Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3440226 A
Publication typeGrant
Publication dateApr 22, 1969
Filing dateOct 21, 1965
Priority dateOct 21, 1965
Publication numberUS 3440226 A, US 3440226A, US-A-3440226, US3440226 A, US3440226A
InventorsCrovatt Lawrence W Jr, Huffman William A H
Original AssigneeErnestine H Huffman, Monsanto Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Polycarbonamides resistant to acid dyes
US 3440226 A
Abstract  available in
Images(5)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,440,226 POLYCARBONAMIDES RESISTANT T0 ACID DYES Lawrence W. Crovatt, Jr., Raleigh, NC, and William A.

H. Huffman, deceased, late of Durham, N.C., by Ernestine H. Huffman, executrix, Antioch, Tenn., assignors to Monsanto Company, St. Louis, Mo., a corporafion of Delaware No Drawing. Filed Oct. 21, 1965, Ser. No. 502,777

Int. Cl. C08g 20/38; D01 7/04 U.S. Cl. 260-78 11 Claims ABSTRACT OF THE DISCLOSURE Fiber-forming linear polycarbonamides modified to contain certain terminal naphthyl disulfonated radicals as an integral part of the polymer chain possess excellent acid dye-resistant properties. Fibers formed from these polycarbonamides may, for example, be combined with standard polycarbonamide fibers to provide a fabric which is dyeable in a single dye bath to different colors or color tones.

This invention relates to fiber-forming synthetic polymeric materials and the shaped articles produced therefrom. More particularly, this invention relates to novel fiber-forming synthetic linear polycarbonamides and shaped articles produced therefrom which are particularly resistant to acid type dyes.

Although textile fibers obtained from fiber-forming polycarbonamides heretofore known are of great value, they are deficient in dying properties in that they all possess the same acid dyeable characteristic and each type will dye to a single shade only. This is a distinct disadvantage since it eliminates the possibility of obtaining other desirable color effects where some of the fibers do not absorb dye or absorb less dye. It is desirable therefore, to produce polycarbonamides which have acid dye resist characteristics so that by combining such polycarbonamides with standard polycarbonamides in varying amounts it would be possible to produce polycarbonamide articles which are dyeable to different tones of the same color.

Heretofore, additives employed for this purpose have not been found to be entirely satisfactory due to their ability to impart only a limited amount of acid dyeresistance to the fibers. For example, U.S. Patent No. 3,039,990 discloses fibers with alkali metal dicarboxybenzene monosulfonates. While these additives serve to make the fibers receptive to basic dyes, they do not impart a sufficient acid dye-resist character to the fibers to make them commercially acceptable for use with acid dyes in the production of a wide range of off-shade fabrics.

It is an object of the present invention to provide novel and useful fiber-forming synthetic linear polycarbonamides.

Another object is to provide shaped articles such as textile fibers, produced from such polycarbonamides, the said article having superior acid dye-resist properties. A further object is to provide a process for the production of polycarbonamides from which shaped articles having superior acid dye-resist properties can be prepared.

These and other objects will become apparent in the course of the following specification and claims.

The polycarbonamides of the present invention are useful in the production of shaped articles by extrusion, molding, or casting in the nature of yarns, fabrics, films, pellicles, bearings, ornaments, or the like. They are particularly useful in the production of textile fibers.

The present invention provides a novel polycarbonamide wherein recurring carbonamide linkages are an integral part of the polymer chain and containing as a 3,440,226 Patented Apr. 22, 1969 component part of the polymer chain between about 0.05 and 2.0 mole percentage and preferably between about 0.1 and about 1.0 mole percentage, based on the molecular weight of the polycarbonamide, of units of the structure:

Moss SOaM wherein Z is a member of the class consisting of X is a member of the class consisting of hydrogen and lower alkyl, M is a member of the class consisting of hydrogen, the ammonium radical and an alkali metal and n is a number from zero to 6 inclusive with the proviso that when Z is and HOOCR-COOH wherein R is a divalent hydrocarbon radical, and a diamine having the formula:

l e H-NR-NH (0) wherein X and R are as defined above, and (B) a monoaminomonocarboxylic acid having the formula:

wherein X and R are as defined above, in the presence of a monofunctional disulfonated compound having the formula:

(CHzhZY MOaS S 03M wherein n, Z and M are as defined above and Y is a member of the class consisting of hydrogen, OH, CL and OR, R' being a monovalent hydrocarbon radical such that R'OH is volatile below the decomposition temperature of the polycarbonamide formed.

