EP0639664A1 - Nylon fibers with improved dye washfastness and heat stability - Google Patents

Nylon fibers with improved dye washfastness and heat stability Download PDF

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Publication number
EP0639664A1
EP0639664A1 EP94112208A EP94112208A EP0639664A1 EP 0639664 A1 EP0639664 A1 EP 0639664A1 EP 94112208 A EP94112208 A EP 94112208A EP 94112208 A EP94112208 A EP 94112208A EP 0639664 A1 EP0639664 A1 EP 0639664A1
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Prior art keywords
polyamide
fibers
fiber
dye
fabric
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EP94112208A
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German (de)
English (en)
French (fr)
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Anil W. Saraf
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BASF Corp
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BASF Corp
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • the present invention is directed to nylon fibers with improved dye washfastness and heat stability in particular it is directed to nylon fibers containing an additive such as water, an alcohol, or an amine and a heat stabilizer such as a phenolic compound or a phoshite containing aryl groups or mixtures thereof and a process for the manufacture thereof.
  • an additive such as water, an alcohol, or an amine
  • a heat stabilizer such as a phenolic compound or a phoshite containing aryl groups or mixtures thereof and a process for the manufacture thereof.
  • Anionic acid dyeing of polyamide yarns involves the reaction of the amino end group of the nylon yarn with the sulfonic acid end group of the dye molecules.
  • the anionic dyes could possess a mono-, or a di-, or a tri-sulfonic acid end group.
  • the reactivity of the dye with the fiber is directly proportional to the number of functional groups present in the dye and/or the fiber. Therefore, it follows that the greater the number of dye molecules that bond with the amine endgroups of the fiber, the better the washfastness of the fiber.
  • Heatsetting of the fabric prior to dyeing is essential to avoid curling of the fabric. Typical heat setting temperatures range between as low as 90°C to very severe temperatures of 200°C. When heat setting is conducted at elevated temperatures such as above 140°C, in air, oxidative degradation of the amino- endgroups occurs destroying the functional groups present in the fiber. This depletion of amino end groups reduces the affinity of the dye molecules to the fiber.
  • dyeing methods are modified. This involves increasing the temperature of the dye bath in some cases and/or reducing the pH of the dye bath, in many cases.
  • the modified dyeing procedure increases the affinity of the dye into the fiber, it is a temporary phenomenon, since after dyeing, the fabric is washed thoroughly to remove the acidity in the fabric.
  • the dye molecules that are thus entrapped in the fiber are loosely bound due to lack of chemically reactive sites in the fiber. Such molecules are susceptible to diffuse out of the fabric during subsequent washings.
  • the physical size of these entrapped dye molecules have a significant influence on the diffusion of the dye out of the fiber and hence, also the dye wash fastness of the fabric.
  • the smaller dye molecules are also those which possess a mono-sulfonic acid group, i.e. the least number of functional groups, and hence a lesser affinity to the fiber.
  • Pre-heat set polyamide yarns dyed with such dyes exhibit the worst washfastness.
  • DE-A 4,131,926 describes a process wherein the dyed substrates like nylon are treated with dispersions of sterically hindered cycloaliphatic amines, which improves light and washfastness.
  • DE-A 3,330,120 discloses an aftertreatment of polyamide textiles, dyed with anionic dyes, with a polybasic compound which was a reaction product of a polyamine with a cyanamide derivative to improve the wetfastness and washfastness.
  • JP 81 53, 293 Yet another method is disclosed in JP 81 53, 293 wherein acid dyed polyamide fibers are treated with a color fixing agent.
  • This color fixing agent is based on a condensation product of a polysulfone, a compound containing amino groups and sulfonic acid groups, and an aldehyde. The washfastness of polyamide fibers treated with this agent is improved.
  • JP 80 71,884 describes a polymeric quaternary ammonium compound which when applied to the face of a printed polyamide fabric, improves the colorfastness of the fabric.
  • U.S. Pat. No. 4,863,664 discloses a high speed process of making polyamide filaments by melt mixing polyamide with some additives like water, alcohols or organic acids prior to spinning. Although, the process claims to improve yarn quality, processability and dye washfastness of the fabric, it does not address the issue of heat stability of the fibers made from such a process. The poor heat stability and the resulting streaky dyeing are significant disadvantages of this process.
