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WO2000046438A1 - Teinture stable par formation in situ de microparticules - Google Patents

Teinture stable par formation in situ de microparticules Download PDF

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Publication number
WO2000046438A1
WO2000046438A1 PCT/US1999/002306 US9902306W WO0046438A1 WO 2000046438 A1 WO2000046438 A1 WO 2000046438A1 US 9902306 W US9902306 W US 9902306W WO 0046438 A1 WO0046438 A1 WO 0046438A1
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Prior art keywords
fiber
micro
recited
particles
solution
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William J. Todd
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Louisiana State University
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Louisiana State University
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Priority to CA002358507A priority patent/CA2358507C/fr
Publication of WO2000046438A1 publication Critical patent/WO2000046438A1/fr
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0076—Dyeing with mineral dye
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/008—Preparing dyes in situ
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/34—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using natural dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds

Definitions

  • This invention pertains to a method to dye fibers by first attaching a nucleating (i.e., reducing) agent to a fiber and then forming insoluble, colored micro-particles at the attachment site of the nucleating agent.
  • a nucleating agent i.e., reducing
  • dye complexes are first formed as colored reagents. These colored reagents are then reacted with fibers of a textile to create a dyed textile. Common mechanisms to attach the pre-formed dyes to the fibers include both the formation of covalent bonds between the dye and the textile and the formation of non-covalent bonds using charge or hydrophobic interactions. The resulting color of the dyed textile has been the same as or similar to that of the colored reagent.
  • Metals are commonly used in the textile industry.
  • the uses include ionic components of organic-metal dye complexes, components of chelating agents to attach dyes to fabrics, and coatings to protect fibers from damage due to photo- bleaching.
  • Metals have been deposited by sputter coating, vacuum deposition, and other methods onto surfaces of textiles to form metallic coatings. See M. Tsutsui, U.S. Patent No. 4,927,683; M. Tsutsui, U.S. Patent No. 5,089,105; Manabe et al. , U.S. Patent No. 4,816,124; and M. Fuerstman, U.S. Patent No. 4,657,807.
  • metals have been incorporated as preformed flakes or particles into the construction of yarns.
  • the appearance of the metal is typically similar to that of the native metal, whether on the surface or within the fabric is typically similar to the native metal; i.e., silver appears as the color of metallic silver and gold appears as the color of metallic gold.
  • Metals attached by such methods are not well integrated into the chemical structure of the fabric, but are adsorbed only on the fiber surface.
  • Submicroscopic particles of gold in solution can have a range of colors including grey, orange, red, or purple, depending upon the size and concentration of the particles.
  • the current procedure to manufacture gold sols is to incubate a mixture of gold ions and a nucleating agent (reducing agent) in an aqueous solution. See J. Smit et al. , "Colloidal Gold Labels for Immunocytochemical Analysis of Microbes,” in Ultrastructure Techniques for Microorganisms,” (H.C. Aldrich and W.J. Todd, eds.), p. 469-516 (1986); and Brooks, Jr. et al, U.S. Patent No. 5,514,602.
  • the process of sol formation is believed to occur through a reducing event.
  • the gold ions are reduced by the nucleating agent to form a gold micro-particle (a nucleation complex) which increases in size by deposition of metal ions from solution until the metal ions are depleted.
  • Methods to make gold micro-particles may differ depending on the nature of the nucleating agent, pH, temperature, and concentrations of the metal ion or nucleating agent solutions.
  • the type of nucleating agent is important in determining the size and quality of the product.
  • the sol particles can be stably coated with a variety of reagents or polymers, including antibodies or other specific ligands.
  • Such coated sols are extensively used in diagnostic immunological assays as signals to detect and identify antigens.
  • Visual diagnostic signals using gold sols are very sensitive because only a few gold sol particles are required to produce a visually detectable, and often robust, signal. See M. Moeremans et al. , "Sensitive colloidal metal (gold or silver) staining of protein blots on nitrocellulose membranes," Analytical Biochemistry, vol. 145, pp. 315-321 (1985); Moeremans et al.
