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US20050011012A1 - Multifunctional antimicrobial dyes - Google Patents

Multifunctional antimicrobial dyes Download PDF

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Publication number
US20050011012A1
US20050011012A1 US10/804,354 US80435404A US2005011012A1 US 20050011012 A1 US20050011012 A1 US 20050011012A1 US 80435404 A US80435404 A US 80435404A US 2005011012 A1 US2005011012 A1 US 2005011012A1
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group
compound
dyes
polymer
independently selected
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Gang Sun
Minghua Ma
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University of California San Francisco UCSF
University of California San Diego UCSD
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University of California San Diego UCSD
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Priority to US10/804,354 priority Critical patent/US20050011012A1/en
Priority to PCT/US2004/008557 priority patent/WO2004083336A2/fr
Assigned to UNIVERSITY OF CALIFORNIA, SAN FRANCISCO reassignment UNIVERSITY OF CALIFORNIA, SAN FRANCISCO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MA, MINGHUA, SUN, GANG
Publication of US20050011012A1 publication Critical patent/US20050011012A1/en
Priority to US11/870,391 priority patent/US20080201871A1/en
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    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
    • C07C225/34—Amino anthraquinones
    • 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone dyes
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention relates to novel antimicrobial cationic dyes and methods for using the same.
  • the antimicrobial cationic dyes of the present invention are useful for the simultaneous dyeing and functional finishing of polymers, e.g., textiles.
  • Textile dyeing and functional finishing are two necessary but traditionally separated processes employed in textile treatments. Textile dyeing and finishing necessitate repeated wet treatments and drying, and thus consume large quantities of energy and produce large amounts of wastewater. Simultaneous dyeing and finishing of textiles in one bath provides both economical and environmental advantages in textile manufacturing. Recent studies have demonstrated that the combination of these two processes is feasible (Lewis et al., J Soc. Dyer Colorist; 113:159 (1997); Choi et al., J. Appl. Polym. Sci.; 54:2107 (1994); Kim et al., Textile Res. J.; 70(8):728 (2000); Kim et al., Textile Res. J; 71(4):318 (2001)). However, such combinations are typically based on the simple mixing of dyes, finishes, and other auxiliaries, compromising dyeing and/or finishing conditions and sacrificing the properties of the resultant textiles.
  • dyes and colorants are compounds whose electronic structures can absorb electromagnetic radiation in the visible range (380-780 nm). Additional properties other than color can be defined as functions. Based on this definition, infrared dyes, laser dyes, and voltage sensitive dyes fall within the category of functional dyes (Griffiths J., Chimia; 45:304 (1991)). However, our concept of a functional dye is more specifically associated with the traditional functions that textile fabrics or clothing materials should possess. These functions can include, for example, antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, and anti-chemical properties.
  • Acrylic fabrics are widely used synthetic fabrics due to a combination of desirable properties, such as a soft, wool-like feel, good elasticity and mechanical properties, and high resistance to outdoor exposure and to many chemical compounds (Burkinshaw, Chemical principles ofsynthetic fibre dyeing , Glasgow: Blackie Academic & Professional, Chapman & Hall (1995)). Although extensive studies have been carried out in the cationic dyeing of acrylic fabrics (Bird et al., The theory of coloration of textiles , London: Dyers Company Publications Trust (1975); Munn, The dyeing of synthetic - polymer and acetate fibres , England: Dyers Company Publications Trust (1979)), little is known about the functional finishing of acrylic fabrics.
  • the present invention provides novel functional finishing dyes comprising at least one functional finishing group covalently attached to a traditional dye via a chemical linkage (see, FIG. 1 ). More particularly, the present invention provides novel antimicrobial cationic dyes comprising a quaternary ammonium salt (QAS) group covalently attached to an aminoanthraquinioid dye via a linker.
  • the dyes are particularly useful for imparting a functional property to a polymer, such as an antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, or anti-chemical property, and for simultaneously dyeing and finishing a polymer.
  • the present invention provides a compound having the formula: wherein:
  • the present invention provides a polymer composition comprising:
  • the present invention provides a method for simultaneously dyeing and finishing a polymer, the method comprising:
  • the compounds i.e., the QAS-dyes
  • polymers e.g., textile materials
  • the QAS-dyes can be treated with the QAS-dyes to provide a biocidal protective coating on the polymers effective against a variety of microorganisms.
  • the treated polymers are suitable for use as clothing in the medical field as well as in related healthcare and hygiene areas.
  • Treated polymers of the present invention can be fabricated into disposable or reusable textile materials.
  • microbiocidal properties of the textiles of the present invention can be advantageously used for women's wear, underwear, socks, and other hygienic purposes such as upholsteries.
  • the microbiocidal properties can be imparted to carpeting materials to create odor-free and/or germ-free carpets.
  • all germ-free environments such as those required in biotechnology and the pharmaceutical industry, can benefit from the use of the microbiocidal textiles of the present invention to prevent any contamination from air, liquid, and/or solid media.
  • FIG. 1 illustrates the structure of a functional finishing dye of the present invention.
  • FIG. 2A illustrates various structures of antimicrobial QAS-dyes of the present invention.
  • FIG. 2B illustrates preferred mono- and bi-QAS substituted dyes of the present invention.
  • FIG. 3 illustrates a synthetic procedure for producing a dye of the present invention.
  • FIG. 4 illustrates the 1 H NMR spectrum of the m-4 dye.
  • FIG. 5 illustrates the 13 C NMR spectrum of the m-4 dye.
  • FIG. 6 illustrates the FTIR spectra of representative mono-QAS substituted dyes.
  • FIG. 7 illustrates the absorption spectra of a mono- and a bi-QAS substituted dye of the present invention in an aqueous solution.
  • FIG. 8 illustrates the three types of hydrogen bonding in aqueous solutions: (a) intramolecular; (b) intermolecular; and (c) with water molecules.
  • FIG. 9 illustrates the effect of dyeing time on an acrylic dyeing process (dye concentration: 1 mMol/L, pH: 3; bath ratio: 1:50; dyeing temperature: 100° C.).
  • FIG. 10 illustrates the effect of dye concentration on an acrylic dyeing process (pH: 3; bath ratio: 1:50; initial dyeing temperature: 95° C. for 50 min.; fixation: 100° C. for 10 min.).