  • Still another object was to provide polyamide fibers for the manufacture of yarns which would possess reduced yellowing and retain the whiteness of the fabric after heat treatment and a process for the manufacture of such yarns.
  • Another object was to provide polyamide fibers for the production of dyed fabrics having improved uniformity after heatsetting and a process for the manufacture of such polyamide fibers.
  • Another object was to provide polyamide fibers which achieve a greater exhaustion of the dye bath at an increased rate thereby reducing the release of effluents of waste dyes and chemicals in waste water and a process thereof.
  • Yet another object was to provide polyamide fibers for the production of dyed fabrics having deeper dye shades and a process for the manufacture of such polyamide fibers.
  • a polyamide fiber which comprises:
  • Fiber forming polyamides (a) are well known by the generic term "nylon” and are long chain synthetic polymers containing amide (-CO-NH-) linkages along the main polymer chain.
  • Suitable fiber-forming or melt spinnable polyamides of interest for this invention include those which are obtained by the polymerization of a lactam or an amino acid, or those polymers formed by the condensation of a diamine and a dicarboxylic acid.
  • Typical polyamides include nylon 6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6/12, nylon 6T, nylon 11, nylon 12 and copolymers therof or mixtures thereof.
  • Polyamides can also be copolymers of nylon 6 or nylon 6/6 and a nylon salt obtained by reacting a dicarboxylic acid component such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid with a diamine such as hexamethylene diamine, meta-xylene diamine, or 1,4-bisaminomethyl cyclohexane.
  • a dicarboxylic acid component such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid
  • a diamine such as hexamethylene diamine, meta-xylene diamine, or 1,4-bisaminomethyl cyclohexane.
  • poly-epsilon-caprolactam polyhexamethylene adipamide (nylon 6/6).
  • nylon 6 is terephthalic acid, isophthalic acid, adipic acid or sebacic acid
  • a diamine such as hexamethylene diamine, meta-xy
  • Suitable additives (b) are water, mono- and polyalcohols, mono- and diamines and mixtures thereof.
  • Suitable monoalkahols are C2 - to C18 - alkohols like ethanol, propanol, butanol, hexanol, decanol, undecanol, octadecanol; arylsubsituted alcohols like benzyl alcohol and benzoin.
  • Suitable polyalcohols are glycols like ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentylglycol, glycerin, trimethylolethan, trimethylolpropan and pentaerythritol.
  • Suitable amines for the additive (b) are mono- and diamines, preferred are diamines like hexamethylene diamine, meta-xylene diamine and 1,4 bis-aminomethyl cylohexane.
  • the preferred additive (b) is triethylene glycol and hexamethylenediamine.
  • the additive (b) is usually used in an amount of from 0.05 to 5% by weight, preferably from 1 to 4% by weight, most preferably from 1.5 to 3% by weight, based on the total amount of the polyamide fiber.
  • Suitable heat stabilizers (c) are phenolic compounds, phosphites containing aryl groups and mixtures thereof.
  • Suitable phenolic compounds are compounds which contain at least one phenolic group with two lower alkyl substitutents in the aromatic ring, at least one of which is in ortho position of the hydroxyl group.
  • the lower alkyl groups are preferably branched groups such as t-butyl. Examples for alkyl substituted phenolic groups are 3-t-butyl-6-methyl-4-hydroxy phenyl and 3,5-dimethyl-4-hydroxyphenyl.
  • phenolic compounds examples include 2,2'-methylene-bis(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis(6-tert.-butyl-4-ethylphenol), 2,2-bis(3,5-di-tert.butyl-4-hydroxyphenyl)-propane, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxphenyl-propionyl)-hexahydro-s-triazine, N,N'-di(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine, 1,3,5-tri(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, pentaerythrito
  • Suitable phosphites containing aryl groups are disclosed for example in U.S. Pat No. 4,187,212, the disclosure thereof is herewith incorporated by reference.