The nature of the radical R- in the acid, the diamine, or the aminoacid is not critical. Preferably, it is a divalent hydrocarbon radical containing no more than about 20 carbon atoms. Typical acids of the class illustrated by the formula designated (b) are oxalic, adipic, suberic, pimelic, azelaic, sebacic, brassylic, octadecanedioic, undecanedioic, glutaric, tetradecanedioic, p-phenylene diacetic, isophthalic, terephthalic, hexahydroterephthalic, and the like, and mixtures thereof.

Typical suitable diamines of the class illustrated by the formula designated (c) above are ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylenediamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, p-xylylenediamine, pphenylenediamine, hexahydro p phenylenediamine, bis(4 aminocyclohexyl)methane, piperazine, dimethylpiperazine, tetramethylpiperazine, the N,N'-dimethyl, the N,N'-diethyl and the N,N'-diisopropyl derivatives of the above, and the like, as well as mixtures thereof.

Typical suitable amino acids of the class represented by the formula designated (d) above are 6-aminocaproic acid, 9-aminononanoic acid, ll-aminoundecanoic acid and 17-aminoheptadecanoic acid.

In place of the above noted dibasic carboxylic acids, diamines, and amino acids, the amide-forming derivatives thereof can be employed to form fiber-forming polymers. Amide-forming derivatives of the dibasic carboxylic acids comprise the mono and di-ester, the anhydride, the monoand di-amide and the acid halide. Amide-forming derivatives of the diamines include carbamate and the N-formyl derivative. Amide-forming derivatives of the amino acids include the ester, anhydride, amide, lactam, acid halide, N-formyl derivative, carbamate, and, in the presence of water, the nitrile.

As indicated above the compounds found useful in the practice of this invention are characterized by two sulfonate groups and one amide-forming group attached to a naphthalene ring and are represented by the formula:

M 8 SOaM wherein n, Z, M and Y are as defined above. Illustrative of such compounds when are: di(potassium sulfonate) naphthalene 2 carboxylic acid, di(ammonium sulfonate) naphthalene 2- carboxylic acid, di(potassium sulfonate) naphthalene- 1 carboxylic acid, di(sulfonic acid) naphthalene 2- carboxylic acid, di(potassium sulfonate) naphthalene- 2-ethanoic acid, di(ammonium sulfonate)-naphthalene- 1 propionic acid, di(sodium sulfonate) naphthalene- 2 pentanoic acid, and di(sulfonic acid) naphthalene- 1 heptanoic acid; and when illustrative compounds are di(potassium sulfonate)- naphthalene 2 methylamine, di(ammonium sulfonate)- naphthalene 2 methylamine, di(sulfonic acid) naphthalene 2 ethylamine, di(potassium sulfonate) naphthalene 1 ethylamine, and di(sodium sulfonate)- naphthalene-Z-pentylamine.

The polycarbonamides of this invention are prepared by procedures well known in the art and commonly employed in the manufacture of simple polyamides. That is, the reactants are heated at a temperature of from 180 C. to 300 C. and preferably from 200 C. to 295 C. until the product has a sufiiciently high molecular weight to exhibit fiber-forming properties, which properties are reached when the polyamide has an intrinsic viscosity of at least 0.4. The reaction can be conducted at superatmospheric, atmospheric, or sub-atmospheric pressure. Often it is desirable, especially in the last stage of the reaction, to employ conditions, e.g. reduce pressure, which will aid in the removal of the reaction by-products. Preferably, the reaction is carried out in the absence of oxygen, for example, in an atmosphere of nitrogen.

Intrinsic viscosity as employed herein is defined as Lim. Logs Nr 0 o in which N is the relative viscosity of a dilute solution of the polymer in m-cresol in the same units at the same temperature, and C is the concentration in grams of polymer per cc. of solution.

