TEXTILE MILL APPLICATIONS OF CELLULOSIC BASED POLYMERS TO PROVIDE APPEARANCE AND INTEGRITY BENEFITS TO FABRICS DURING LAUNDERING AND IN-WEAR TECHNICAL FIELD The present invention relates to textile mill applications of certain cellulosic based polymer or oligomer materials which impart appearance and integrity benefits to fabrics and textiles during laundering and in-wear. The applications can be stand alone or incorporated into traditional textile mill processes such as dyeing and finishing.

BACKGROUND OF THE INVENTION It is, of course, well known that alternating cycles of using and laundering fabrics and textiles, such as articles of clothing and apparel, will inevitably adversely affect the appearance and integrity of the fabric and textile items so used and laundered. Fabrics and textiles simply wear out over time and with use. Laundering of fabrics and textiles is necessary to remove soils and stains which accumulate therein and thereon during ordinary use. However, the laundering and in-wear, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles.

Deterioration of fabric integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering and abrasion/rubbing during in-wear. These dislodged fibers may form lint, fuzz or "pills"which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundry-wear cycles of fabrics and textiles, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color.

Given the foregoing, there is clearly an ongoing need to identify materials which could be added to textile mill applications which reduce or minimize the tendency of fabric/textiles to deteriorate in appearance during laundering and in-wear. Any applications of such materials should, of course, be able to benefit fabric appearance and integrity without unduly interfering with other fabric/textile properties such as fabric feel or hand feel, draping, softness, smoothness, etc.. The present invention is directed to the use of cellulosic based polymer or oligomer materials in textile mill application which perform in this desired manner.

SUMMARY OF THE INVENTION Cellulosic based polymer or oligomer materials which are suitable for textile mill applications and provide the desired fabric appearance and integrity benefits can be characterized by the following general formula: wherein each R is selected from the group consisting of R2, RC, and wherein: -each R2 is independently selected from the group consisting of H and C1-C4 alkyl ; - each RC is wherein each Z is independently selected from the group consisting of M, R2, Rc, and RH ; -each RH is independently selected from the group consisting of C5-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, Cl-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2- hydroxyalkyl, (R4) 3 N-alkyl, (R4) 3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl, - each R4 is independently selected from the group consisting of H, C1-C20 alkyl, Cs-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl ; -each R5 is independently selected from the group consisting of H, C 1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2N-alkyl, and (R4) 3 N-alkyl ; wherein: M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and 1/2Mg ; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that: - the Degree of Substitution for group RH is between about 0. 0001 and 0.1, more preferably between about 0.0005 and 0.05, and most preferably between about 0.0008 and 0.01 ; - the Degree of Substitution for group R wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1, 0, and most preferably between about 0.4 and 0.7 ; - if any RH bears a positive charge, it is balanced by a suitable anion; and - two R4's on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.

The cellulosic based polymer or oligomer materials defined above can be used as an additive in dyeing, dyeing aftertreatments, softener finishing, hand building finishing, durable press finishing, antibacterial finishing, soil release finishing, and even mechanical finishings, etc.

The materials can be applied onto yarns/fabrics/textiles/garments via pad-dry processes or exhaustion methods The amount of the cellulosic based fabric treatment materials of the present invention needed in the textile mill applications to provide the best fabric appearance benefits depends on many factors such as yarn/fabric constructions, types of textile processes and types of textile equipment. Based on weight of fabrics, from about 0.005% to 10% of the cellulosic based materials is needed to impart fabrics with the best fabric appearance and integrity. The preferred amount is from about 0. 01% to 3% based on weight of fabrics treated with the cellulosic based materials. Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness.

All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an example of the pad-dry treatment process.

Figure 2 is an example of the exhaustion treatment method.

DETAILED DESCRIPTION OF THE INVENTION A) Cellulosic Based Polymer or Oligomer Materials The essential component of the compositions of the present invention comprises one or more cellulosic based polymer or oligomer. Such materials have been found to impart a number of appearance benefits to fabrics and textiles after applied onto fabrics during textile mill applications. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The cellulosic based fabric treatment materials used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in other preferred textile properties such as fabric feel/hand, draping, softness, smoothness, etc.