  • Preferred phosphites are: tris-(2,5-ditert.-butylphenyl)-phosphite, tris-(2-tert.-butylphenyl)-phosphite, tris-(2-phenylphenyl)-phosphite, tris-(2-(1,1-dimethylpropyl)-phenyl]-phosphite, tris-[2,4-di-(1,1-dimethylpropyl)-phenyl]-phosphite, tris-(2-cyclohexylphenyl)-phoshite, and tris-(2,4-ditert.-butylphenyl)-phosphite, and tris- (2-tert.-butyl-4-phenylphenyl)-phosphite.
  • Particularly useful are mixtures of phenolic compounds with phosphites.
  • the heat stabilizer (c) is usually used in an amount of from 0.01 to 3% by weight, preferably from 0.1 to 1.5% by weight, most preferably from 0.15 to 1.25% by weight, based on the total weight of the polyamide fiber.
  • a process for the manufacture of polyamide fibers comprises:
  • the draw ratio usually is from 1.0 to 4.0, most preferred from 1.0 to 3.0.
  • the heat stabilizers (c) may be added before or during the polymerization of the polyamide and the additive (b) may be added before or during processing of the polyamide into a fiber.
  • both the heat stabilizers (c) and the additives (b) may be added simultaneously or separately before or during polymerization of the polyamide and the mixture may be processed into a fiber in the next step.
  • the heat stabilizers (c) and additives (b) may be mixed together homogeneously and added to the polyamide during its processing in the form of fibers.
  • the addition of the heat stabilizers (c) and additives (b) to the polyamide during processing of the fibers could be performed in several ways.
  • the components (b) and (c) may be volumetrically or gravimetrically fed individully or as a mixture to the extruder using a suitable feeding system eg.
  • the components (b) and (c) may be mixed homogeneously in a suitable non-reactive inert liquid and the mixture may be injected in the extruder to achieve a melt mixing with the polyamide.
  • the mixture could be injected directly into the extruder without dispersing it into the inert liquid.
  • the mixture of the two components (b) and (c) may be melted and the melt may be injected into the extruder using a liquid injection system.
  • Another preferred embodiment to process the polyamide fibers of the present invention would be by preparing a concentrated master-batch of polyamide chips containing high levels of one or both components (b) and (c) and mixing that master-batch with the polyamide polymer to achieve the desired levels of the components in the fiber.
  • the mixing of the two polymers, namely, the masterbatch chips and the polyamide chips could be done using a volumetric or a gravimetric feeding system at the opening of the extruder or could be done using a side-arm on the main extruder wherein the molten streams of the two polymers may be mixed.
  • the homogeniety in the two streams could be achieved using in-line static mixers.
  • the methods described herein may be used as depicted or may be used as a combination with two or more processes. Further processing of this mixture may be performed as follows:
  • the melt mixing may be performed in an extruder at a temperature of 20° to 40°C above the melting temperature of the polyamide being used.
  • the additive (b) and the heat stabilizer (c) may be added together or separately to the polymer chips or grannules before they enter the extruder, or may be added into the opening of the extruder together with the polyamide or may be added through a side extruder directly into the melt, where the mixing to a homogeneous mixture takes place.
  • the homogeneous mixture of fiber forming polyamide (a), additive (b) and heat stabilizer (c) may be spun through a conventional spinnerette to form fibers, which are solidified by quenching them with air.
  • the fibers may be treated with a finish such as a lubricating oil or a mixture of oils and an antistatic agent.
  • finish provides an efficient runnability of the fiber on the spinning machine and in subsequent processing steps.
  • the fibers may be spun in any one of the following ways:
  • An optional step is texturizing the fibers with, for example, and air jet, gear crimping, stuffer box, or edge crimping process.
  • drawing and texturizing could also be performed in a single step, such as in case of a one step bulked continuous filament (BCF) yarn process for carpet enduse.
  • BCF bulked continuous filament
  • the fibers of the present invention usually have an amine end group (AEG) content of from 15 to 70 meq/kg, preferably from 35 to 50 meq/kg, and a relative viscosity (RV) (measured in formic acid at 25°C, but given values are calculated values corresponding to a measurement in sulfuric acid at a concentration of 1 g of fiber per 100 ml in 96% strength by weight sulfuric acid at a temperature of 25°C) of from 2.0 to 3.2, preferably from 2.2 to 3.0.