  • FIG. 11 illustrates the effect of initial dyeing temperatures on an acrylic dyeing process (dye concentration: 1 mMol/L; pH: 3; bath ratio: 1:50; initial dyeing: 50 min.; fixation: 100° C. for 10 min.).
  • FIG. 12 illustrates the FTIR spectra of (A) untreated Orlon; (B) Orlon dyed with m-4 (dye concentration: 1 mMol/L; pH: 3; bath ratio: 1:50; initial dyeing: 100° C. for 50 min.; fixation: 100° C. for 10 min.); (C) difference spectrum of B and A (i.e., subtracting A from B); and (D) pure m-4.
  • FIG. 13 illustrates the FTIR spectra of (A) untreated Orlon; (B) Orlon treated with bi-12 (dye concentration: 1 mMol/L; pH: 3; bath ratio: 1:50; initial dyeing: 100° C. for 50 min.; fixation: 100° C. for 10 min.), (C) difference spectrum of B and A (i.e., subtracting A from B); and (D) pure bi-12.
  • FIG. 14 illustrates the FTIR spectra of (A) untreated Orlon; (B) Orlon treated with m-4; (C) Orlon treated with m-8; (D) Orlon treated with m-12; (E) Orlon treated with bi-4; (F) Orlon treated with bi-8; and (G) Orlon treated with bi-12 (dye concentration: 1 mMol/L; pH: 3; bath ratio: 1:50; initial dyeing: 100° C. for 50 min.; fixation: 100° C. for 10 min.).
  • FIG. 15 illustrates surface resistivity of an inventive Orlon fabric.
  • FIG. 16 illustrates the DSC curves of a mono-QAS substituted dye.
  • FIG. 17 illustrates the TGA curves of a mono-QAS substituted dye.
  • FIG. 18 illustrates the UV-vis absorption spectra of m-4 at pH 5 and at 100° C. (original dye concentration: 0.4 mMol/L).
  • FIG. 19 illustrates the 1 H NMR spectrum of 1-amino anthraquinone (solvent: DMSO-d 6 ).
  • FIG. 20 illustrates the 1 H NMR spectrum of carboxymethyl-butyl-dimethyl ammonium chloride (CBDAC).
  • FIG. 21 illustrates the 13 C NMR spectrum of CBDAC.
  • FIG. 22 illustrates the 1 H NMR spectrum of 1,4-diaminoanthraquinone.
  • FIG. 23 illustrates the stability of a mono-QAS substituted dye at different pH and at 100° C. (original dye concentrations: 1 mMol/L).
  • FIG. 24 illustrates the stability of a bi-QAS substituted dye at different pH and at 100° C. (original dye concentrations: 1 mMol/L).
  • Alkyl refers to a saturated linear monovalent hydrocarbon radical or a saturated branched monovalent hydrocarbon radical containing from 1 to 20 carbon atoms.
  • the alkyl radical contains from 1 to 4 carbon atoms (i.e., C 1 -C 4 alkyl) or from 4 to 18 carbons atoms (i.e., C 4 -C 18 alkyl).
  • Exemplary alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, 2-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like.
  • Alkylene refers to a saturated linear divalent hydrocarbon radical or a saturated branched divalent hydrocarbon radical containing from 1 to 20 carbon atoms.
  • the alkylene radical contains from 1 to 12 carbon atoms (i.e., C 1 -C 12 alkylene).
  • Exemplary alkylene groups include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, and the like.
  • cycloalkyl refers to a cyclic alkyl radical containing from 3 to 8, preferably from 3 to 6, carbon atoms.
  • exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • cycloalkylene refers to a cyclic carbocycle radical containing from 4 to 8, preferably 5 or 6, carbon atoms and one or more double bonds.
  • exemplary cycloalkylene groups include, but are not limited to, cyclopentylene, cyclohexylene, cyclopentadienylene, and the like.
  • aryl refers to a carbocyclic aromatic radical selected from the group consisting of phenyl, naphthyl, indenyl, indanyl, azulenyl, fluorenyl, anthracenyl, and the like; or a heterocyclic aromatic radical selected from the group consisting of furyl, thienyl, pyridyl, pyrrolyl, oxazolyly, thiazolyl, imidazolyl, pyrazolyl, 2-pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,3,5-trithianyl, indolizinyl, indolyl, isoindolyl,
  • the aryl group can also have from one to five substituents selected from the group consisting of hydrogen, halogen, hydroxyl, amino, nitro, trifluoromethyl, trifluoromethoxy, alkyl, alkylene, alkynyl, 1,2-dioxymethylene, 1,2-dioxyethylene, alkoxy, alkenoxy, alkynoxy, alkylamino, alkenylamino or alkynylamino, alkylcarbonyloxy, aliphatic or aromatic acyl, alkylcarbonylamino, alkoxycarbonylamino, alkylsulfonylamino, N-alkyl, N,N-dialkyl urea, and the like.
  • alkoxyl refers to an alkyl ether radical containing from 1 to 20 carbon atoms.
  • exemplary alkoxyl groups include, but are not limited to, methoxyl, ethoxyl, n-propoxyl, iso-propoxyl, n-butoxyl, iso-butoxyl, sec-butoxyl, tert-butoxyl, and the like.
  • alkylamino refers to a mono- or di-alkyl-substituted amino radical (i.e., a radical having the formula: alkyl-NH— or (alkyl) 2 —N—), wherein the term “alkyl” is as defined above.
  • exemplary alkylamino groups include, but are not limited to, methylamino, ethylamino, propylamino, iso-propylamino, t-butylamino, N,N-diethylamino, and the like.
  • aralkyl refers to an aryl radical, as defined herein, attached to an alkyl radical, as defined herein.
  • cycloalkylalkyl refers to a cycloalkyl radical, as defined herein, attached to an alkyl radical, as defined herein.
  • heteroatom refers to any atom that is not carbon or hydrogen.
  • exemplary heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, phosphorus, boron, and the like.
  • the term “functional finishing dye” refers to a dye containing at least one functional finishing group covalently attached to the dye via a chemical linkage.
  • the term “functional finishing group” refers to a moiety that is present in a functional finishing dye which imparts a particular functional property to the dye-treated polymer.
  • ⁇ refers to a particular non-inherent and/or enhanced physical property of the polymer due to the presence of a functional finishing group.
  • exemplary functional properties include, but are not limited to, antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, and anti-chemical properties, as well as a combination of two or more properties thereof.