  • Iron oxides which are traditional pigments, are known to form a film on the surface of textiles and to even polymerize on the fiber surface. However, there is no reduction of the iron within the fiber, only a surface adsorption with or without polymerization in a single step process. See H.H. Kuhn, "Adsorption at the liquid/solid interface: Metal oxide coated textiles," from Book of Papers, 1998 International Conference and Exhibition of American Association of Textile Chemists and Colorists, pp. 281-289 (1998).
  • Chemical groups capable of functioning as nucleating agents to reduce metal ions to form sols are already used in the textile industry. Indeed, some of the weaker reducing groups are constituents of some fibers, for example acetate polymers. Reagents capable of forming nucleation reactions possess other properties of importance to the textile industry. The best example is the tannin family of compounds. Tannins are used as mordants in the textile dye industry and are used with soluble metal-containing compounds to form particles in solution that adsorb onto the fibers of the textiles. See Pai, U.S. Patent No. 5,516,338. The concentration of tannic acid when used as a mordant is typically 15 to 30% by weight depending on the fabric weight.
  • Metal solutions have also been used as a mordant or otherwise to improve the color produced by a natural or synthetic dye. See Paffini, U.S. Patent No. 4,486,237; Gurley, U.S. Patent No. 5,403,362; and Gurley, U.S. Patent No. 5,631,795.
  • micro-particles of metals can be generated as an integral part of a fiber by first attaching a nucleating agent to the fiber, and then adding a solution of metal ions.
  • the ions are reduced by the nucleating agent in the fiber, and micro-particles are generated in or on the fiber.
  • a strong color signal results with a low concentration of metal micro-particles, making the method cost effective even for gold or titanium ions.
  • Various colors were generated by changing the size and spacing of the micro-particles, the metal or metal complex used, and the characteristics of the fiber. The colors produced have included pink, red, purple, yellow, orange, peach, brown, gold, silver, grey, green, and black. Colors so produced resisted bleaching by either chemicals or light.
  • a two-step method to chemically convert soluble metals into colored micro-particles firmly integrated in the fibers of textiles has been developed.
  • the first step usually was the attachment of a nucleating agent (i.e., a reducing agent), usually by simple absorption and diffusion onto the surface and into the substructure of the fiber of a textile.
  • the second step was to immerse such treated textiles (with the attached nucleating agent) into a solution containing ions of the desired metal. After incubation, colored micro-particles form at the nucleation sites.
  • the extent of particle formation depended on the ability of the nucleating agent to reduce the ions in solution, the concentration of the ions, the temperature, and the duration of the reaction.
  • the character of the final color was influenced by the size and spacing of the micro-particles, the chemical composition of the micro-particles, and the composition of the textile fibers.
  • micro-particle as used in the specification and the claims is intended to mean a particle formed at the site of the attached nucleation agent by reduction of a soluble form of a metal at that nucleation site; the "micro-particle” may be a particle of a metal, a metal complex, a metal ion, or a polymer nucleus coated with a metal or a metal compound.
  • the micro-particles may be of the metals themselves, complexes with other metals, or compounds of metals such as oxides, hydroxides, salts, and minerals, or of polymer nuclei coated with metals or compounds.
  • metals useful in practicing this invention include platinum, gold, silver, iron, copper, selenium, chromium, vanadium, titanium, manganese, zirconium, ruthenium, tungsten, palladium, molybdenum, nickel, cobalt, and other transition metals.
  • micro-particles of this invention were formed in situ in and around the textile fibers. Initially, the textile was exposed only to the nucleating agent. The nucleating agent infiltrated and attached to the fibers. Only after removing the solution (and optionally drying the textile) was the textile exposed to the metal ion solution. The metal ions infiltrated the fibers, and particles formed at the sites of the nucleating agent.
  • the nucleating agent and the metal ions are smaller than a preformed micro-particle, greater penetration into the fiber and substructure of the textile was achieved by this method than by the prior method of preforming the micro-particles before dyeing.
  • the process of forming the micro-particles within the substructure of the fiber also leads to particles more firmly bound to the fiber, presumably because portions of the substructure of the fiber were incorporated into the micro- particle as it formed.
  • Such intimate association of the micro-particle and fiber may explain the variation in color that occurred when the same technique and solutions were applied to different types of fabrics (See Example 2 below). This theory was further supported by the ultrastructure of the micro-particles. (See Example 7 below).
