to about 7% of a monomer of formula III, IV, V or VI, or a mixture thereof: 0 / \ CH2-CH-CH2-O-C (O) - (R2) = CH2 III Cl-CH2-CH (0H) CH2-0-C (0) -C (R2) = CH2 IV; (R6) 0C (0) C (R6) = CH2 V; or CH2 = CC12 VI wherein each R2 is independently H or an alkyl radical of 1 to about 4 carbon atoms, and each R is independently H or an alkyl of 1 to about 8 carbon atoms. Preferably, the monomer of the formula I is a perfluoroalkylethyl acrylate. In more preferably, the length distribution of carbon chain perfluoroalkyl weight is ce about 50% of 8-carbon, about 29% of 10-carbon, about 11% of 12 carbons and with smaller percentages of 6 carbon, 14-carbon and longer chain lengths. The proportion of monomer (a) of formula I is at least about 30% relative to the total weight of the copolymer. If present in lower amounts, the polymer becomes more hydrophilic and the oleorescence drops to an undesirable level. In the method and the treated fabric or the mixture of fabrics of the present invention, the monomer portion (a) of the formula I is less than about 90%. If present in higher amounts, the amounts of the solubilizing monomer (b) of the formula HA and / or HB will be too low, which results in poor dispersibility. In the copolymer composition of the present invention, the proportion of the monomer (a) of the formula I in the copolymer is between about 30% and about 49% by weight. This last interval is preferred for the best balance of dirt release, hydrophilicity and oleophobicity in the currently anticipated applications of the treatment of; fabrics and fabric mixtures. More preferably, the proportion of monomer (a) of formula I in the copolymer is between about 30% about 45% by weight. Other proportions may be more desirable for other applications. In fact, one of the main advantages of the inventive composition is that its hydrophilic and oleophobic properties can be varied over a wide range for different applications by simply varying the relative amounts of the monomers (a) of the formula I and (b) of the formula HA and / or HB, while still maintaining its properties as an agent for the release of dirt, effective. That is, the copolymer is modified to make the treated fabric more oleophobic and water repellent by increasing the proportion of the monomer (a) of the formula I within the above range, or is modified to make the treated fabric more hydrophilic (to provide due to that the absorbency by capillarity) by increasing the proportion of the monomer (b) of the formula HA and / or HB. This flexibility has not been found possible with the most expensive, existing dirt release agents. Preferably, the monomer (b) of the formula HA is derived from diethylaminoethyl methacrylate by partial or complete salinization. The free amine portions of the resulting copolymer are then reacted with a salting agent such as acetic acid, which results in the conversion of part or all of the amine portions to the corresponding acetate. This should be at least about 40% salinized by an adequate solubilization effect, but can be as high as 100% Preferably, the degree of salinization is between about 50% and about 100%. Alternatively, the salination reaction is carried out in the amine group before the polymerization reaction with equally good results. The salinization group is an acetate, halide, sulfate, tartarate or other known salinization group. The proportion of monomer (b) in the formula HA, HB, HC or a mixture thereof must be at least about 10% for adequate solubilization. While a copolymer with the proportions of this monomer (b) above about 70% can be satisfactory in the dirt release properties, a proportion of this kind will produce polymers with very high viscosity, which makes the process and handling difficult. . Preferably, the proportion of the monomer (b) of the formula HA, HB, HC or a mixture thereof in the copolymer is between about 50% and about 65% by weight for the best balance of the dirt release, the hydrophilicity, oleophobicity and viscosity in the applications currently planned. Other proportions may be more desirable for other applications. All percentages by weight are based on the weight of the quaternized monomer. The amine oxide monomers of formula HB have the formula (O) (R3) (R4) N- (CH2) r-Z-C (O) -C (R) = CH2 as described above wherein NR3R (0) represents -N + -R3 0- These are prepared by reacting the aforementioned acrylate or methacrylate ester or the corresponding acrylamide or methacrylamide with conventional oxidation agents such as hydrogen peroxide or peracetic acid. The quaternary ammonium monomers of the formula HC are prepared by reacting the esters of acrylate or methacrylate or the corresponding acrylamide or methacrylamide with a di- (lower alkyl) sulfate, a lower alkyl halide, trimethyl phosphate or triethyl phosphate. Dimethylcryl sulfate and diethyl sulfate are the preferred quaternizing agents. The presence of the monomer (c) of the formula III, IV, V or VI is optional, depending on the particular application for the copolymer. While there are some applications for which it is not necessary, for most of the currently planned applications it is present to achieve a satisfactory bond to the fibers. While not wishing to be bound by this theory, it is believed that monomer (c) of formula III and IV acts as a reactive site for the polymer to be covalently bound to the surface of the substrate. The monomers V and VI can be incorporated to improve the compatability of the copolymer with the substrate of the fabric. To have a noticeable effect on this property, it must be present in a proportion of at least about 1%. An amount above about 7% is unnecessary and can not further improve this performance. Preferably, for many applications, the proportion of monomer (c) of formula III, IV, V or VI in the copolymer is from about 1% to about 5% by weight. Preferably, (c) is glycidyl methacrylate. The monomers of formula III, IV, V and VI are prepared by conventional methods known in the art. The polymerization of the comonomers (a), (b) and (c) is carried out in a solvent such as acetone, methyl isobutyl ketone, ethyl acetate, isopropanol and other ketones, esters and alcohols. Polymerization is conveniently initiated by azo inhibitors such as 2,2'-azobis (2,4-dimethylvaleronitrile). These initiators are sold by E.l. du Pont de Nemours and Company, Wilmington, Delaware, commercially under the name of "VAZO" 67, 52 and 64 and by Wako Puré Industries Ltd. Richmond, Virginia, under the name "V-501". The present invention further comprises a method for treating fabrics or blends of fabrics comprising the application to the surface of the fabric or fabric mixture of an effective amount of a copolymer as described above. The copolymers are applied to the fabric or the mixed fabric to be treated with aqueous dispersions, either alone or in a mixture with other agents for the treatment of textiles or aprestos. Dispersions are generally applied to fabrics by spraying, immersion treatment, mordant impregnation, or other well-known methods. After the excess liquid has been removed, for example by squeezing cylinders, the treated fabric is dried and then cured by heating, for example at 100 ° C to 190 ° C, for at least 30 seconds, typically 60- 180 seconds Such a cure increases the release of dirt and the durability of the release of dirt. While these healing conditions are typical, some commercial apparatus may operate outside these ranges due to their specific design characteristics. The present invention also comprises a fabric or a mixture of fabrics which has been treated to transmit the dirt release properties thereto by applying an effective amount of a copolymer as described above. The treated fabric has a fluorine content of from about 0.05% to about 0.5% by weight. The treated fabric has superior soil release properties along with desired properties of repellency and capillarity absorbency. The copolymers and the method of the present invention are useful for increasing the release of dirt from fabrics or fabric blends during washing. The dirt release property is durable, and is specifically effective for fabric blends with permanent prints. The fabrics and blends of treated fabrics of the present invention are useful in a variety of applications such as for textiles, clothing, accessories and the like. The copolymers of the present invention are advantageous in that they are safer to manufacture than the isocyanate-type copolymer, and that it is easy to adjust the degree of hydrophilicity of the copolymer and the cloth or mixture of fabrics treated over a wide range by modifying The level of the monomers of formulas I against HA and HB allows a variety of end-use applications. The inventive compositions are made at a lower material cost than isocyanate-based soil release agents, in part because the gas / liquid reactions required to make phosgene and isocyanates are eliminated.