  • Leaving group has the meaning conventionally associated with it in synthetic organic chemistry, i.e., an atom or a group capable of being displaced by a nucleophile, and includes halo (such as chloro, bromo, and iodo), alkanesulfonyloxy, arenesulfonyloxy, alkylcarbonyloxy (e.g., acetoxy), arylcarbonyloxy, mesyloxy, tosyloxy, trifluoromethanesulfonyloxy, aryloxy (e.g., 2,4-dinitrophenoxy), methoxy, N,O-dimethylhydroxylamino, and the like.
  • halo such as chloro, bromo, and iodo
  • alkanesulfonyloxy arenesulfonyloxy
  • alkylcarbonyloxy e.g., acetoxy
  • arylcarbonyloxy mesyloxy, tosyl
  • antimicrobial refers to the ability to kill at least some types of microorganisms, or to inhibit the growth or reproduction of at least some types of microorganisms.
  • the polymers prepared in accordance with the present invention have microbicidal (i.e., antimicrobial) activity against a broad spectrum of pathogenic microorganisms.
  • the polymer is a textile
  • the textiles have microbicidal activity against representative gram-positive (e.g., Staphylococcus aureus ) and gram-negative (e.g., Escherichia coli ) bacteria.
  • quaternary ammonium salt group refers to an amphipathic molecule that contains both a hydrophilic portion and a hydrophobic portion and is covalently attached to a dye.
  • the quaternary ammonium salt group has the formula: —N(R 3 )-L-N + (R 4 )(R 5 )(R 6 )-X ⁇ , Ia wherein:
  • the term “treating,” “contacting,” or “reacting” refers to adding or mixing two or more reagents under appropriate conditions to produce the indicated and/or the desired product. It should be appreciated that the reaction which produces the indicated and/or the desired product may not necessarily result directly from the combination of two reagents which were initially added, i.e., there may be one or more intermediates which are produced in the mixture which ultimately leads to the formation of the indicated and/or the desired product.
  • the present invention provides novel functional finishing dyes comprising at least one functional finishing group covalently attached to a traditional dye via a chemical linkage. More particularly, the present invention provides novel antimicrobial cationic dyes comprising a quaternary ammonium salt (QAS) group covalently attached to an aminoanthraquinioid dye via a linker.
  • the dyes are particularly useful for imparting a functional property to a polymer, such as an antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, or anti-chemical property, and for simultaneously dyeing and finishing a polymer.
  • Polymers suitable for use in the present invention include, but are not limited to, textiles.
  • Suitable textiles include, without limitation, fibers from plants, polymers from animals, natural organic polymers, synthetic organic polymers, inorganic substances, and combinations thereof.
  • the textile is selected from the group consisting of fibers from plants such as cellulose, cotton, linen, hemp, jute, wood pulp, paper, and ramie; polymers derived from animals such as wool, mohair, vicuna, and silk; manufactured fibers that are based on natural organic polymers such as rayon, lyocell, acetate, triacetate, and azlon; synthetic organic polymers such as nylon, polyester, a polyester/cellulose blend, acrylic, aramid, olefin, spandex, vinyon, vinyl, graphite, an aromatic polyamide; inorganic substances such as glass, a metallic material, and a ceramic material; and combinations thereof.
  • plants such as cellulose, cotton, linen, hemp, jute, wood pulp, paper, and ramie
  • polymers derived from animals such as wool, mohair, vicuna, and silk
  • manufactured fibers that are based on natural organic polymers such as rayon, lyocell, acetate, triacetate, and azl
  • Various textiles are preferred to practice the invention. These include, but are not limited to, a fiber, a yarn, or a natural or synthetic fabric.
  • Various fabrics include, but are not limited to, a nylon fabric, a polyester fabric, an acrylic fabric, NOMEX®, KEVLAR®, a triacetate fabric, an acetate fabric, a cotton fabric, a wool fabric, and a fabric that is made from a combination of two or more materials thereof.
  • NOMEX® is made of an aromatic polyamide material and is available from DuPont (Wilmington, Del.). NOMEX® is used in fire fighting equipment.
  • acrylic fiber refers to any manmade fiber derived from acrylic resins comprising a minimum of 85% acrylonitrile.
  • Acrylic fiber is a manufactured fiber in which the fiber forming substance is any long-chain synthetic polymer comprising at least 85% by weight of acrylonitrile units (—CH 2 —CH[CN]—) x .
  • Suitable acrylic fibers for use in the present invention include, but are not limited to, Orlon®, MicroSupreme®, CresloftTM, Creslan® Plus, BioFreshTM, WeatherBlocTM (commercially available from Sterling Fibers, Inc.), DralonTM (commercially available from Bayer Inc.), Acrilan®, Bounce-Back®, Duraspun®, Pil-Trol®, Sayelle®, Sno-BriteTM, The Smart Yarns®, Wear-Dated®, Wintuk® (commercially available from Solutia Inc.), Acrilin® acrylic, Dolan®, Dralon®, Vinyon N®, Dynel®, Verel®, and SEF modacrylic®. Those of skill in the art will know of other manufactures and trade names of acrylic fibers suitable for use in the present invention.
  • Additional polymers suitable for use in the present invention include, but are not limited to, plastics, rubber, paint, a surface coating, an adhesive, and a combination of two or more thereof.
  • Suitable plastics include, without limitation, polyethylene, polypropylene, polystyrene, polyvinylchloride, polyamideimide, polyethersulfone, polyarylsulfone, polyetherimide, polyarylate, polysulfone, polycarbonate, polyetherketone, polyetheretherketone, polytetrafluoroethylene, nylon-6,6, nylon-6,12, nylon-11, nylon-12, and acetal resin plastic materials, as well as combinations thereof.
  • finished textiles can advantageously be used in the preparation of the following articles/garments: surgeon's gowns, caps, masks, surgical covers, patient drapes, carpeting, bedding materials, underwear, socks, uniforms, and the like.
  • finished textiles of the present invention can advantageously be used for a variety of other purposes, such as in hotel-use towels, bedding materials, hygienic products, clothing to protect against pesticides and other toxic chemicals, and the like.
  • the functional finishing dyes of the present invention are comprised of a functional finishing group covalently attached to a dye moiety via a linker (see, FIG. 1 ).
  • a linker see, FIG. 1 .