The amount of additive which may be present as a component part of the polymer chain of the polycarbonamides of this invention may vary depending upon the type of polymer desired and the particular shaped article in which it is to find its end use. It has been found necessary to employ between about 0.05 and 2.0 mole percentage based on the molecular weight of the polycarbonamide. At least 0.05 mole percentage of additive is required in order that a significant level of acid dye-resist properties be obtained. It has been found that the best results are obtained when between about 0.1 and about 1.0 mole percentage of additive based on the molecular weight of the polycarbonamide are employed. Amounts greater than 2.0 mole percentage have an adverse effect on the viscosity of the polycarbonamide produced. Since the additives employed in this invention contain only one functional group, i.e., one carboxyl or one amino group, it can be seen that they react in such a manner as to terminate the polymer chain of the polycarbonamide. This type of reaction is similar to the reaction which occurs upon the addition of additives which are termed by the art as chain terminators or viscosity stabilizers. Thus, the greater amount of additive which is employed in the present invention, the shorter will be the polymer chain of the polycarbonamide and the lower will be the viscosity of the polycarbonamide. As noted above, it has been found preferable to employ amounts of additives between about 0.1 and 1.0 mole percentage since when employing such amounts the polycarbonamide produced has been found to possess excellent acid dye-resist properties and to have a viscosity in the fiber-forming range.

In order to illustrate the invention and the advantages thereof with greater particularity, the following specific examples are given; it is to be understood that they are intended to be only illustrative and not limitative. Parts are given by Weight unless otherwise indicated.

EXAMPLE I This example illustrates preparation of a conventional polycarbonamide namely, polyhexamethylene adipamide. This polymer and the fiber therefrom are to be used as a standard of comparison with the modified polycarbonamides of the present invention.

To a stainless steel evaporator there was added 8.47 moles of water containing 0.562 mole of hexamethylene diammonium adipate salt dissolved therein. The unit was purged with nitrogen and then pressurized to 13 pounds per square inch gauge. The salt solution was then heated to 137 C. with continuous removal of steam condensate. At this point the salt concentrate was piped under pressure into a stainless steel high pressure autoclave which had been purged previously with nitrogen. In this reactor, which contained a stirrer for agitation, the pressure was immediately raised to 250 pounds per square inch gauge and the temperature was raised to 220 C. The steam was removed until the polymer melt temperature reached 243 C. At this point the reactor pressure was gradually reduced over a 25 minute period to atmospheric pressure and the polymer melt allowed to equilibrate for 30 minutes at 278 C.

This finished polymer so produced was melt spun at 280 C. through a 13 hole spinnerette yielding white multifilament yarns. These yarns were drawn over hot pins (90 C.) at a maximum draw ratio of 5.65 times their original length.

Dyeing of these yarns was carried out by immersing in an acid dye bath containing 3 percent, based on the weight of the yarn, of Scarlet 4RA Conc. CF .(C.I. Acid ployed in Example II exhibited an increase acid dye resistance of nearly 122 percent over the additive employed in Example III.