TEST METHODS The following tests were used in the evaluation of the examples herein.

Dirt release The copolymer materials were subjected to a test as a soil release agent as described in AATCC 130-1981, designed to measure the ability of a fabric to release oily stains during a typical household wash. In this method, an oily spot is produced in a test sample or specimen by using a weight to force a given amount of stain into the fabric. The dirty fabric is washed, and the residual stain is compared on a scale of 1 to 5 using a standard soil release model. The number '5 represents the most effective dirt release properties and the number 1 the least. The intermediate values are assigned between 1 and 5. Specifically, the tests were carried out as follows. Five drops of an oily, specific soiling agent are placed in the approximate center of a fabric test sample. Then a square of glass paper is placed on the cloth, covering the puddle, followed by a weight of 2.3 kg (5 Ib) on the paper crj¡rétal. This is allowed to settle for 60 seconds, then the weight and the glass L is removed. The test sample is then washed within 15 to 60 minutes at a temperature of 41 ° C using 140 grams of "Tide" detergent available from Procter and Gamble Company, Cincinnati, Ohio, in a standard washing machine, along with the ballast of the Test sample to make a total weight of 1.8 kg, during a period of 12 minutes. The full load of the sample washer and the ballast is then placed in a dryer and dried at a maximum air outlet temperature of 70 ° C for 45 minutes. The test samples, dried then judged in comparison with the normal scale as described above.