  • the functional finishing group can be covalently attached to the dye moiety without the use of a linker.
  • Suitable dyes include, without limitation, cationic dyes such as basic red 9, basic blue 9, basic blue 69, basic blue 22, basic orange 14, basic green 1, basic yellow 1, basic violet 2, basic brown 1, and other basic dyes; acid dyes such as an Acid Black dye, an Acid Blue dye, an Acid Orange dye, an Acid Red dye, an Acid Violet dye, and an Acid Yellow dye; disperse dyes such as Disperse Blue 1, Disperse Yellow 7 and Disperse Yellow 9; and combinations thereof.
  • Direct dyes and reactive dyes are also suitable for use in the present invention.
  • the dye is an aminoanthraquinioid dye such as 1-aminoanthraquinone and 1,4-diaminoanthraquinone.
  • Suitable functional finishing groups are also well known to those skilled in the art.
  • the functional finishing group imparts a particular non-inherent and/or enhanced physical property, i.e., a functional property, to the polymer.
  • exemplary functional properties include, but are not limited to, antimicrobial, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, and anti-chemical properties, as well as a combination of two or more properties thereof.
  • the functional finishing group is a quaternary ammonium salt group that imparts antimicrobial and/or anti-static properties to the polymer.
  • a wide variety of functional finishing dyes can be prepared in accordance with the present invention.
  • Such functional finishing dyes allow polymers (e.g., textile materials) to be dyed and functionalized simultaneously in a single treatment process, thereby reducing the overall cost and time for producing dyed and functionalized polymers.
  • a linker between the dye and the functional finishing group can be optional depending on the reactive groups that are present on the dye and the functional finishing group.
  • complementary reactive groups are present in the dye and the functional finishing group, they can be covalently attached without the need for any additional linker.
  • the reactive groups that are present in the dye and the functional finishing group are not complementary reactive groups, one of the reactive groups can be converted to a complementary reactive group, or a linker having appropriate complementary reactive groups can be used to covalently link the dye and the functional finishing group.
  • the linker comprises a 1-12 carbon atom chain that can be interrupted with one or more heteroatoms. Suitable carbon atom chains include, without limitation, an alkylene group, a —C(O)R group, wherein R is an an alkylene group, and an alkylamino group.
  • the functional finishing dye is a QAS-aminoanthraquinioid dye conjugate, i.e., QAS-dye, having the formula: wherein:
  • the quaternary ammonium salt group has the formula: —N(R 3 )-L-N + (R 4 )(R 5 )(R 6 )-X ⁇ , Ia wherein:
  • the R 4 and R 5 groups in the quaternary ammonium salt group are each independently selected C 1 -C 4 alkyl groups, and R 6 is a C 4 -C 18 alkyl group.
  • the R 4 and R 5 groups in the quaternary ammonium salt group are methyl groups, and R 6 is a C 4 -C 18 alkyl group.
  • Suitable R 6 groups include, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups.
  • the R 6 group is an octyl or a dodecyl group.
  • X is independently selected from the group consisting of F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , and combinations thereof.
  • the substituent group is independently selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, sulfonate, hydroxyl, alkoxyl, amino, and alkylamino groups.
  • m is 0.
  • n is 1 or 2.
  • a particularly preferred compound of formula I is of the formula: wherein R 1 , R 2 , and m are as defined above.
  • the compound of formula IIa has the following structure: wherein:
  • R 4 and R 5 are methyl groups.
  • R 6 is an octyl or a dodecyl group.
  • R 7 is a —CH 2 or a —C(O)CH 2 group.
  • X is independently selected from the group consisting of F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , and combinations thereof.
  • the compound of formula IIb has the following structure: wherein
  • R 4 , R 5 , R 10 , and R 11 are methyl groups.
  • R 6 and R 12 are independently selected octyl or dodecyl groups.
  • R 7 and R 9 and independently selected —CH 2 or —C(O)CH 2 groups.
  • X is independently selected from the group consisting of F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , and combinations thereof.
  • FIG. 2A shows various structures of the antimicrobial QAS-dyes according to one embodiment of the present invention.
  • the functional finishing dyes of the present invention can be prepared by a variety of methods known to one skilled in the art, including, without limitation, solid-phase, solution-phase, and combinatorial synthesis. It should be appreciated that although the following schemes for producing compounds of Formula I often indicate exact structures, methods of the present invention apply widely to analogous compounds of Formula I as well as to other dyes known to one skilled in the art given an appropriate consideration to protection and deprotection of reactive functional groups by methods standard to the art of organic chemistry. For example, in order to prevent unwanted side reactions, hydroxyl groups sometimes need to be converted to ethers or esters during chemical reactions at other sites in the molecule. The hydroxyl protecting group is then removed to provide the free hydroxyl group.
  • amino groups and carboxylic acid groups can be derivatized to protect them against unwanted side reactions.
  • Typical protecting groups, and methods for attaching and cleaving them, are described fully in, for example, T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3 rd edition, John Wiley & Sons, New York, 1999, and Harrison and Harrison et al., Compendium of Synthetic Organic Methods, Vols. 1-8 (John Wiley and Sons, 1971-1996), which are incorporated herein by reference in their entirety.
  • the presence of a linker between the dye and the functional finishing group is optional depending on the reactive groups that are present on the dye and the functional finishing group.
  • the following is intended to be a mere illustration of one particular synthetic strategy that can be employed in producing the functional finishing dyes of the present invention. It should be appreciated that methods for preparing functional finishing dyes are not limited to those specifically disclosed herein as one skilled in the art can readily adapt other synthetic strategies and chemical reactions that are generally known to such a skilled artisan to derive other functional finishing dyes.
  • the linker compound 2 comprises two different reactive functional groups such that one of the reactive functional group reacts preferentially with the amino group of the anthraquinone compound 1.
  • the linker compound 2 can comprise an activated acyl group, e.g., acyl halide, alkyl halide, epoxide, or anhydride, and a leaving group for a nucleophilic substitution reaction.
  • the activated acyl group i.e., X 1
  • Suitable reaction conditions for coupling an amino group with an activated acyl group are well known to one skilled in the art and typically involve reacting the two groups at reduced temperature, e.g., 0° C.
  • a base and/or a coupling catalyst can optionally be added to the reaction mixture to neutralize any acid that may be generated and/or to facilitate the coupling reaction, respectively.