EXAMPLE VII 5 Acid dye-resist poly-epsilon-caproamide was prepared Red 18) and Percent f f acld' Welght rattle by introducing 100 grams of epsilon-caprolactam and 1.94 of dye bath to fiber was maintau ied at 40.1 and dfl 3 grams of di(potassium sulfonate)-naphthalene-2-carboxwas conducted for 2 hours at 100 and at 3 PH ylic acid into a stainless steel high pressure autoclave. These Y absorbed 'P dyestufi' After purging with nitrogen the autoclave was pressurized EXAMPLE II 10 to 250 pounds per square inch gauge and the temperature was raised to 250 C. while steam was continuall re- Dflpotassmm sulfmiate)'naphthalenia-carbozglic g moved. At this point the pressure was gradually red iiced fi prepared by treatmg 100 grams 0 i'gi sg ig over a 25 minute period to atmospheric pressure and the 211th 752 r i if- 5 pertzfmt z 5 3 2 a to r temperature of the molten polymer reached 265 C. The ours at 100 e mac Ion pro f f 250 vacuum cycle was then applied to the autoclave by gradu- 1000 grams of followed by w mom 0 grams ally lowering the pressure over a 30 minute period to 25 of potassium bicarbonate. A precipitated product formed inches of mfircury and the p y melt allowed to which was redissolved by adding 3 hters of Water and heate uilibrate under tliese conditions for minutes before the solution to 70 C. followed by treatment with 2 q mg returning the autoclave to atmospheric pressure by allowgrams of activated charcoal. To the hot filtered solutiordr ing nitrogen to bleed back into the System The polymer was p added 225 gran}? of potassium chloride an was immediately melt spun at 265 C. directly from the precipitation of the finely divided 'whlte product, di(potasautoclave as 13 multifilament White y sium sulfonate)naphthalene-2-carboxyl1c acid, occurred. The y g procedure and Conditions outlined in Exam T product was filtered OE and punfied by redlssolvl-Hg ple I were repeated and these yarns were found to absorb 1n 2300 cc. of water at 70 C. followed by treatment with O 60 percent Scarlet 4RA Cone CF I Acid Red 1 gram of activated charcoal. After filtration while hot, p to 1.08 percent absor'ption lwl'lich was observed 100 grams 9 chlonde was g gg g gon conventional poly-epsilon-caprylamide yarns contain- Proquct preqlpltated m form ne 5 lte ing 0.536 mole percent potassium-3,S-dicarboxybeuzene pamcles which after coohng were Isolate tratlon' sulfonate which were prepared and dyed under identical The procedure of Example I was repeated with the exconditions ception that the above-prepared di(potassium sulfonate)- EXAMPLE VIII naphthalene2-carboxylic acid in an amount sufficient to provide a finished polyhexamethylene adipamide contain- Poly-hexamethylene sebacamide modified in accordance ing 0.555 mole percent additive, was added along with with the present invention was prepared by charging a the salt into the autoclave. This modified nylon polymer stainless steel evaporator with 0.393 mole of hexamethylthus produced was melt spun at 280 C. through a 13-hole ene diammonium sebacate dissolved in 20.8 moles of water spinnerette yielding white multifilarnent yarns. These yarns containing 0.968 gram of di(potassium sulfonate)- were drawn over hot pins (90 C.) at a maximum draw naphthalene-Z-carboxylic acid. After purging the evaporaratio of 4.60 times their original length. These yarns were tor with nitrogen the unit was pressurized to 13 pounds found to absorb 0.36 percent Scarlet 4RA Conc. CF (C. I. per square inch gauge and heated to 137 C. with removal Acid Red 18) acid dye stuff when dyed under identical of steam condensate. At this temperature the concentrated procedure and dye bath composition as outlined in Exsalt was then piped under pressure to a high pressure ample I, autoclave, which was previously purged with nitrogen, and EXAMPLE III 4 the unit pressurized to 250 pounds per square inch gauge 5 and the temperature raised to 230 C. with the continual ag g i?2 L3 gf gzz ggs gg g removal of steam. At this temperature the pressure in the f E Z e sulfolllate y gi is descgibed in autoclave was gradually reduced over a 25 minute period lca oxy en ene h to atmospheric pressure while the polymer melt tempera- Patent.303.9 yam g i g W tfiate ture was raised to 265 C. The melt was then allowed to under ldentlca con moms as emp eye In Xamp e was stand and equilibrate for a period of 30 minutes prior to fg g g fgg Percent Scarlet 4RA Cone CF melt spinning at 265 C. directly from the autoclave c1 e I EXAMPLES IV VI glllrrolugh a 13 hole spinnerette yielding whlte multlfilament The procedures outlined in the above examples were re- The spun yarns were drawn over hot pins (90 C.) at peated with the exception of the particular additive ema maximum draw ratio of 4.50 times their original length. ployed and in the amount in which it was employed. The The yarns were dyed in accordance with the procedure results obtained are illustrated in Table I. and conditions outlined in Example I, and were found to TABLE I Mole Increase Dye-Resist.

Percent Amoun Additive Additive of Dye Ex. IV Ex. IV

in Absorption vs. vs. Polymer Ex. V, Ex. VI, Percent Percent Example:

IV (a) Di(potassium sulfonate)-naphthalene-2-carboxylic acld 0.139 0.71 IV (b)- --do. 0.780 0.21 V (a)... Potassium 3 5 dicarboxy-benzene sulfonate 0.139 0.98 V(b)- o- 0.780 0.52 VI (3) -sulfobenzo1e acid monosodium salt. 0. 139 0. 94 VI (b)- do 0. 780 0. 49

These experimental findings clearly show the pronounced superiority of the additives of this invention over the difunctional monosulfonate salt and the monofunctional monosulfonate salt when used in corresponding amounts. Besides the increased acid dye resistance indicated in Table I, it should be noted that the additive emabsorb 0.39 Scarlet 4RA Conc. CF (C. 1. Acid Red 18). Yarns prepared in an identical manner with the exception that potassium-3,S-dicarboxybenzene sulfonate was the additive used were found to absorb 0.70 percent of the same dye. It will be observed that yarns containing the additive of the present invention exhibit an increase in acid dye-resist properties of 79.5 percent over yarns containing additives disclosed by the prior art.