Water repellency The water repellency of a treated substrate was measured according to the DuPont technical Laboratory Method as summarized in the Teflon ® Global Specifications and Quality Control Tests information package. The test determines the resistance of a treated substrate to wetting by aqueous liquids. Droplets of alcohol-water mixtures of surface tensions, variants on the fabric and the degree of wetting of the surface are visually determined. The test provides an approximate Index of resistance to aqueous stains. The higher the water repellency rating, the better. resistance of a substrate prepared to stain poi substances based on water. The composition of normal test liquids is shown in the following table.

Table 1 Oleorescence The treated fabric samples were subjected to an oil-repellency test by a modification of AATCC Standard Test Method No. 118, conducted as follows. A fabric sample, treated with an aqueous dispersion of a polymer previously described, is conditioned for a minimum of 2 hours; at 23 ° C + 20% relative humidity and 65 ° C + 10% relative humidity. A series of organic liquids, identified later in Table I, were then applied dropwise to the samples of the fabric. Starting with the test liquid of the lowest number (Repellence Rating No. 1), one drop (approximately 5 mm in diameter or 0.05 mL volume) is placed in each of three separate locations at least 5 mm. The drops were observed for 30 seconds. If, at the end of this period, two of the three drops are still spherical in their shape without capillarity absorbency around the drops, three drops of the next liquid of the highest number are placed at adjacent sites and are observed similarly for 30 seconds. seconds. The procedure is continued until one of the test liquids results in two of the three drops failing to remain spherical or hemispherical, or that the wetting and absorbency occurs by capillarity. The evaluation of the oleorescence of the fabric is the test liquid of the highest number for which two of the three drops remained spherical to hemispherical, without absorbency by capillarity for 30 seconds. In general, fabrics treated with a rating of 5 or more are considered good to excellent; Fabrics that have a rating of one or more can be used in certain applications.

Table 1A Oleorespecific Testing Lines Note: NUJOL is a trademark of Plow, Inc., for a mineral oil that has a Saybolt viscosity of 360/390 at 38 ° C and a specific gravity of 0.880 / 0.900 at 15 ° C.

The following preparative examples were used in the evaluation of the "** properties of the fabric and the blends of the treated fabrics with the inventive copolymers and the comparative copolymers.

*** Example 1 A vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 673. 5 parts by weight of fluoromonomer (a) having the formula: CF3CF2 (CF2) xC2H4OC (O) -C (H) = CH2, where x = 6, 8, 10, 12, 14, 16 and 18 in the respective relative amounts of about 3%, 50%, 31%, 10%, 3%, 2 and 1%, the monomer having a weight average molecular weight of 569; 119.5 parts by weight of monomer (b), N, -diethylaminoethyl methacrylate; 19.0 parts by weight of the monomer (c), glycidyl methacrylate; and 505 parts by weight of methyl isobutyl ketone (MIBK). The charge was purged with nitrogen at 40 ° C for 30 minutes. Then "VAZO" 67 (0.6 parts by weight), or 2,2-azobis (2,4-dimethylvaleronitrile) available from E. I. du was added.

Pont de Nemours and Company, Wilmington, Delaware, to initiate polymerization and the batch was stirred for 16 hours at 70 ° C under nitrogen. A mixture of water (2435 parts) acetic acid (59.5 parts) was added at room temperature to the copolymer mixture, above 70 ° C. The reflux condenser was replaced with a distillation column and the MIBK was removed under reduced pressure. A total of 3103 parts of the copolymer solution was obtained. The copolymer solids (23.1%) contained 82.2% of perfluoroalkylethyl acrylate units, 15.4% of N, N-diethylaminoethyl methacrylate units and 2.4% of glycidyl methacrylate units.