  • the di-substituted aminoanthraquinone 3 can optionally be purified prior to reacting with a tri-substituted amine compound 4 to produce a quaternary ammonium salt substituted anthraquinone 5.
  • this second coupling reaction typically involves a nucleophilic substitution reaction where the amino group of the tri-substituted amine compound 4 displaces the leaving group X 2 on the di-substituted aminoanthraquinone 3.
  • Suitable reaction conditions for a nucleophilic substitution reaction are known to one skilled in the art and often involve elevated reaction temperatures, i.e., >25° C. and preferably >50° C.
  • FIG. 3 shows a representative synthetic scheme for the mono-QAS substituted dyes of the present invention.
  • the present invention also provides a polymer that is coated with the functionalized finishing dyes described above.
  • the present invention provides a polymer composition comprising:
  • Such polymers can be readily prepared using any one of conventional dyeing processes known to one skilled in the art. However, unlike conventional dyeing processes, methods of the present invention utilize the functional finishing dye described herein. In this manner, what is typically a two-step process of dyeing and finishing a polymer is achieved in a single process, thereby significantly reducing the overall cost and time.
  • a polymer to be treated is immersed in a treating solution, typically an aqueous solution.
  • the treating solution comprises a functional finishing dye of the present invention.
  • the polymer is immersed in the treating solution for a period of time and under conditions appropriate to achieve a sufficient amount of polymer coating to produce a desired or favorable functional finishing dye-coated polymer, i.e., dye-treated polymer.
  • the treated polymer is removed from the treating solution and dried.
  • the present invention provides a method for simultaneously dyeing and finishing a polymer, the method comprising:
  • the method further comprises removing excess aqueous treating solution from the polymer.
  • the excess aqueous treating solution can be removed with or without washing the polymer.
  • the method further comprises drying the article after removing excess aqueous treating solution to produce a dried polymer.
  • the aqueous treating solution further comprises a wetting agent.
  • wetting agent refers to a substance that increases the rate at which a liquid spreads across the polymer surface, i.e., it renders the polymer surface nonrepellent to a liquid.
  • suitable wetting agents include, but are not limited to, Triton X-100 (Sigma Chemical Co., St. Louis, Mo.), SEQUAWET® (Sequa Chemical Inc., Chester, S.C.), and AMWET® (American Emulsions Co., Dalton, Ga.).
  • Other wetting agents suitable for use in the present invention will be known to and used by those of skill in the art.
  • additives can also be present in the aqueous treating solution to impart additional characteristics to the polymer.
  • additives include, but are not limited to, anti-static, softening, water-repellent, fire-resistant, soil-repellent, anti-UV, anti-chemical, and other antimicrobial agents, as well as a combination of two or more agents thereof.
  • agents known to and used by those of skill in the art are also suitable additives.
  • softeners which can be added to the aqueous treating solution include, but are not limited to, MYKON® and SEQUASOFT®, both of which are commercially available from Sequa Chemical Inc. (Chester, S.C.).
  • water-repellent agents which can be added to the aqueous treating solution include, but are not limited to, SEQUAPEL® (Sequal Chemical Inc., Chester, S.C.), SCOTCHGARD (3M, St. Paul, Minn.), and other water-repellent finishing solutions known to and used by those of skill in the art.
  • the concentration of the various components of the treating solution can be varied widely depending on the particular components employed and the results desired.
  • the functional finishing dye is present at a concentration of at least about 0.5% wt/vol. (g/mL). More typically, the functional finishing dye is present at a concentration ranging from about 0.1% wt/vol. to about 10% wt/vol., preferably at a concentration ranging from about 0.5% to about 5%, and more preferably at a concentration ranging from about 0.5% to about 2%. It will be readily apparent to those of skill in the art that higher functional finishing dye concentrations (e.g., 50% or more) can be employed, but such higher concentrations are not required to impart functionality to the polymer.
  • the wetting agent is typically present at a concentration ranging from about 0.1% to about 3%, preferably at a concentration ranging from about 0.2% to about 1%.
  • the pH of the treating solution will typically range from a pH of about 2 to about 6 and, preferably, from a pH of about 2.5 to about 4.5. In a particularly preferred embodiment, the pH of the treating solution is about 3.
  • the polymer is preferably a textile.
  • the textile can be roving, yarn, or fabric regardless of whether spun, knit, or woven, or can be non-woven sheets or webs.
  • the textile can be made of cellulosic fibers, polyester fibers, or a blend of these.
  • other polymer materials having reactive functional groups e.g., —OH groups
  • Such polymer materials include, but are not limited to, polyvinyl alcohol (PVA), starches, and proteins.
  • PVA polyvinyl alcohol
  • ordinary textile equipment and methods suitable for batchwise or continuous passage of roving, yarns, or fabrics through an aqueous solution can be used, at any speed permitting thorough and uniform wetting of the textile material.
  • the excess treating solution can be removed by ordinary mechanical methods such as by passing the treated polymer between squeeze rolls, by centrifugation, by draining, or by padding. In a preferred embodiment, the excess treating solution is removed by padding.
  • the treated polymer is then typically dried at a temperature ranging from about 50° C. to about 90° C., and more preferably at a temperature ranging from about 75° C. to about 85° C. for a period of time ranging from about 3 to about 8 minutes, preferably for about 5 minutes. Drying of treated polymer can be carried out using any ordinary means such as oven drying, line drying, or tumble drying in a mechanical clothes dryer.
  • the present invention provides a composition for finishing polymers such as textiles.
  • the composition comprises a functional finishing dye described herein.
  • the composition can also include a wetting agent.
  • the composition further includes one or more additives to impart favorable characteristics.
  • the description above pertaining to the functional finishing dyes, wetting agents, additives, and their various concentrations are fully applicable to this composition and, thus, such discussions will not be repeated again.
  • the pH of the composition typically range from a pH of about 2 to about 6, and preferably from a pH of about 2.5 to about 4.5.
  • the above composition can be prepared in a concentrated form or, alternatively, in a form suitable for immediate use, i.e., at appropriate reagent concentrations.