  • the method of in situ formation allowed the formation of mixed metal alloys and metal coats that are difficult, if not impossible, to achieve in free solution.
  • micro- particles When micro- particles are formed in free solution, their surface charge is negative and the addition of positive ions will typically result in precipitation.
  • the particle growth and composition can be controlled either by washing out the first metal ion solution and subsequently infiltrating a compatible second metal ion or by infiltrating solutions containing more than one type of metal ion. Reaction mixtures of ions from different metals can be directly applied in a variety of ratios which affects the final color.
  • micro-particles of only vanadium gave a grey-to-black color on silk, while micro-particles of titanium gave a yellow-to-orange color.
  • a mixed particle was made of vanadium and titanium, the result was a green color, the shade dependent upon the ratio of vanadium to titanium.
  • An additional unique factor of this invention was the requirement for low concentrations of reagents. All of the ions of elements and compounds used to form the micro-particles by this in situ method were effective at a concentration of 0.01 % W/V, with a range extending at least over the interval of 0.1 % to 0.001 % . For titanium, a 0.001 % solution gave good results, indicating that titanium could be diluted even further. Advantages in using such low concentrations include lower cost, less potential pollution, and lowered exposure to reagents with some toxicity.
  • Concentration of the nucleating agents was in a range extending at least over the interval of 1 % to 0.001 % W/V. Although all nucleating agents are reducing agents, not all reducing agents are effective nucleating agents. Additionally, a nucleating agent may be effective only for some metals but not others. For example, sodium citrate and sodium acetate were effective nucleating agents for gold, but not for titanium. Tannic acid at a concentration of 0.1 % was effective for all the metals tested and was the most commonly used nucleating agent.
  • the textile was immersed in the nucleating agent solution for a time which depended on the temperature; i.e., from a few minutes at a boiling temperature to a few hours at an ambient temperatures. Then the textile was typically dried at 60° C and stored until exposure to the metal ion solution.
  • the pH of the metal ion solution varied the tone of the color formed, probably by affecting the reduction reaction between the metal ion and the nucleating agent.
  • the gold reaction with tannic acid worked better below pH 6, preferably between pH 3 and 5.
  • the temperature of the reaction also played a role: at higher temperatures (greater than 60°C to boiling), the nucleation reaction (or micro-particle formation) was faster. Because some of the reagents tended to decompose at high temperatures, most reactions were conducted at ambient temperature.
  • the colors produced by this invention were also determined by controlling the micro- particle density in the fiber and the size of the micro-particles.
  • concentration of the chosen nucleating agent primarily controlled the denisty of micro-particle formation; while the size of micro-particles was determined by the concentration of the gold ions relative to the concentration of the nucleating agent.
  • This principle was used in this invention to control micro-particle density and size; i.e., the relative concentration of the nucleating agent and the metal ion was varied to change the resulting color.
  • the color formed may be the result of forming a pure metal, a metal oxide, or other compound.
  • the character of the color was influenced not only by the metal or metal compound used, but also by the structure and chemistry of the fibers of the fabric.
  • the textiles were all purchased from Testfabrics Inc., Middlesex, New Jersey. Most tests were performed on AATCC Multifiber Adjacent Fabric, Style 1 (Lot #9464). This test fabric has strips of six different fabrics in the following order: spun acetate, bleached cotton, spun polyacrylamide (nylon 6.6), spun silk, spun vicose, and worsted wool. Larger pieces of certain fiber types used were silk habutae (Lot. #11206, style #609); acetate satin bright (Lot.
  • the first step was to incubate the textile in a nucleating agent, usually a 0.1 % aqueous solution of tannic acid.
  • a nucleating agent usually a 0.1 % aqueous solution of tannic acid.
  • the incubation time was sufficient for the nucleating agent to penetrate throughout the fibers of the fabric; e.g., for tannic acid, 30 min with heating to 65° or overnight at room temperature.
  • the incubation method depended on the density of the fiber and the amount of heat the fiber could withstand.
  • the textile was removed from the nucleating agent, rinsed in distilled water, and preferably baked dry at about 60 °C for 1 hr.