Examples 2 The process of Example 1 was repeated using the same monomers and other ingredients, but in the following proportions: Monomer (a), 40.0 g; monomer (b), 57.6 g; monomer (c), 2.4 gm; "VAZO" 67, 1.6 g; MIBK, 136 g, water 387.6 g, acetic acid, 28.9 g. After the MIBK was removed, the copolymer solids contained 40.0% of perfluoroalkylethyl acrylate units, 57.6% of N, -diethylaminoethyl methacrylate units and 2.4% of glycidyl methacrylate units.

Comparative Example A This is an example of a fluorourethane with polyethylene oxide units, "ZONYL" 7910 commercially used for the purposes of soil release. ("ZONYL" 7910 is available from E.l. du Pont de Nemours and Company, Wilmingtoi, Delaware). The fabric used in the following tests was a 50% / 50% polyester / cotton fabric treated with the fluorochemical products previously described of Examples 1, 2 and Comparative Example A. The oily materials used in the following tests were Kaydol 4 ( a normal mineral oil), corn oil, and motor oil as dirt. Absorbency by capillary action (hydrophilicity) represents the time in seconds for a drop of water to be completely absorbed on the surface of the fabric. The results are shown in Table 2 below.

Table 2 Tests of Fluorochemical Products in Polyester / Al odón In the above tests, the composition of Example 2 proved to be better than that of Example 1, and almost equivalent to Comparative Example A more expensive. In the capillarity absorbance test, Example 2 showed complete absorption in 45 seconds, while for Example 1 and Comparative Example A the water drop never penetrated the fabric. The comparison of »Examples 1 and 2 show the difference in absorbency! by capillary action that can be obtained by varying the ratio of the monomers (a) and (b). In the following tests, the fluorocarbon polymer was applied to a 100% cotton fabric for trousers by a sizing print. Both baths contained a resin (Permafresh MSC available from Sequa Chemicals, Inc., Chester, South Carolina) at 16 grams / liter. The fabric samples were dried at 166 ° C for 2 minutes. After washing, the cloths were dried with a rotating drum and evaluated for oil and water repellency and dirt release (using Kaydol mineral oil 4). The number of home washes is listed in the table as LC.

Comparative Tests of Fluorochemical Products in Cotton The above results clearly showed the advantage in oil and water repellency for Example 1 against the more expensive ethoxylated isocyanate composition (Comparative Example A).

Example 3 One vessel was charged with 75.0 parts by weight of fluoromonomer (a) having the formula: CF3CF2 (CF2) xC2H4OC (0) -C (H) = CH2, wherein x = 6, 8, 10, 12, 14, 16 and 18 in the respective relative amounts of about 3%, 50%, 31%, 10%, 3%, 2% and 1%, the monomer having a weight average molecular weight of 569; 25.0 parts by weight of N, N-diethylaminoethyl methacrylate; 2.5 parts by weight of glycidyl methacrylate and 100.0 parts by weight of isopropyl alcohol. The charge was purged with nitrogen for 30 minutes at 45 ° C. Then "VAZO" 67 (1.4 parts) was added as in Example 1 to initiate the polymerization and the batch was stirred at 65 ° C for 16 hours. Paracetic acid (32.0 parts, 32% in acetic acid available from Aldrich Chemical Co., Milwaukee, Wl) was added over a period of about 1 hour while the temperature was maintained at about 70 ° C. The mixture was maintained at 70 ° C for an additional hour after the addition of the peracetic acid was complete.

Example 4 A mixture of 70 parts by weight of the fluoromonomer CF3CF2 (CF2) sC2H402CC (CH3) = CH2, wherein s = 2, 4, 6, 8, 10 and 12 and 30 parts by weight of the methacrylate monomer of N, N-diethylaminoethyl (DEAM) was polymerized at 80 ° C at 83 ° C, in 43 parts by weight of methyl isobutyl ketone as the solvent, using 0.5 parts by weight of azobis (isobutyronitrile) as an initiator.