  • Quaternary ammonium salts are antimicrobial compounds. QAS inactivate microorganisms by disturbing their cytoplasmic membrane and have been widely used as surface disinfectants and antimicrobial finishing agents in textiles. See, for example, Kim et al., Textile Res. J.; 70:728 (2000); Kim et al., Textile Res. J.; 71:318 (2001); and Latlief et al., J. Pediatrics; 39:730 (1951). Meanwhile, anthraquinioid structures are excellent chromophores and have been widely used as dyes. Therefore, by incorporating both QAS and anthraquinone structures, compounds of Formula I can be used simultaneously as dyes and functional finishing groups.
  • the polymers treated with a compound of formula I have microbiocidal activity against a broad spectrum of pathogenic microorganisms.
  • such polymers have microbiocidal activity against representative gram-positive (e.g., Staphylococcus aureus ) and gram-negative bacteria (e.g., Escherichia coli ).
  • finished textiles can advantageously be used in the preparation of the following articles/garments: surgeon's gowns, caps, masks, surgical covers, patient drapes, carpeting, bedding materials, underwear, socks, uniforms, and the like.
  • finished textiles of the present invention can advantageously be used for a variety of other purposes, such as in hotel-use towels, bedding materials, hygienic products, clothing to protect against pesticides and other toxic chemicals, and the like.
  • the polymers of the present invention can be used as microbiocidal protective clothing for personnel in the medical field as well as in related healthcare and hygiene areas.
  • the functional properties of the dyes of the present invention can be imparted to carpeting materials to create odor-free and germ-free carpets.
  • all germ-free environments such as those required in biotechnology and in the pharmaceutical industry, can benefit from the use of the microbicidal polymers of the present invention to prevent any contamination from air, liquid, and/or solid media.
  • the treated polymers of the present invention are effective against a wide range of microorganisms including, but not limited to, bacteria, protozoa, fungi, viruses and algae.
  • the treated polymers described herein can be employed in a variety of disinfecting applications, such as water purification. They will be of importance in controlling microbiological contamination or growth of undesirable organisms in the medical and food industries.
  • they can be used as preservatives and preventatives against microbiological contamination in paints, coatings, and on surfaces.
  • 1,4-diaminoanthraquinone (90%, Aldrich) was purified by repeated crystallization from acetone.
  • 1-aminoanthraquinone (97%, Aldrich), chloroacetyl chloride (98%, Acros), N,N-dimethylbutylamine (99%, Aldrich), N,N-dimethyloctylamine (97%, Acros), N,N-dimethyldodecylamine (95%, Acros) were used as received.
  • the melting points of the samples were measured using a Shimadzu DSC-50 instrument at a heating rate of 10° C. min ⁇ 1 under a N 2 atmosphere.
  • FTIR spectra were taken on a Nicolet Magana IR-560 spectrometer using KBr pellets. The samples were made thin enough to ensure that the Beer-Lambert law was obeyed.
  • 1 H-NMR and 13 C-NMR spectra were recorded on a Varian Mercury 300 spectrometer.
  • Electronic absorption spectra were recorded on a Hitachi U-2000 spectrophotometer.
  • Acetylation of the ⁇ -aminoanthraquinioid (AQ) group was achieved according to the procedures disclosed by Martelli et al. in J. Med. Chem.; 31(10):1956 (1988).
  • the second step was a quaternization of the primary chloride with different tertiary amines.
  • the synthetic procedure is outlined in FIG. 3 .
  • the structures of the compounds prepared are presented in FIG. 2B .
  • This example illustrates the antimicrobial activities of some of the representative compounds of Formula I.
  • the antimicrobial properties of some of the functional finishing dyes of Formula I were evaluated using a minimum inhibitory concentration (MIC).
  • MIC is the concentration at which no growth of bacteria was observed following such a procedure. See, for example, Kaminski et al., J. Pharm. Sci. 65(12):1737 (1976).
  • determining the MIC involved placing 1 mL of an aqueous suspension containing 10 6 -10 7 colony-forming units (CFU)/mL of Staphylococcus aureus (Gram-positive) or Escherichia coli (Gram-negative) into 9 mL of aqueous solutions containing different concentrations of the QAS-dyes of the present invention. After 24 hours, a 100 ⁇ L aliquot of the resultant solution was serially diluted by sterilized distilled water. 100 ⁇ L of the dilution was placed onto a nutrient agar plate and incubated at 37° C. for 24 hours. The same procedure was applied to a distilled water solution without the compounds as a control.
  • the MIC values of the QAS-dyes from Examples 1-6 against S. aureus and E. coli are shown in Table 1 below. TABLE 1 The MIC of the compounds from Examples 1-6. Compound of Example: 1 2 3 4 5 6 (m-4) (m-8) (m-12) (bi-4) (bi-8) (bi-12) MIC S. aureus (ppm) >800 80 20 800 60 20 MIC E. coli (ppm) >800 50 20 600 20 20 20 MIC is expressed in ppm (parts per million) of the compound.
  • the bi-QAS substituted dyes typically had higher antimicrobial activities than the mono-QAS substituted dyes (i.e., m-4, m-8, and m-12).
  • these compounds generally had better antimicrobial efficacy against gram-negative bacteria (e.g., E. coli ) than Gram-positive bacteria (e.g., S. aureus ).
  • This example illustrates the Fourier Transform Infrared (FTIR) Spectra of some of the representative compounds of Formula I.
  • the FTIR spectra of the compounds from Examples 1-3 are shown in FIG. 6 .
  • the starting material 1-aminoanthraquinone (I a )
  • This example illustrates the absorption spectra in aqueous solution of some of the representative compounds of Formula I.
  • intramolecular hydrogen bonding can lead to a bathochromic shift through a combination of two effects: (a) enhancing the electron-donating ability of the amide group and the electron-withdrawing ability of the carbonyl group; and (b) holding the groups in a planar conformation. See, for example, Gordon et al., Organic chemistry in colour , New York: Springer-Verlag Berlin Heidelberg; (1983). However, it is believed that the formation of the other two types of hydrogen bonding has no such effect.
  • bi-QAS substituted dyes it is believed that with an increase in the alkyl chain length in the QAS, steric hindrance is increased, which can also increase the relative amount of intramolecular hydrogen bonding but decrease the proportion of the other two types of hydrogen bonding. Therefore, increasing QAS chain length resulted in greater bathochromicity for the bi-QAS substituted dyes.
  • the steric hindrance effect of the alkyl chain was not obvious with mono-QAS substituted dyes.
  • ⁇ max is a widely-accepted measurement of tinctorial strength.