  • AEG amine end group
  • RV relative viscosity
  • the polyamide fibers of the invention on hand are having an improved heat stability measured in a spectrophotomatic yellowing value ⁇ b of less than about eight (8) after two minutes exposure to 380°F (193°C).
  • polyamide fibers of the invention on hand are having a dye uptake with a dye saturation value of at least 3% based on weight of fabric.
  • the polyamide fibers of the invention on hand are having an improved dye washfastness measured by the cigar bleed test stain rating of at least 3.5 on color matched samples.
  • polyamide fibers of the invention on hand are having a tenacity of from 2 to 5.5 g/den and an elongation of from 25 to 75%.
  • Nylon 6 (Ultramid® BS 700F, BASF Corporation, Freeport, TX) was extruded at a temperature of 272°C through a 12 hole round cross section spinneret of hole diameter 200 microns and capillary length of 400 microns.
  • Triethylene glycol (TEG) was injected at the throat of the extruder during spinning by means of a Zenith metering pump at different levels.
  • the filaments were cooled in a quench cabinet where air at 55° F (12.8°C) and 65% relative humidity was blown at 100 ft/min (30.5 m/min).
  • the filaments passed through a tangling jet and were taken up by a set of godets running at 5000 m/min.
  • the yarn then went through a steam chamber where steam at a temperature of 130°C was maintained at a pressure of 65 psi (448 kPa).
  • the yarn was wound on a Barmag SW-6 winder at a speed of 5390 m/
  • Table I indicates the relative viscosity, the amine end group content (AEG) and the mechanical properties of the yarn obtained using different levels of triethylene glycol (TEG) addition.
  • TEG (% b.w.) Rel. Visc.
  • AEG (meq/kg) Denier Ten (gpd) Elo (%)
  • BWS (%) 1 0 2.79 34.6 42.1 3.82 53.5 7.53 2 1 2.57 39.5 42.1 4.11 52.2 7.87 3 1.5 2.53 41.9 42.1 4.07 51.8 7.53 4 2 2.47 44.5 42 4.02 50.6 8.17 5 2.5 2.4 47.1 41.8 3.91 49.7 8.33 6 3 2.36 49.7 41.97 3.83 49.9 8.20
  • TABLE II Example Density (g/cc) % Alpha % Gamma % Crystallinity 1 1.13672 52.0 48.0 30.5 2 1.13843 46.8 53.2 32.2 3 1.13951 38.8 61.2 33.6 4 1.13904 40.7 59.3 33.0 5 1.14134
  • the morphological properties of the fibers are listed in Table II.
  • the density of fibers was measured using a Quantachrome® Helium pycnometry. No correction was made for additive volumes.
  • a typical high speed spun polyamide fiber exhibits two types of crystal structures, namely, alpha and gamma.
  • the percent composition of each of the crystal types present can be obtained using Wide Angle X-ray Diffraction (WAXD) techniques.
  • WAXD Wide Angle X-ray Diffraction
  • a theta-two theta equatorial WAXD scan of nylon 6 can be resolved into 5 peaks, 4 of which are assigned as crystalline peaks, namely, ⁇ 200, ⁇ 001, ⁇ 200 and ⁇ 002.
  • the relative fractions of alpha and gamma crystals can be obtained from ratios of the integrated intensities of the resolved peaks.
  • Equatorial ⁇ -2 ⁇ difractometer scans were obtained on a Siemens D500 x-ray generator with a Cu-K ⁇ radiation generated at 40 kV and 25 mA.
  • the five-line model developed by Heuvel and Huismann (H. M. Heuvel and R. Huismann, J. Appl. Polym. Sci., Polym. Phys. Ed., 19, 121 (1981)) was used to resolve peaks and obtain the ⁇ / ⁇ ratios.
  • the crystallinity was calculated based on the fiber densities obtained from the He-pycnometer and the ⁇ - ⁇ crystal ratios, using the formula: where X c is the volume fraction crystallinity, ⁇ is the density of fiber, ⁇ a is the density of amorphous phase (1.10 gm/cc) and, ⁇ c is the density of the pure crystalline phase, which is obtained from the following equation, Density of pure alpha phase is taken as 1.23 gm/cm3 and that of pure gamma phase is assumed to be 1.21 gm/cm3). "Polymer Handbook," Ed. J. Brandup and E. H. Immergut, Publ. J. Wiley and Sons, N.Y. (1989)].