  • the effective concentration range for most nucleating agents was from about 0.01 % to 1 % in water, although other solvents such as alcohol were also used in some experiments.
  • the second step was to immerse the treated textile into a solution containing the chosen metal or compound to generate the color in situ in the fibers.
  • concentration of the metal was usually about 0.01 % W/V in water or other suitable solvent, with an effective range extending at least over the interval from about 0.001 % to about 0.1 %.
  • the incubation time necessary to produce visible colors varied widely, from a few seconds to overnight. The incubation time depended on the metal ion, the nucleating agent, the temperature, the pH, and the type of fabric.
  • different metal ions or compounds were mixed prior to immersion of the treated textile.
  • one ion was first reduced to form a core particle, and then a second ion was added to form a coating on the core.
  • a gold solution was prepared by dissolving chloroauric acid (J.T. Baker Inc.; Gold Chloride trihydrate, No. 2146-03) in distilled water and diluting to a final concentration of 0.01 % (Unless otherwise noted, all concentrations in all examples are W/V). With chloroauric acid, the final pH of the solution was about pH 4 without adjustment, which was in the desired range of about pH 3.0 to about pH 6.0. Two different nucleating agents were tested, 0.1 % tannic acid and 0.1 % sodium acetate, in two sets of experiments.
  • the textile sample was a Multifiber Fabric, style 1 (Testfabrics, Inc.) with the six different fabric types as described above in Example 1.
  • the Multifiber fabric was incubated overnight in the tannic acid solution by placing the fabric and solution in a plastic bag placed on a rocker platform at room temperature. The treated textile was then removed, rinsed in distilled water, dried at 60°C, and stored at room temperature. The dried textile was later immersed in a 0.01 % chloroauric acid solution, and again incubated in a plastic bag on the rocker platform at room temperature. After about 4 hr, the reaction was terminated by removing the textile from the gold solution. The dyed textile was rinsed in distilled water and dried. Alternatively, the gold solution and fabric may be heated to near boiling to decrease the incubation time. The colors generated by this technique are given in Table 1.
  • an acetate solution (formed by diluting a mixture of equal volumes of 0.2 M acetic acid and 0.2 M sodium acetate) was used as the nucleating agent.
  • the procedure was as described above, except that after incubating in the acetate solution, the textile was not rinsed.
  • the acetate was directly baked on the textile at 60 °C for 1 hr. To generate sufficient color, overnight incubation in 0.01 % chloroauric acid was required at room temperature.
  • the visual colors are given in Table 1.
  • the colors of the different strips were quantified using the CIELAB system of color measurement. See B.J. Collier et al. , "Ch. 10. Color and Colorfastness," in Textile Testing and Analysis, pp.197-235, eds. B.J. Collier and H. H. Epps, Prentice-Hall, Inc., New Jersey (1999).
  • the CIELAB system comprises three scales.
  • the parameter "L*” is a ratio scale measuring lightness/darkness with values ranging from zero (black) to one hundred (white).
  • the "a*” scale ranges from negative infinity (green) to positive infinity (red).
  • the "b*” scale ranges from negative infinity (blue) to positive infinity (yellow).
  • the parameter "C*” measures the vividness/dullness, with values from zero to infinity. The more positive values indicate a more vivid color.
  • the parameter "h°” measures the hue angle; a value close to 0° indicates a red color; 90°, yellow; 180°, green; and 270°, blue. Table 1 shows that using acetate as a nucleating agent resulted in lighter colors; i.e. , the L* values were higher for all fabric types. By looking at the a* (high positive numbers) and b* values (values close to zero), gold micro-particles tended to dye these fabrics a red to pink color.
  • cranberry juice was tried because the juice is known to contain a tannin (proantocyanidin). See A.B. Howell et al. , "Inhibition of the adherence of P-fimbriated Escherichia coli to uroepithelial-cell surfaces by proanthocyanidin extracts from cranberries," New England Journal of Medicine, vol. 339, pp. 1085-1086 (1998). Cranberry juice proved to be an effective nucleating agent for gold.
  • titanium was substituted for the gold solution.