EXAMPLE IX Di(sulfonic acid)-napththalene-Z-carboxylic acid was prepared by treating a dilute aqueous solution of di(potassium sulfonate)-naphthalene-Z-carboxylic acid with a cation exchange resin in an ion-exchange column. The treated solution was then evaporated to dryness yielding a white product, di(sulfonic acid)-naphthalene-2-carboxylic acid. The preparation of modified poly-hexamethylene adipamide containing 0.60 mole percent of di(sulfonic acid)-naphthalene-Z-carboxylic acid was carried out by the same procedure and conditions described in Example I. The additive was incorporated into the polymer preparation in the same method as described in Example II.

The resultant polymer was melt spun at 280 C. directly from the preparatory autoclave into 13 multifilament white yarns which were drawn at a maximum draw ratio of 5.70 times their original length.

These yarns were found to absorb 0.73 percent of Scarlet 4RA Conc. CF (C.I. Acid Red 18) when dyed according to procedure and conditions outlined in Example I. This dye absorption represents very nearly 41.6 percent improvement in the dye-resist character over conventional polyhexamethylene adipamide which absorbs 1.25 percent of the same dye.

EXAMPLE X Di( ammonium sulfonate)-naphthalene 2 carboxylic acid was prepared by reacting 1 mole ratio of di(sulfonic acid)-naphthalene-Z-carboxylic acid with 2 mole ratios of ammonium hydroxide in an aqueous solution and the diammonium salt product allowed to remain in solution. Modified polyhexamethylene adipamide containing 0.60 mole percent of the diammonium salt was carried out by the same procedure and conditions described in Example I. The additive was incorporated into the polymer preparation in the same manner as described in Example II.

The resultant polymer was melt spun at 280 C. into 13 multifilament white yarns which could be cold drawn. These yarns were found to absorb 0.67 percent Scarlet 4RA Conc. CF (C.I. Acid Red 18) when dyed according to procedures and conditions outlined in Example I. This dye absorption represents very nearly 46.4 percent improvement in the acid dye resist character over the standard polyhexamethylene adipamide yarns which absorb 1.25 percent of the same dye.

As can be seen from the above results, fibers made from the polycarbonamides of the present invention all possess a resistance to acid type dyes. This enables manufacturers to produce fibers having the same basic polycarbonamide molecular structure as conventional polycarbonamides but different affinities for acid dyes. This in turn otters dyeing diversification for fabric color-on-white effects and toneon-tone effects heretofore not readily obtainable.

We claim:

1. A fiber-forming synthetic linear polycarbonamide wherein recurring carbonamide linkages are an integral part of the polymer chain and containing as a component part of the polymer chain between about 0.1 and 2.0 mole percentage, based on the molecular weight of the polycarbonamide of units of the structure:

Moss $03M wherein Z is a member of the class consisting of II C and X is a member of the class consisting of hydrogen and lower alkyl, M is a member of the class consisting of hydrogen, the ammonium radical and an alkali metal and n is a number from zero to 6 inclusive with the proviso that when Z is then It is at least 1.

2. The fiber-forming synthetic linear polycarbonamide as set forth in claim 1 wherein the polycarbonamide is poly-hexamethylene adipamide.

3. The fiber-forming synthetic linear polycarbonamide as set forth in claim 1 wherein the polycarbonamide is poly-epsilon-caproamide.

4. The fiber-forming synthetic linear polycarbonamide as set forth in claim 1 wherein the polycarbonamide is poly-hexamethylene sebacamide.

5. A fiber-forming synthetic linear polycarbonamide wherein recurring carbonamide linkages are an integral part of the polymer chain and containing as a component part of the polymer chain between about 0.05 and 2.0 mole percentage based on the molecular weight of the polycarbonamide of units of the structure:

KOaS 803K 6. Polyhexamethylene adipamide containing as a component part of the polymer chain between about 0.05 and 2.0 mole percentage based on the molecular weight of the polyhexamethylene adipamide of units of the structure:

7. Polyhexamethylene adipamide containing as a component part of the polymer chain between about 0.05 and 2.0 mole percentage, based on the molecular weight of the polyhexamethylene adipamide of units of the structure:

HOaS SOaH 8. Polyhexamethylene adipamide containing as a component part of the polymer chain between about 0.05 and 9 10 2.0 mole percentage, based on the molecular weight of the of the polyhexamethylene sebacamide of units of the polyhexamethylene adipa-mide of units of the structure: structure:

K038 SOaK NHtoaS soaNH 11. A textile fiber consisting essentially of the poly- 9. Poly-epsilon-caproamide containing as a component capbonamlde as defined m Clalm part of the polymer chain between about 0.05 and 2.0 mole percentage, based on the molecular weight of the References cued poly-epsilon-caproamide of units of the structure: UNITED ES ATENTS 0 3,039,990 6/1962 Huffman 260-78 1 3,142,662 7/1964 Huffman 26078 3,184,436 5/1965 Magat 260-78 3,296,204 1/1967 Caldwell 26078 3,328,484 6/1967 Lugaz et al. 260-78 K038 $03K WILLIAM H. SHORT, Przmary Examzner.