The DEAM units were functionalized after the polymerization by conversion to any amine acetate or amine oxide salt or a mixture thereof. The functionalization of DEAM was carried out by heating (50 ° C to 60 ° C) the copolymer dispersion with at least the equivalent amounts of acetic acid, sulfuric acid, 30% hydrogen peroxide, 40% peracetic acid or mixtures thereof in a Aqueous solvent of methyl isobutyl ketone. The solvent is; distilled under reduced pressure. The resulting non-volatile solids content of the copolymer solution was determined by drying a sample of 0.4 to 0.6 parts for 2 hours at 110 ° in a vacuum oven at 20-22 Hg inlets. The copolymer solids were 23.6%. The following samples were then applied to a blend of 65% white polyester / 35% cotton and 100% cotton in equal fluoride loads on the fabrics. All the baths contained a permanent Permafresh 113B printing resin available from Segua Chemicals Inc., Chester, South Carolina, and the catalyst at about 30 g / L and acetic acid at 1 g / L. The cloth was dried and cured by heating at 193 ° C (390 ° F) for 3 minutes. Oleorescence, water repellency and dirt release (Kaydol mineral oil) were determined as previously described. The capillary absorbency performance in this experiment was not evaluated.

Table 4 Example 5-6 The process of Example 1 was repeated using the following components. Monomer (a) in these examples had the formula CF3CF2 (CF2) xC2HOC (O) -C (CH3) = CH2, where x = 2, 4, 6, 8, 10, and 12, in the relative amounts, respectively of about 3%, 35%, 30%, 17%, 8% and 6%, the monomer having a weight average molecular weight of 543 available from EI du Pont de Nemours and Co. , Wilmington, DE, as "ZONYL" TM; The monomer (b) for Example 5 was methyl chloride salt of N, N-dimethylaminoethyl methacrylate (70% aqueous solution), and monomer (b) for Example 6 was methyl methacrylate sulfate. of N, N-dimethylaminoethyl. Both monomers are available from Monomer-Polymer & Dajac Laboratories, Inc. of Trevose Pennsylvania. In Examples 5 and 6 component (a) was present in 70% by weight and component (b) was present in 30% by weight. "VAZO" 67 was used, (0.5 g) as described in Example 1, as the initiator of the polymerization and the solvent used in both cases was isopropyl alcohol (60 g). After heating at 60 ° C for 3 hours, water (470 g) was added and the polymeric material was dispersed with stirring. Isopropanol was not eliminated in these examples. Examples 5 and 6 were applied to a twill or 100% cotton weave fabric and to a 65% / 35% cotton polyester fabric as previously described at 35 g / L and 31 g / L respectively with 80 g / L Permafresh MSC permanent printing resin available from Segua Chemicals Inc., Chester, South Carolina. The fabrics were cured at 166 ° C (330 ° F) for two minutes and the fabrics were evaluated for dirt release and repellency to oil and water initially and after washing as previously described. The results are shown in Table 5. LC indicates the number of home washes.

As can be seen from Example 5 and 6 (compared to Example 1 for 100% cotton fabric), the dirt release properties were transmitted to the fabrics without providing a high level of repellency (Example 6) or in no repellence at all (Example 5).

Examples 7-13 The process of Example 5 was repeated using the copolymer composition as described in Table 6. Monomer (a) in these examples had the formula CF3CF2 (CF2) xC2H4OC (0) -C (CH3) = CH2, where x = 3, 4, 6, £, 10 and 12, in the relative amounts, respectively, of about 3%, 35%, 30%, 17%, 8% and 6%, the monomezo having a weight average molecular weight of 543 available from EI du Pont de Nemours and Co., Wilmington, DE, as "ZONYL" TM. In Example 13, 2- (N) -ethylperfluorooctanesulfonamide, available from "FLUORAD" FX-14 of the Minnesota Mining and Manufacturing Co., Minneapolis, MN, was used. Monomer (b) was N, N-diethylaminoethyl methacrylate (DEAM) and monomer (c) was as described in Table 6. "VAZO" 67 was used, as described in Example 1, as the initiator of the polymerization and the solvent used in both cases was isopropyl alcohol.

Table 6 * N, N-diethylaminoethyl methacrylate After the polymerization as described in Example 5, water (470 g) and acetic acid (1 molar equivalent to monomer b) were added and the polymeric material was dispersed with stirring. In the cases of Examples 7-11, various types and amounts of the monomer (c) are shown. In the case of Example 121, 1 molar equivalent of tartaric acid was used to form the salt of the amine portions of the monomer (b). Isopropanol was also eliminated in these examples. Examples 7-13 were applied to the fabrics and subjected to a test for oil repellency; and to water and dirt release as described in Example 5-6. The results are shown in Table 7. LC indicates the number of home washes.