  • a titanium standard solution Tianium Atomic Absorption Standard Solution, T-7646, SIGMA Chemical Co, St. Louis, Missouri
  • inexpensive titanium salts e . g . , titanium chloride and potassium bis(oxalato)oxotitanate(iv)
  • Tannic acid 0.1 %) was used as the nucleating agent.
  • the concentration of titanium was constant at 0.01 % .
  • the process steps were varied to find ways to intensify or change the coloring effects of titanium for different fabrics.
  • the Multifiber Fabric dyed by the procedure in Example 3 was used as a control.
  • the visual colors produced by each procedure were noted.
  • the color differences between each procedure and the control were calculated by the following method.
  • ⁇ a* and ⁇ b* can be calculated.
  • the overall color difference between two specimens can be designated by a single value, ⁇ E*, a term which incorporates the differences in the individual terms, L*, a*, and b*. This term ⁇ E* is calculated using the following formula:
  • ⁇ K the Kubelka-Munk coefficient of absorption
  • Procedure 2 Pretreatment with Polyethylenimine (PE). To test whether a mordant would affect binding of the tannic acid to negatively charged fiber types, the positively charged polymer polyethylenimine was tested. The Multifiber Fabric was pretreated with a 0.1 % aqueous polyethylenimine (PE) solution by incubating at 60° for 1 hr.
  • PE Polyethylenimine
  • Example 3 The procedure as described in Example 3 was followed except that a 0.1 % aqueous titanium solution was diluted to a final titanium concentration of 0.01 % with 95% ethanol.
  • the color differences are listed in Table 3. The major differences were seen in the ⁇ E* values of spun polyamide (nylon) and spun viscose, both showing a more intense color.
  • Procedure 4 Boiling the fabric with the nucleating agent; using an alcohol solution of titanium. To test whether boiling would increase the penetration of the nucleating agent into the fibers of the fabric, Procedure 3 above was repeated, except that the fabric was boiled in the tannic acid solution for 30 min. The color differences between this fabric and the fabric from Example 3 are seen in Table 3. Large increases in color density as indicated by the visual color changes and the value of ⁇ E* were seen in spun polyamide (nylon), silk, and worsted wool. Visually, the nylon changed from no color to peach (light yellow-orange), the silk from yellow to dark gold, and the wool from yellow to gold.
  • Procedure 1 Simultaneous combination of two metals.
  • the fabric was treated with 0.1 % tannic acid for 30 min at 65°, then dried for 1 hr at 60°, and then either used immediately or stored until use.
  • the dried fabric was placed in a single solution which contained the two metals of interest.
  • the combinations and concentrations of metals tested were as follows: a. Titanium and gold:
  • Titanium and Vanadium A solution of 0.01 % titanium and 0.01 % vanadium tribromide was incubated with the Multifiber Fabric at 25° for 1 hr. The colors seen in the various fabrics are given in Table 5.
  • Titanium and Zirconium A solution of 0.01 % titanium and 0.01 % vanadium tribromide was incubated with the Multifiber Fabric at 25° for 1 hr. The colors seen in the various fabrics are given in Table 5.
  • the Multifiber Fabric strip was treated with 0.1 % tannic acid for 30 min at 65°, then dried for 1 hr at 60°, and then either used immediately or stored until use.
  • the dried fabric was incubated in a solution with one metal for a set time, removed and immediately then incubated in another solution containing the second metal.
  • the combinations of metals and incubation times were as follows: a. Titanium and Palladium:
  • the Multifiber Fabric was first incubated in an aqueous 0.005% titanium dichloride solution for 30 min at 25°. The fabric was then transferred into an aqueous 0.01 % palladium chloride solution and was incubated at 25° for 2 hr.
  • the colors seen in the various fabrics are given in Table 5. b.
  • the Multifiber Fabric was first incubated in an aqueous 0.01 % ruthenium trichloride solution for 30 min at 25°. The fabric was then transferred into an aqueous 0.01 % ammonium dichromate solution and was incubated at 25° for 2 hr. The colors seen in the various fabrics are given in Table 5.