  • the tenacity (Ten) is defined as breaking load (gms)/denier (den).
  • the elongation (Elo) is defined as
  • BWS boiling water shrinkage
  • lengths of skeins ( l o ) of 90 m of yarn were measured at a pretension of 0.056 gm/den and were allowed to shrink freely in a boiling water bath for 1 min.
  • the length of skeins ( l ) were remeasured at the same pretension and the percent shrinkage was calculated based on dl / l o , where dl is the change in length of the sample, ( l o - l ).
  • Relative viscosity of yarns were measured by a single point method. Flow times of solutions (t s ) of 1% by weight yarns in formic acid were measured using a Ubelhode viscometer and were compared to those of pure solvent (t o ). The relative viscosity (RV) was calculated as t s /t o . The RVs thus obtained were converted to those that would have been obtained using sulfuric acid as solvent using a, calibration curve.
  • the amino end group (AEG) concentration was obtained by standard potentiometric titration method.
  • a 3.33% by weight (b.w.) solution of dry polymer or yarn was prepared in 68% b.w. phenol/32% b.w. methanol and titrated against 0.02 N hydrochloric acid to a predetermined pH.
  • the AEG was calculated from a calibration curve obtained using polymar chips of known AEGs.
  • the yarns were knitted into fabrics and dyed using the following procedure.
  • the greige fabrics were preheatset at 193° C for 60 seconds.
  • a dye bath with a liquor ratio of 15:1 was prepared which contained 1% owf Irgalev PBF, 2% owf Ammonium sulfate and 2% owf Acetic acid of a concentration of 56%.
  • Critical commercial swimwear shades were used to test these samples. Shade Dye Formula Red 1.0% b.w. Intrazone Red G190% (Crompton & Knowles) 2.5% b.w. Erio Acid Red XB (Ciba Geigy) Blue 2.5% b.w. Erionyl Brilliant Blue RL 200% (Ciba Geigy) 1.0% b.w. Solophenyl Turquoise Blue GRC 250% (Ciba Geigy)
  • Dyeing was carried out at 96°C for one hour. After dyeing the samples were rinsed and treated in a bath of 1.0% b.w. acetic acid (28%), 3% b.w. tannic acid and 4.0% b.w. fixing agent XP-10 (Piedmont Chemical Industries, Inc.) for 30 minutes. These aftertreated samples were rinsed in a bath of 0.5% b.w. Peregal ST with a liquor ratio of 40:1 at 60°C for 10 minutes. The rinsed samples were later dried and tested for washfastness.
  • Dye washfastness of the samples was measured by using a "cigar bleed" test, described as follows. 2" X 4" (5.08 cm x 10.16 cm) samples of the dyed fabric were wrapped in a 2" x 4" (5.08 cm x 10.16 cm) white nylon fabric in the shape of a cigar. The cigar roll kept in a wet bath at room temperature of 24 hours. The fabrics were dried and the level of staining obtained on the white fabric was graded on a scale of 1 through 5, 5 being the least stained. Table III shows the cigar bleed test results conducted in examples 1 through 6. No attempts were made to match the shade to the control. TABLE III Example Cigar Bleed Rating Blue shade Red shade 1 2.0 2.0 2 2.5 2.5 3 3.0 3.0 4 4.5 3.5 5 4.5 3.5 6 4.5 3.5
  • the percent reflectance, (% R), an indicator of the amount of light reflected from samples dyed with blue shade was measured using a CS-5 Chroma Sensor® spectrophotometer made by Applied Colored Systems, Inc.
  • the spectrophotometer was run in the specular-included measurement mode with an area of view of 0.236" (0.6 cm) and an angle of view of 10°;
  • the ratio of the absorption coefficient to the scattering coefficient (K/S), an indicator of the degree of the depth of shade was calculated using the Kubleka-Munk approximation: Table IV depicts the results obtained from the spectrophotometer in examples 1-6.
  • Tristimulus values and CIE L*a*b* coordinates were calculated from the reflectance data over the range of wavelengths (400 nm to 700 nm).