Examples 14-16 The process of Example 5 was repeated using the copolymer compositions described in Table 8. The monomer (a) in, these examples had the formula CF3CF2 (CF2) xC2HOC (O) -C (CH3) = CH2, where x = 2 , 4, 6, 8, 10 and 12, in the respective relative amounts of about 3%, 35%, 30%, 17%, 8% and 6%, the monomer having a weight average molecular weight of 543 available from EI du Pont de Nemours and Co., Wilmington, DE, as "ZONYL" TM; monomer (b) for Examples 14-16 was N, N-diethylaminoethyl methacrylate (DEAM). Monomer (c) was not used in these examples. "VAZO" 67 was used, as described in Example 1, as the initiator of the polymerization and the solvent used in Examples 14-16 was isopropyl alcohol.

Table 8 After the polymerization as described in Example 5, peracetic acid or hydrogen peroxide (both available from Aldrich Chemical Co., Mil aukee, Wl, 1 molar equivalent to monomers b) was cautiously added and heated for 1 hour. Then water was added and the polymeric material dispersed with agitation. Isopropanol was not separated in these examples either. Examples 14-16 were applied to the fabrics as in Example 5, and were subjected to a test for oil and water repellency and soil release as previously described. The results are. shown in Table 9. LC indicates the number of washes; homemade Table 9: Comparative Tests on Alkodon and Polyester Alkodon Example 17-21 The process of Example 14 was repeated using the copolymer compositions described in Table 10. Component (a) had the formula CF3CF2 (CF2) xC2H4OC (O) -C (H) = CH2, where x = 4, 6, 8, 10 and 12+ in the respective relative amounts of about 3%, 50%, 29%, 11% and 7%, the monomer having a weight average molecular weight of 543, available "ZONYL" TA-N from He DuPont de Nemours and Co., Wilmington, DE; component (b) for Example 17 was N, N-diisopropylethylaminoethyl methacrylate (DIPAM); Component (c) was glycidyl methacrylate (GMA). For Examples 18-21, component (b) was N, N-diethylaminoethyl methacrylate (DEAM). For Example 18, component (c) was chlorohydroxypropyl methacrylate (CHPM). For Examples 19-21, component (c) was glycidyl methacrylate (GMA). "VAZO" 67 was used, as described in Example 1, as the initiator of the polymerization and the solvent used in both cases was isopropyl alcohol. After the polymerization as described in Example 5, peracetic acid (available from Aldrich Chemical Co., Milwaukee, Wl; 1 molar equivalent to component b) was cautiously added and heated for 1 hour. Then water was added and the polymeric material dispersed with agitation. Isopropanol was not separated in these examples either. Examples 17-21 were applied to the fabrics as in Example 5 and subjected to a test for oil and water repellency and soil release as previously described. The results are shown in Table 11. LC indicates the number of home washes.

Table 10 Monomer a Monomer b Monomer b Monomer c Zonyl salt TAN DEAM GMA = glycidyl methacrylate. CHPM = chlorohydroxypropyl methacrylate DIPAM = N, N-diisopropyl aminoethyl methacrylate For Example 7, a monomer containing amine (DIPAM) was used which showed that the performance as a dirt / repellent release is general for this component. Example 18 showed the utility of 2-chorohydroxypropyl methacrylate and its effect on the durability of oil and water repellency. Examples 19-21 showed the effects of a range of relationships from Component (a) to Component (b). Example 19 had the highest ratio of Component (a) to component (b) and also had the most durable oil and water repellency and the highest stain release performance.

Example 22 In a Warring mixing machine the following materials were combined; "ZONYL" TM, as described in Examples 14-16 (70.0 parts); methyl chloride salt of N, N-diethylaminoeti methacrylate (30.0 parts); the cationic amine N, N-dimethyloctadecyl surfactant (10.0 parts); and acetic acid (1.0 parts). The mixture was combined for 30 seconds then microfluidized by 2 steps at 4.14 x 107 Pa (6,000 psi). A vessel equipped with a stirred :: thermometer, and the reflux condenser was charged with the resulting emulsion and purged with nitrogen for 30 minutes. Azobis isobutyramidine hydrochloride (V-50, 0.5 g) available from Wako Chemical, Richmond, Virginia, in water (10.0 g) was then added to initiate the polymerization and the batch was stirred for 10 hours at 60 ° C under nitrogen. The resulting emulsion was applied to the 100% cotton twill fabric and cured as described in Example 5. The results are shown in Table 12. LC indicates the number of household washes.