  • Iron and Chromium Iron and Chromium:
  • the Multifiber Fabric was first incubated in an aqueous 0.05% ferric chloride solution for 5-7 min at 25°. The fabric was then transferred into an aqueous 0.01 % ammonium dichromate solution and was incubated at 25° for 1.75 hr. The colors seen in the various fabrics are given in Table 5. d. Iron and Molybdenum:
  • the Multifiber Fabric was first incubated in an aqueous 0.05% ferric chloride solution for 5-7 min at 25°. The fabric was then transferred into an aqueous 0.01 % molybdenum dichloride dioxide solution and was incubated at 25° for 1.75 hr. The colors seen in the various fabrics are given in Table 5. e. Molybdenum and Ruthenium:
  • the Multifiber Fabric was first incubated in an aqueous 0.01 % ruthenium chloride solution for 30 min at 25°. The fabric was then transferred into an aqueous 0.01 % molybdenum dichloride dioxide solution and was incubated at 25° for 2 hr.
  • the colors seen in the various fabrics are given in Table 5.
  • the Multifiber Fabric was first incubated in an aqueous 0.01 % molybdenum dichloride dioxide solution for 2 hr at 25°. The fabric was then transferred into an aqueous 0.01 % palladium chloride solution and was incubated at 25° overnight.
  • the colors seen in the various fabrics are given in Table 5.
  • Procedure 3 Combination of three metals.
  • the fabric was treated with 0.1 % tannic acid for 30 min at 65°, then dried for 1 hr at 60°, and either used immediately or stored until use.
  • the dried fabric was then incubated either with all metals at once or in a sequence of metals as described below: a. Titanium, zirconium, and gold (in alcohol)
  • the Multifiber Fabric was first incubated in an aqueous solution comprising 0.01 % titanium and 0.05% zirconyl chloride for 30 min at 25°. The fabric was then transferred into a 0.01 % chloroauric acid solution in 47% ethanol overnight at 25°. The colors seen in the various fabrics are given in Table 5.
  • the Multifiber Fabric was first incubated in an aqueous solution comprising 0.01 % titanium and 0.05% zirconyl chloride for 1 hr at 25°. The fabric was then transferred into a 0.01 % ruthenium chloride solution for 1 hr at 25°. The colors seen in the various fabrics are given in Table 5. c. Vanadium, titanium, and zirconium
  • Samples of silk habutae and acetate satin bright were each incubated in an aqueous solution containing 0.01 % titanium, 0.01 % zirconyl chloride, and 0.04% vanadium tribromide for 1 hr at 25°.
  • the color generated on both fabric types was green.
  • the intensity and hue of the green could be changed by varying the ratios of the ions and the time of incubation.
  • the visual colors ranged from grey-green to yellow-green.
  • a Multifiber Fabric was dyed using titanium, zirconium, and gold as described above in Example 6, Procedure 3a, and then placed in a, 3% hydrogen peroxide solution overnight.
  • the fibers of spun diacetate and spun acrylamide did not change color.
  • the other fibers changed colors as follows: cotton changed from yellow-brown to light purple; spun silk, from yellow to green; spun vicose, from gold to light purple; and worsted wool, from beige to light purple beige.
  • hydrogen peroxide was able to change the hue of the fabric color after the deposition of the micro-particles, when ethanol was used in the solvent for the gold overlay.
  • the hydrogen peroxide did not change the color of any of the fibers.
  • the slices were examined under a Zeiss EM-10 electron microscope. Discrete electron dense gold particles were found dispersed throughout the fibers of both the silk and the viscose rayon. The gold particles seen were more irregular in shape and more varied in size than gold particles formed in solutions as sols. The electron micrographs confirmed that the micro-particles had become an integral part of the fiber. For example, the irregular features of the micro-particles often appeared to be closely associated with and continuous with the fibers; and the micro- particles were also seen scattered throughout the substructure of the fibers, indicating good penetration of the reagents into the fibers. The approximate size range of the particles formed within the fibers was from about 5 to 80 ran in diameter. The particles formed throughout the silk fibers were smaller and in greater numbers than those formed throughout the vicose fibers.
  • Four samples of viscose were tested: one dyed with gold; one with titanium; one with platinum; and one without color.
  • Two samples of TENCEL ® were tested: one colored with a combination of titanium and zirconium; and one without color.