H. D. ANDERSON, Assistant Examiner.

10. Polyhexamethylene sebacamide containing as a component part of the polymer chain between about 0.05 and 2.0 mole percentage based on the molecular weight 26078; 8--55; 57--140

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3039990 *Oct 19, 1959Jun 19, 1962Monsanto ChemicalsInterpolyamides and process for preparing same
US3142662 *Oct 19, 1959Jul 28, 1964Monsanto CoModified polyamides containing the benzenesulfonate moiety
US3184436 *Sep 4, 1959May 18, 1965Du PontPolycarbonamides of improved dye affinity having the benzene sulfonic acid salt moiety as an integral part of the polymer chain
US3296204 *Feb 20, 1962Jan 3, 1967Eastman Kodak CoSulfonated polyamides
US3328484 *Feb 10, 1964Jun 27, 1967RhodiacetaPolypropylene or polyester compositions of improved dyeability containing a linear polyamide and a linear sulfonated polyamide
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3542743 *Jul 15, 1968Nov 24, 1970Monsanto CoBasic dyeable acid dye resistive polyamides containing terminal aryl disulfonated groups
US3684775 *Jul 15, 1970Aug 15, 1972Du PontChain terminated polyhexamethylene adipamide
US5155178 *Aug 8, 1990Oct 13, 1992E. I. Du Pont De Nemours And CompanyAntistain block copolymer compositions of modified nylon copolymers and high carbon nylons
US5164261 *Aug 8, 1990Nov 17, 1992E. I. Du Pont De Nemours And CompanyDyed antistain nylon with cationic dye modifier
US5242733 *Jun 8, 1992Sep 7, 1993E. I. Du Pont De Nemours And CompanyCarpets and fabrics of antistain block copolymer compositions of modified nylon copolymers and high carbon nylons
US5468554 *Jun 15, 1994Nov 21, 1995E. I. Du Pont De Nemours And CompanyDyed antistain nylon with cationic dye modifier
US6117550 *Oct 22, 1997Sep 12, 2000Prisma Fibers, Inc.Acid dye stain-resistant fiber-forming polyamide composition containing masterbatch concentrate containing reagent and carrier
US6133382 *Nov 12, 1998Oct 17, 2000Prisma Fibers, Inc.Fiber-forming polyamide composition containing polyamide and a sulfonated polyester concentrate
US6420044Apr 12, 2000Jul 16, 2002Prisma Fibers, Inc.Stain-resistant polyamide composition and fibers and method of production thereof
US6433107Aug 28, 2000Aug 13, 2002Prisma Fibers, Inc.Fiber-forming polyamide with concentrate of polyamide and sulfonated aromatic acid
US6537475Aug 31, 1995Mar 25, 2003Prisma Fibers, Inc.Melt extrusion spinning polyamide fibers with sulfonated reagent
US6635346Mar 19, 2002Oct 21, 2003Prisma Fibers, Inc.Stain-resistant polyamide composition and fibers and method of production thereof
US6680018 *Apr 30, 2002Jan 20, 2004Prisma Fibers, Inc.Melt extrusion spinning polyamide fibers with sulfonated reagent and thermoplastic carrier
US6753385 *Jan 31, 2003Jun 22, 2004Prisma Fibers, Inc.Fiber-forming polyamide and sulfonated acid for disabling acid dye sites
US6861480 *Feb 5, 2004Mar 1, 2005Prisma Fibers, Inc.Yarn-forming composition of polyamide and sulfonated acid dye disabler
US20040152840 *May 23, 2003Aug 5, 2004Studholme Matthew BenjaminStain resistant polyamide composition and fibers and method of production thereof
US20040154110 *Feb 5, 2004Aug 12, 2004Matthew StudholmeStain-resistant polyamide composition and fibers
Classifications
U.S. Classification528/310, 528/346, 528/313, 528/323, 528/347, 528/335, 528/341, 528/336, 528/326
International ClassificationC08G69/00, C08G69/42
Cooperative ClassificationC08G69/42
European ClassificationC08G69/42