Table 12: Comparative Tests on Cotton and Polyester cotton 100% cotton Repellency Repellency Oil Release to Initial Dirt Water 5 LC Initial 5 LC Initial Example 22 Example 5 It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which results, of course, from the present description of the invention.

Having described the invention as above, the content of the following claims is claimed as property.

Claims (9)

1. A copolymer composition for the treatment of fabrics and fabric mixtures for transmitting dirt release properties, characterized in that it comprises copolymerized monomers in the following percentages by weight: (a) from 30% to 49% of at least one monomer of the Formula I: Rf-Q-A-C (O) -C (R) = CH2 I wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to 20 carbon atoms, R is H or CH3, A is O, S or N (R '), wherein R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR' ( CnH2n) -, wherein R 'is H or an alkyl of 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is 1 to 15; (b) from 5% to 65% of at least one monomer or mixture of selected monomers of formula IIA, formula IIB and formula IIC: (R?) 2N- (CH2) rZC (0) -C (R2) = CH2 HA (0) (R3) (R4) N- (CH2) rZC (0) -C (R2) = CH2 IIB X "( R5) (R4) (R3) N + - (CH2) rZC (0) -C (R2) = CH2 IIC wherein Z is -0- or -NR5-; Ri is an alkyl group of 1 to 3 carbon atoms; R2 is H or an alkyl radical of 1 to 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a ring of morpholine, pyrrolidine, or piperadine; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for the HA formula the nitrogen is from 40% to 100% salinized; Y, ' (c) from 1% to 7% of a monomer of formula III, IV, V or VI or a mixture thereof: 0 / \ CH2-CH-CH2-0-C (0) - (R2) = CH2 III Cl-CH2-CH (0H) CH2-0-C (0) -C (R2) = CH2 IV; (R6) 0C (0) C (R6) = CH2 V; or CH2 = CC12 VI wherein each R2 is independently H or a radical of: alkyl of 1 to 4 carbon atoms and each Re is. independently H or an alkyl of 1 to about 8 carbon atoms.

2. The composition according to claim 1, characterized in that the monomer of the formula I, Rf is a straight-chain fluoroalkyl group of 2 to 20 carbon atoms, A is O, and Q is alkylene of 1 to 15 carbon atoms.

3. The composition according to claim 1, characterized in that formula I is perfluoroalkylethyl acrylate, formula II is diethylaminoethyl methacrylate, and formula III is glycidyl methacrylate. * -ft ^ «. s. "^" S ^ Yes ^^ i.

4. The composition according to claim 3, characterized in that the monomer of the formula I is CF3CF2 (CF2) XC2H0C (O) -C (H) = CH2 wherein x is still an integer from 6 to 18 or mixtures thereof .

5. A method for treating fabrics or blends of fabrics for transmitting dirt release properties, characterized in that it comprises the application to the surface of the fabric or fabric mixture of an effective amount of a composition comprising copolymerized monomers in the following percentages by weight: (a) from 30% to 90% of at least one monomer of formula I: wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to 20 carbon atoms, R is H or CH3, A is O, S or N (R '), wherein R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, - (CnH2n) (OCqH2q) B-, -S02-NR '(CnH2n) -, or -CONR' (CnH2n) -, wherein R 'is H or an alkyl of 1 to 4 carbon atoms, n is 1 to about 15, q is 2 to 4, and m is 1 to 15; (b) from 10% to 70% of at least one monomer or mixture of monomers selected from the formula HA, formula IIB and formula IIC: (R?) 2N- (CH2) rZC (0) -C (R2) = CH2 HA (O) (R3) (R4) N- (CH2) rZC (0) -C (R2) = CH2 IIB X "( R5) (R4) (R3) N + - (CH2) rZC (0) -C (R2) = CH2 IIC wherein Z is -0- or -NR5-; Ri is an alkyl group of 1 to 3 carbon atoms; R2 is H or an alkyl radical of 1 to 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R3 and R4 together with the nitrogen atom form a ring of morpholine, pyrrolidine, or piperadine; R5 is H or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R5 together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for the HA formula the nitrogen is from 40% to 100% salinized; Y, (c) from 0% to 7% of a monomer of formula III, IV, V or VI or a mixture thereof: O / \ CH2-CH-CH2-0-C (0) - (R2) = CH2 III Cl-CH2-CH (0H) CH2-0-C (O) -C (R2) = CH2 IV; (R6) 0C (0) C (R6) = CH2 V; or CH2 = CC12 VI wherein each R2 is independently H or an alkyl radical of 1 to 4 carbon atoms and each Re is independently H or an alkyl of 1 to 8 atoms d = carbon.