  • the sources of all fabrics and chemicals are as described in Example 1. After dyeing, the CIELAB Coordinates of all samples were measured and are shown in Table 6, part I.
  • a second set of measurements to monitor color change ratings was the AATCC Gray Scale for Color Change.
  • the samples and the L4 blue wool standard were rated after 20 hr, 40 hr, and 60 hr light exposure. The values are shown in Table 7. After 20 hr, all samples rated 5 (no change) or 4-5 (slightly noticeable change), thus showing little color change after 20 hr exposure.
  • the purple (Au-viscose), dark yellow (Ti-silk), light yellow (Ti-viscose), light brown (chromate-silk), and the white fabrics were given ratings of 5 or 4-5. The only exception was the white TENCEL ® control fabric, which appeared to be contaminated with color prior to exposure.
  • the fabric samples showing the most color change after 60 hr exposure were the viscose, colored with titanium to light yellow, and the TENCEL ® , colored with titanium and zirconium to light orange. However, as seen in Table 7, overall the fabrics were quite resistant to photobleaching.
  • K/S value is the ratio of radiation absorbance to light scattering at a given wavelength
  • 540 ran K/S values were taken before light exposure and then at 20 hr, 40 hr and 60 hr light exposure. The values are shown in Table 8. In most samples-, the K/S values for all exposure times are close to the pre-exposure value. This is further indication that the fabrics were colorfast after exposure for up to 60 hr of light. The greatest change in K/S values was seen for TENCEL ® colored with titanium and zirconium. The results from the K/S measurements further support the results seen from CIELAB color differences and gray scale ratings.
  • the bleach effect on the gold-colored silk was a value of two, while the effect of the bleach on the control silk was below the recordable range.
  • the bleach altered the color of the control silk substantially more than the bleach altered the color of the gold-colored silk.
  • nucleating agents including for example sodium citrate, sodium acetate, tannic acid, other tannins including but not limited to proanthocyanidin, formaldehyde, phosphorus, sodium malate, sodium ascorbate, sodium borohydride, acetone, acetylene, ethanol, oxalic acid, and substituted amines such as hydroxylamine and hydrazine.
  • other tannins including but not limited to proanthocyanidin, formaldehyde, phosphorus, sodium malate, sodium ascorbate, sodium borohydride, acetone, acetylene, ethanol, oxalic acid, and substituted amines such as hydroxylamine and hydrazine.
  • the negative surface charge of colloidal gold sols can be used to add additional products to the surface of the particle. However, if left unblocked, the charge could attract cations and dirt, which could change the character of the color. For example, by reacting the gold dye with sodium ions, the color is changed to a brownish red. It may be desirable to block the surface, either by standard industry methods, or by using high molecular weight polyethylene glycol, a known blocker of gold sols, to prevent undesired binding.
  • Agents known to be protecting agents for hydrophobic colloidal particles include polyacrylic acid hydrazide, gelatin, polyvinylpyrrolidone, casein, amorphous egg albumin, ovomucoid, polyvinylalcohol, gum arabic, chondroitin sulfate, polyacrylamide, polyacrolein, heparin, gum tragacanth, crystallized egg albumin, polyacrylic acid, sodium alginate, pepsin, polyethylenimine, trypsin, potato starch, copolymer of 4-vinylpyridine and methyl vinyl ketone, dextrin (British gum), cane sugar, and urea. See K. Park et al. , 1989.
  • transition element or “transition metal” means the elements on the periodic table from atomic number 21 through 30 (scandium through zinc), 39 through 48 (yttrium through cadmium), 57 through 80 (lanthanum through mercury), and 89 through 92 (actinium through uranium). (The transuranic elements, while theoretically usable in the present invention, would not be practical for obvious reasons.)