As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000. One suitable type of cellulosic based polymer or oligomer fabric treatment material for use herein has an average molecular weight of from about 5,000 to'about 2, 000,000, preferably from about 50,000 to about 1,000, 000.

One suitable group of cellulosic based polymer or oligomer materials for use herein is characterized by the following formula: wherein each R is selected from the group consisting of R2, Rc, and wherein: - each R2 is independently selected from the group consisting of H and C1-C4 alkyl ; -each Rc is wherein each Z is independently selected from the group consisting of M, R2, Rc, and RH ; - each RH is independently selected from the group consisting of Cs-C20 alkyl, Cs-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, Cl-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4) 2N-alkyl, (R4) 2N-2- hydroxyalkyl, (R4)3N-alkyl, (R4)3 N-2-hydroxyalkyl, C-CT ? aryloxy-2-hydroxyalkyl, each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl ; each R5 is independently selected from the group consisting of H, C1-C20 allyl, Cs-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2N-alkyl, and (R4) 3 N-alkyl ; wherein: M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and 1/2Mg ; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that: - the Degree of Substitution for group RH is between about 0. 0001 and 0.1, more preferably between about 0. 0005 and 0.05, and most preferably between about 0.0008 and 0.01 ; - the Degree of Substitution for group Re wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7 ; - if any RH bears a positive charge, it is balanced by a suitable anion; and - two R4's on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.

The"Degree of Substitution"for group RH, which is sometimes abbreviated herein "pH", means the number of moles of group RH components that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above.

The"Degree of Substitution"for group Re, which is sometimes abbreviated herein "DSRC", means the number of moles of group Rc components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above. The requirement that Z be H or M is necessary to insure that there are a sufficient number of carboxy methyl groups such that the resulting polymer is soluble. It is understood that in addition to the required number of Re components wherein Z is H or M, there can be, and most preferably are, additional Rc components wherein Z is a group other than H or M.

Other suitable cellulosic based polymer and/or oligomer materials are described in WO 97/31950 published on September 4,1997 and WO 98/56825 published December 17,1998.

The production of materials according to the present invention is further defined in the Examples below.

B) Textile Mill Applications The cellulosic based polymer or oligomer materials defined above can be used as an additive in dyeing, dyeing aftertreatments, softener finishing, hand building finishing, durable press finishing, soil release finishing, antibacterial finishing and even mechanical finishings, etc.

The materials can be also used either by themselves alone or in conjunction with other textile additives such as but not limited to wetting agents, chelating agents, pH control agents, softeners, soil release agents, water repellants, dye fixatives, durable press finishing agents, antibacterial agents, etc.. With regard to the textile processing process, the cellulosic based polymer or oligomer materials are commonly utilized during the dyeing and/or finishing stages The materials can be applied onto yarns/fabrics/textiles/garments via both pad-dry processes and exhaustion methods as shown in Figures 1 and 2 respectively or via spray application (not shown). The materials can be applied to woven fabric, knit fabric, nonwoven fabric, or combinations thereof. The pad-dry process is common for the dyeing and finishing of woven fabrics. No curing is necessary to fix the materials onto fabrics although they are safe to go through high temperature curing processes. Examples of high temperature curing processes include but are not limited to finishes such as durable press finishes and antibacterial finishes.

The exhaustion method is commonly used to treat knit fabrics in the textile mill applications although some knit fabrics may be treated in the pad-dry process.

The amount of the cellulosic based fabric treatment materials of the present invention needed in the textile mill applications to provide the best fabric appearance benefits depends on many factors such as yarn/fabric constructions, types of textile processes and types of textile equipment. Based on the weight of the fabric, from about 0.005% to 10% of the cellulosic based materials is needed to impart fabrics with the best fabric appearance and integrity. The preferred amount is from about 0. 01% to 3% based on the weight of the fabric treated with the cellulosic based materials. Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness.