  • ⁇ L* a measure of a change in lightness of shade
  • ⁇ E* a measure of an overall color difference in comparison to the control (example 1) were obtained using standard methods [F.W. Billmeyer, Jr. and M. Saltzman, "Principals of Color Technology," Pub. J. Wiley & Sons, NY (1981)].
  • Examples 7 and 8 in Table VII are results of a separate experiment conducted under processing conditions similar to those in examples 1-6, however, the amount of additives and the polymer viscosities were different.
  • a homogeneous slurry of TEG, Irganox® B-1171 and TiO2 was prepared using a Waring blender in the ratio (76% b.w. TEG, 14% b.w. TiO2 and 10% b.w. Irganox® B1171 and the mixture was injected at the throat of the extruder.
  • the injection method was similar to the one used in examples 2-6. The rate of injection was adjusted so as to get 1.6% b.w. TEG, 0.25% b.w.
  • Examples 1 through 8 were knitted into fabrics and heat set at 380°F (193°C) for 1 min and 2 mins. The degree of yellowing was measured on a spectrophotometer. ⁇ b values indicate the degree of yellowing compared to that of the non-heatset fabrics. Higher ⁇ b values indicate greater yellowing. Tables VI depicts the ⁇ b values for examples 1-8. TABLE VIII Example ⁇ b 380°F - 1 min 380°F - 2 min 1 6.03 9.83 2 7.41 10.2 3 10.89 11.64 4 7.09 9.53 5 8.10 11.19 6 8.50 11.66 7 7.7 12.8 8 5.5 6.6
  • example 8 exhibits a much higher rate of dyeing as well as a greater dye uptake.
  • examples 7 and 8 were dyed to saturation and the residual equilibrium dyebath concentration was measured in each case.
  • the amount of dye on the fabric was calculated after normalizing for weights of the samples in the baths.
  • the data in Table X confirms the higher amount of dye uptake for the sample containing TEG and Irganox® B1171.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP94112208A 1993-08-16 1994-08-02 Nylon fibers with improved dye washfastness and heat stability Withdrawn EP0639664A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US107392 1987-10-08
US10739293A 1993-08-16 1993-08-16
US10683793A 1993-08-16 1993-08-16
US106837 1993-08-16

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US5858586A (en) 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5908495A (en) 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
EP0962581A1 (de) * 1998-06-02 1999-12-08 Ciba SC Holding AG Verbesserung der Ozonstabilität von gefärbtem und ungefärbtem polyamidhaltigem Material
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
FR2780987A1 (fr) * 1998-07-10 2000-01-14 Rhodia Performance Fibers Procede de fabrication de fibres en polyamide
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
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US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
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US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
EP1041109A3 (en) * 1999-03-30 2001-10-31 Ube Industries, Ltd. Polyamide compositions having good fluidity
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
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CN112410925A (zh) * 2020-11-26 2021-02-26 华峰化学股份有限公司 一种酸性可染氨纶纤维的制备方法

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US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
EP0962581A1 (de) * 1998-06-02 1999-12-08 Ciba SC Holding AG Verbesserung der Ozonstabilität von gefärbtem und ungefärbtem polyamidhaltigem Material
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
WO2000003076A1 (fr) * 1998-07-10 2000-01-20 Rhodia Performance Fibres Procede de fabrication de fibres en polyamide
FR2780987A1 (fr) * 1998-07-10 2000-01-14 Rhodia Performance Fibers Procede de fabrication de fibres en polyamide
US6719937B1 (en) * 1998-07-10 2004-04-13 Rhodia Performance Fibres Method for making polyamide fibers
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
EP1041109A3 (en) * 1999-03-30 2001-10-31 Ube Industries, Ltd. Polyamide compositions having good fluidity
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
WO2011094542A3 (en) * 2010-01-29 2011-12-08 E. I. Du Pont De Nemours And Company Polyamide compositions with improved salt resistance and heat stability
CN112410925A (zh) * 2020-11-26 2021-02-26 华峰化学股份有限公司 一种酸性可染氨纶纤维的制备方法
CN112410925B (zh) * 2020-11-26 2022-05-03 华峰化学股份有限公司 一种酸性可染氨纶纤维的制备方法

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AU7025994A (en) 1995-02-23

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