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Des microparticules de métaux de transition ou de leurs composés peuvent être produites comme faisant partie intégrante d'une fibre textile, d'abord par fixation d'un agent de nucléation à la fibre puis par adjonction d'une solution d'ions métalliques. Ces ions sont réduits par l'agent de nucléation dans la fibre et les microparticules sont produites dans ou sur la fibre. En raison de l'intense signal de couleur résultant d'une faible concentration des microparticules de métal, ce procédé est rentable même lorsqu'on utilise des ions d'or ou de titane. Diverses couleurs ont été produites par modification de la taille et de l'espacement des microparticules, par modification du métal ou du complexe métallique utilisé et par modification des caractéristiques du textile. Après teinture, le textile présentait des couleurs comprises dans la gamme des couleurs rose, rouge, pourpre, jaune, orange, pêche, brun, or, argent, gris, vert et noir. Ces couleurs ont résisté au blanchiment par des agents chimiques ou par la lumière.
PCT/US1999/002306 1999-02-03 1999-02-03 Teinture stable par formation in situ de microparticules Ceased WO2000046438A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018166A1 (fr) * 2001-08-20 2003-03-06 Zimmer Aktiengesellschaft Procede de retrait de metaux lourds contenus dans des substances comprenant des metaux lourds au moyen d'un corps moule en lyocell, corps moule cellulosique ayant adsorbe des metaux lourds et son utilisation
DE102006049108A1 (de) * 2006-10-13 2008-04-17 Largentec Gmbh Bioaktive, rutheniumhaltige Beschichtung und Vorrichtung
FR2997101A1 (fr) * 2012-10-18 2014-04-25 Holding Textile Hermes Procede de fabrication d'un textile a effet de coloration variable contenant de l'or ou au moins un alliage contenant de l'or sous forme de particules et textile a effet de coloration variable.
CN114517417A (zh) * 2022-01-06 2022-05-20 常州大学 一种植物染料染色抗菌纺织品的制备方法

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US3140878A (en) * 1962-10-05 1964-07-14 Thomas E Davis Sled
US3290703A (en) * 1964-09-24 1966-12-13 K & W Entpr Inc Pillow covering
US4910055A (en) * 1987-03-23 1990-03-20 Wigutow Jerald N Insulated sleeping bag
US5246401A (en) * 1992-03-02 1993-09-21 Albert Boatwright Flexible sled and slide construction

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Publication number Priority date Publication date Assignee Title
US3140878A (en) * 1962-10-05 1964-07-14 Thomas E Davis Sled
US3290703A (en) * 1964-09-24 1966-12-13 K & W Entpr Inc Pillow covering
US4910055A (en) * 1987-03-23 1990-03-20 Wigutow Jerald N Insulated sleeping bag
US5246401A (en) * 1992-03-02 1993-09-21 Albert Boatwright Flexible sled and slide construction

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018166A1 (fr) * 2001-08-20 2003-03-06 Zimmer Aktiengesellschaft Procede de retrait de metaux lourds contenus dans des substances comprenant des metaux lourds au moyen d'un corps moule en lyocell, corps moule cellulosique ayant adsorbe des metaux lourds et son utilisation
US7314570B2 (en) 2001-08-20 2008-01-01 Zimmer A.G. Method for removing heavy metals from media containing heavy metals by means of a Lyocell moulded body, cellulosic moulded body comprising absorbed heavy metals, and the use of the same
DE102006049108A1 (de) * 2006-10-13 2008-04-17 Largentec Gmbh Bioaktive, rutheniumhaltige Beschichtung und Vorrichtung
US9701848B2 (en) 2006-10-13 2017-07-11 Agxx Intellectual Property Holding Gmbh Bioactive, ruthenium-containing coating and device
DE102006049108B4 (de) * 2006-10-13 2019-05-02 Agxx Intellectual Property Holding Gmbh Bioaktive, rutheniumhaltige Beschichtungen, deren Verwendung und Verfahren zur Beschichtung einer Vorrichtung
FR2997101A1 (fr) * 2012-10-18 2014-04-25 Holding Textile Hermes Procede de fabrication d'un textile a effet de coloration variable contenant de l'or ou au moins un alliage contenant de l'or sous forme de particules et textile a effet de coloration variable.
CN114517417A (zh) * 2022-01-06 2022-05-20 常州大学 一种植物染料染色抗菌纺织品的制备方法
CN114517417B (zh) * 2022-01-06 2023-05-23 常州大学 一种植物染料染色抗菌纺织品的制备方法

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CA2358507A1 (fr) 2000-08-10

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