With regard to the pad-dry process, referring to Figure 1, the concentration of the cellulosic based materials in the padding solution 20 should be determined by wet pick-up. For example, 1% of the aqueous solution is needed in the padding bath 40 if the wet pick-up is controlled as 100% based on the weight of the fabric 10 and 1% of the cellulosic based materials are needed to deliver the fabric 10 appearance and integrity benefits.

Referring to Figure 2, for the exhaustion method, the amount of the cellulosic based materials added into the exhaustion bath 60 is determined by the weight of the fabric 10. A non- limiting example would be, if a 1% add-on level of the cellulosic based materials to the fabric 10 is desired, this would be accomplished for example by adding 1 kg of the cellulosic based materials to the exhaustion bath 60 to treat 100 kg of fabric 10.

The pH range for fabric treatment is preferably from about 3 to 12 and more preferably from about 4 to 10.

EXAMPLES The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

EXAMPLE I Material composition for pad-dry application with a fabric softener Materials Composition Cellulose Based Polymer 0.5% Wetting Agent 0. 1 % Fabric Softener 2.0% Water 97. 4% pH 6-7 EXAMPLE II Material composition for pad-dry application with durable press Materials Composition Cellulose Based Polymer 10 g/1 Crosslinker Agent 60 g/1 Catalyst 15 g/1 Fabric Softener 20 g/l Wetting Agent 3 g/l Chelating Agent 5 g/l pH 4-5 EXAMPLE III Material composition for exhaustion application after dyeing Materials Composition Knitted Fabric 100 kg Cellulose Based Polymer 1 kg pH 7-8 EXAMPLE IV Synthesis of modified CMC Materials The carboxylation of cellulose to produce CMC is a procedure that is well known to those skilled in the art. To produce the modified CMC materials of this invention, one adds during the CMC making process the material, or materials, to be substituted. An example of such as procedure is given below. This same procedure can be utilized with the other substituent materials described herein by replacing the hexylchloride with the substituent material, or materials, of interest, for example, cetylchloride. The amount of material that should be added to the CMC making process to achieve the desired degree of substitution will be easily calculated by those skilled in the art in light of the following Examples.

Synthesis of Hexvlether of CMC This example illustrates the preparation of a carboxymethyl hydrophobically modified carboxymethyl cellulose and is representative of preparation of all of the cellulose ether derivatives of this invention.

Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and ethanol (150 g) are charged into a 500 ml glass reactor. The resulting alkali cellulose is stirred 45 minutes at 25°C. Then monochloroacetic acid (15 g) and hexylchloride (1 g) are added and the temperature raised over time to 95°C and held at 95°C for 150 minutes. The reaction is cooled to 70°C, and then cooled to 25°C. Neutralization is accomplished by the addition of a sufficient amount of nitric acid/acetic acid to achieve a slurry pH of between 8 and 9. The slurry is filtered to obtain a hexylether of CMC.

Table D Specific Polymer Parameters ID Polymer Type of Types of Chemistry Modification** *A Hexyl CMC Hexyl ether Chlorohexane added to CMC making process *B Decyl CMC Decyl ether Chlorodecane added to CMC making process C C12-C13 alkoxy-2 C12-C13 alkoxy-2 C12-C13 alkyl glycidyl ether hydroxypropyl CMC hydroxypropyl added to CMC making ether process *D Hexadecyl CMC Hexadecyl ether Chlorohexadecane added to CMC making process *E Chloride salt of 3-chloride salt of 3-2, 3-epoxypropyltrimethyl trimethylammonio-2-trimethylammonio-ammonium chloride added to hydroxypropyl ether 2-hydroxypropyl the CMC making process of CMC ether *F [- (C (O)- Cetyl Ketene Dimer added to CH (C16H33)- CMC making process.

C (O) CH2 (C16H33)] ester of CMC or 1,3- dioxo-2- hexadecyloctadecyl ester of CMC CMC = Carboxymethylcellulose * Manufactured by Noviant Specialty Chemicals **DSRH for these materials was in the range of from about 0. 001 to about 0. 1 While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.