  • assessing the tinctorial strength of dyes is quite difficult and, in some cases, controversial results are obtained. Id. For example, an empirical rule states that for a given series of dyes, the tinctorial strength increases as the dyes become more bathochromic, whereas molecular orbital theory predicts that the tinctorial strength of dyes should decrease as ⁇ max increases.
  • steric hindrance always causes a reduction in tinctorial strength. Id.
  • This example illustrates the simultaneous dyeing and antimicrobial finishing of acrylic fabrics using the compounds of the present invention.
  • Sulfonate-containing acrylic fabrics e.g., spun Orlon 75 (#864), were purchased from Testfabrics Inc. The fabrics were scoured in a solution of 5 g/L nonionic surfactant (Triton X-100, EM Science) at 60° C. for 30 minutes, then rinsed thoroughly in tap water and dried in the open air. Sodium sulfate (EM Science), sulfuric acid (EM Science), sodium acetate (EM Science), and acetic acid (99%, EM Science) were used as received.
  • Triton X-100 Triton X-100
  • EM Science sulfuric acid
  • EM Science sodium acetate
  • acetic acid 99%, EM Science
  • the dyeing of acrylic fabrics follows a traditional exhaustion dyeing procedure (Munn, The dyeing of synthetic - polymer and acetate fibres , England: Dyers Company Publications Trust (1979)).
  • Dye solutions were prepared with the QAS-dyes of the present invention, sodium sulfate (2 g/L), and Triton X-100 (0.05%).
  • the pH of the dyeing bath was adjusted to 3 by buffer solutions containing sulfuric acid, sodium acetate, and acetic acid. The bath ratio was kept at 1:50.
  • the Orlon fabrics were immersed into the dyeing bath at initial dyeing temperatures for a certain period of time, and then fixed at 100° C. for another period of time to elevate the interactions between the fabrics and the QAS-dyes.
  • a Hitachi U-2000 UV-vis spectrophotometer was used to measure the UV-vis absorbance of the dye solutions before and after exhaustion.
  • the concentration of the QAS-dyes was calculated based on a previously established absorbance-concentration relationship at the ⁇ max of the compound. Unfixed compound from the samples was extracted by hot water and also measured by the UV-vis spectrophotometer.
  • the amount of QAS-dye fixed on the fabric was calculated by Eq.
  • N 0 ( ⁇ Mol) is the initial QAS-dye quantity before exhaustion
  • N 1 ( ⁇ Mol) is the residual QAS-dye amount after exhaustion
  • N 2 ( ⁇ Mol) is the amount of unfixed QAS-dye present in the extracted solution
  • W (g) is the weight of untreated Orlon fabric.
  • the antimicrobial activities of the treated Orlon fabrics were evaluated against Escherichia coli ( E. coli , Gram-negative) and Staphylococcus aureus ( S. aureus , Gram-positive) according to AATCC test method 100-1999.
  • E. coli Escherichia coli
  • S. aureus Staphylococcus aureus
  • AATCC test method 100-1999 disposable petri dishes containing fabric swatches weighing about 1 g were challenged with 1.0 ⁇ 0.1 mL of bacteria inoculum. After a certain period of contact time, the challenged fabric swatches were transferred to 250 mL containers with 100 mL of sterilized water, and the resultant supernatant was diluted 10 1 , 10 2 , 10 3 , and 10 4 times.
  • the surface resistivity of the treated fabrics was measured by a portable surface resistivity/resistance meter purchase from Monroe Electronics, Inc (Model 272A).
  • the visual color yields of the dyed fabrics were measured by GretagMacbethTM Color-Eye® 7000A spectrophotometer.
  • the visual color yields of the fabrics were expressed by K/S values, which were derived from the reflectance measurement.
  • the treated fabric was washed in a Launder-Ometer® according to AATCC Test Method 61-2001 to evaluate the wash durability of the treated fabrics. In this method, one cycle of a Launder-Ometer wash is equivalent to five machine washes using a home laundry machine.
  • thermodynamic characteristics of the dyeing process It is well established that the dyeing of most fibers is a thermodynamically reversible process. Therefore, it is permissible to apply thermodynamic functions to the dye-fiber systems (Bird et al., The theory of coloration of textiles , London: Dyers Company Publications Trust (1975)). In a dye-fiber system, dyes are distributed in both the fiber and the dyebath.
  • ⁇ ° is referred to as the standard affinity and is a measure of the tendency of the dye to move from its standard state in the dyebath onto the fiber. If Van der Waals interactions between dyes and fabrics are stronger, as the value A f increases, the value of ⁇ ° also increases. In other words, with the increase of Van der Waals interactions between dyes and fabrics, more dyes may tend to move from the dyebath to the fiber, leading to higher fixation and/or dyeing results.
  • the bi-QAS substituted dyes contain two positively charged nitrogen atoms in each structure. As such, compared to the mono-QAS substituted dyes, they are more favorable to stay in the dyebath. Both ⁇ ° and the amount of fixation are lower for the bi-QAS substituted dyes.
  • an increase in the alkyl chain length in the QAS results in an increase in hydrophobicity, indicating that the QAS-dyes can become less favorable to stay in the dyebath.
  • the Van der Waals interactions between the fabric and the QAS-dye increase.
  • longer alkyl chains in the QAS result in increased ⁇ ° and higher fixation for both mono- and bi-QAS substituted dyes.
  • FIG. 9 shows that the mono-QAS substituted dyes approached equilibrium after 120 minutes, while the bi-QAS substituted dyes needed as long as 300 minutes to level off. Without being bound to any particular theory, it is believed that these results can be explained by the thermodynamic characteristics of the dyeing process. Compared to the bi-QAS substituted dyes, the mono-QAS substituted dyes are less favorable to stay in the dyebath. As such, they are more favorable to the fiber. Because the A f and ⁇ ° values can be higher for the mono-QAS substituted dyes, more dye can be driven to the fiber to occupy the dye sites, and an equilibrium is achieved faster.
  • the fixation of m-12 is around 60 mMol/kg, very close to the theoretical value, and the fixation of bi-12 is around 30 mMol/kg, half of the calculated value. Without being bound to any particular theory, it is believed that this can be caused by the fact that each mono-QAS substituted dye occupies one dye site within the fabric during fixation, while each bi-QAS substituted dye occupies two dye sites.
  • dyes with shorter QAS alkyl chains, such as m-4, m-8, bi-4, and bi-8 showed lower fixation levels compared to the calculated value.