6. The method according to claim 5, characterized in that the effective amount is such as to deposit from 0.05% to 0.5% by weight of fluorine.

7. The method according to claim 6, characterized in that the formula I is perfluoroalkylethyl acrylate, formula II is diethylaminoethyl methacrylate, and formula III is glycidyl methacrylate.

8. A fabric or fabric mixture characterized in that it has been treated to transmit dirt release properties thereto with a composition comprising copolymerized monomers in the following percentages by weight: (a) from 30% to 90% of at least one monomer of the formula I: Rf-Q-A-C (O) -C (R) = CH2 I wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to 20 carbon atoms, R is H or CH3, A is O, S or N (R '), wherein R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR' ( CnH2n) -, wherein R 'is H or an alkyl of 1 to 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to 15; (b) from 10% to 70% of at least one monomer or mixture of monomers selected from the formula HA, the formula HB and the formula IIC: (R?) 2N- (CH2) rZC (0) -C (R2) = CH2 HA (O) (R3) (R4) N- (CH2) rZC (0) -C (R2) = CH2 HB X "( R5) (R4) (R3) N + - (CH2) rZC (0) -C (R2) = CH2 IIC wherein Z is -O- or -NR5-; Rx is an alkyl group of 1 to 3 carbon atoms; R2 is H or an alkyl radical of 1 to 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R;, and R4 together with the nitrogen atom form ur ring of morpholine, pyrrolidine, or piperadine; R5 is or an alkyl of 1 to 4 carbon atoms, or R3, R4 and R = together with the nitrogen atom form a pyridine ring; r is 2 to 4; and wherein for the HA formula the nitrogen is from 40% to 100% salinized; and, (c) from 1% to 7% of at least one monomer of formula III, IV, V or VI or a mixture thereof: 0 / \ CH2-CH-CH2-0-C (0) - ( R2) = CH2 III Cl-CH2-CH (OH) CH2-0-C (0) -C (R2) = CH2 IV; (R6) OC (0) C (R6) = CH2 V; or CH2 = CC12 VI wherein each R2 is independently H or an alkyl radical of 1 to 4 carbon atoms, and each Re is independently H or an alkyl of 1 to 8 carbon atoms.

9. A fabric or mixture of fabrics according to claim 8, characterized in that it has a fluorine content of 0.05% to 0.5% by weight. SUMMARY OF THE INVENTION A copolymer composition and its use as an agent for the release of dirt for fabrics comprising copolymerized monomers in the following percentages by weight: (a) from about 30% to about 49% of at least one monomer of the formula (I): Rf-QAC (O) -C (R) = CH2, wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH3, P is 0, S or N (R '), wherein R' is H or an alkyl of 1 to about 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, (CnH2n) (OCqH2q) m -, -S02-NR '(CnH2n) -, or -CONR' (CnH2n) -, where R 'is H or an alkyl of 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15; (b) from about 10% to about 70% of at least one monomer or a mixture of monomers selected from the formulas (HA): (Rx) 2N- (CH2) rZC (O) -C (R2) = CH2, ( IIB): (O) (R3) (R4) N- (CH2) rZC (0) -C (R2), (IIC): X- (R5) (R4) (R3) N + - (CH2) rZC (O ) -C (R2) = CH2, where Z is -O- or -NR5-, Ri is an alkyl group of 1 to about 3 carbon atoms. carbon; R2 is H or an alkyl radical of 1 to about 4 carbon atoms; R3 and R4 are each an alkyl of 1 to 4 carbon atoms, hydroxyethyl; benzyl, or R3 and R4 together with the nitrogen atom form a ring of morpholine, pyrrolidine or piperadine; R 5 is H or an alkyl of 1 to 4 carbon atoms, or R 3, R 4 and R 5 together with the atom of. nitrogen form a pyridine ring; r is 2 to 4; and wherein for the formula (HA) the nitrogen is from about 40% to 100% salinized; and (c) optionally other monomers.