  • Weaker Van der Waals interactions present between the QAS-dyes and the fabrics, which makes A f smaller and ⁇ ° lower, can account for the lower fixation levels. Therefore, compared to m-12 or bi-12, these QAS-dyes are more favorable to the dyebath, and as such, do not fully occupy all of the dye sites on the fabrics.
  • the size of the dye can also play an important role in the dyeing process. Smaller dyes can diffuse faster into the fabric, while larger ones can diffuse more slowly. However, a calculation of the sizes of the QAS-dyes of the present invention indicates that all them have maximum diameters within 1 ⁇ 2.5 nm, as shown in Table 2. Since these QAS-dyes are small and their size differences are not significant, they have similar diffusion properties and the size of the compounds has little or no influence on the level of fixation. TABLE 2 Molecular sizes of the QAS-dyes calculated by “HyperChem” software (edition 7.0) using semi-empirical, AM1, and geometry optimization. Dyes m-4 m-8 m-12 bi-4 bi-8 bi-12 Maximum diameter (nm) 1.19 1.25 1.35 1.80 2.16 2.20
  • FIG. 9 also shows that QAS-dye saturation is achieved at about 120 minutes for the mono-QAS substituted dyes and at about 300 minutes for the bi-QAS substituted dyes.
  • the number of cations present in the QAS-dyes of the present invention can also contribute to different dye fixation values.
  • the bi-QAS substituted dyes occupy twice the amount of dye sites within the fabrics compared to the mono-QAS substituted dyes. Therefore, theoretically, the value of fixed bi-QAS substituted dyes should be only half the amount of the mono-QAS substituted dyes if the dye sites are constant and fully occupied. However, the data from FIGS. 9 and 10 indicate that the dyes sites are not fully occupied. As such, the number of cations present in the QAS-dyes is not a major factor in determining the amount of fixed QAS-dye.
  • FIG. 11 shows that, below 80° C., only a small amount of QAS-dyes was fixed onto the Orlon fabric. However, when the temperature was increased from 80° C. to 90° C., an increase of about two-fold was observed for all compounds. Furthermore, when the temperature was increased from 90° C. to 100° C., an increase of about three-fold was observed for the mono-QAS substituted dyes, and about two-fold for the bi-QAS substituted dyes.
  • Tg glass transition temperature
  • FIG. 12 shows a typical example of the FTIR spectra in the range of 1000-2000 cm-1 for m-4.
  • FTIR FTIR analysis
  • the peak at 1706 cm ⁇ 1 can be attributed to the amide carbonyl group in the QAS-dye, and the band around 1673 cm ⁇ 1 may be caused the carbonyl group present in the anthraquinone ring of the QAS-dye.
  • FIG. 13 shows the spectrum of Orlon treated with bi-12 (b). It can be seen that around 1630 cm ⁇ 1 , the shoulders become less obvious. However, after subtracting (A) from (B), their difference spectrum (C) also exhibited a new peak at 1718 cm ⁇ 1 , corresponding to the amide carbonyl group in the QAS-dye.
  • FIG. 14 summarizes the FTIR spectra of Orlon fabrics treated by both mono- and bi-QAS substituted dyes. It can be seen that all of the fabrics treated with the mono-QAS substituted dyes show very similar results, as do the fabrics treated with the bi-QAS substituted dyes. Therefore, it can be concluded that all of the synthesized antimicrobial cationic dyes (i.e., QAS-dyes) of the present invention can be incorporated into Orlon fabrics by following the traditional cationic dyeing process.
  • QAS-dyes synthesized antimicrobial cationic dyes
  • a further increase in contact time may use up all of the available QAS-dye, resulting in the favorable the growth of bacteria and decreased antimicrobial efficacy.
  • the bacterial concentration is higher than 10 7 CFU/mL
  • the QAS-dye concentration is relatively low compared to that of the bacteria, so even in the beginning, low antimicrobial efficacy is observed. All of the available QAS-dye may be used up quickly in this case, and as a result, a further increase of contact time does not cause bacterial reduction.
  • the treated Orlon fabrics were further challenged against E. coli and S. aureus . As shown in Table 4, prior to washing, all of the treated fabrics provide efficient antimicrobial activity, but to different degrees depending on the QAS-dye. Generally, for both mono- and bi-QAS substituted dyes, an increase in the alkyl chain length in the QAS resulted in higher fabric antimicrobial efficacy. For example, the Orlon fabric treated by m-4 can kill 95.7% of E. coli , and the Orlon fabric treated by m-12 can kill 99.9%. In most cases, the fabrics treated by the bi-QAS substituted dyes exhibited higher antimicrobial efficiency compared to the dyes treated by the corresponding mono-QAS substituted dyes.
  • the fabric treated by bi-8 can kill 93.9% of S. aureus
  • the fabric treated by m-8 can kill 92.4%.
  • all the treated fabrics show higher antimicrobial efficacy against E. coli than S. aureus .
  • the active antimicrobial component of the QAS-dye kills bacteria by disturbing their cytoplasmic membranes.
  • Shorter alkyl chains on the QAS e.g., less than 8 carbons
  • the higher antimicrobial activities of the fabrics treated with the bi-QAS substituted dyes are caused by the higher QAS content in the dyes, and the higher antimicrobial efficacy against E. coli is related to the fact that E. coli shows less resistance to mechanical rupture compared to S. aureus (Hugo, J. Appl. Bact., 30:17 (1967)).
  • Table 4 shows that the wash durability of the treated fabrics was low. For example, after 5 washes, the fabric treated by m-12 killed 81.3% of E. coli ; after 10 washes, the antimicrobial activities disappeared except for bi-8 and bi-12. Fabrics treated with bi-12 achieved the best results: after 5 washes, the fabric killed 99.3% of E. coli ; after 10 washes, the antimicrobial efficiency was 60.0%. Without being bound to any particular theory, it is believed that the low washing durability of the treated Orlon fabrics is caused by the loss of the QAS-dyes during washing. To confirm this assumption, the surface resistivity (i.e., anti-static property) of these fabrics was measured. As shown in FIG.
  • the QAS-dyes of the present invention are also suitable for use as anti-static agents. With an increase in the number of washes, the surface resistivity increased (i.e., more static), indicating a decrease in the conductivity of the fabrics. Without being bound to any particular theory, it is believed that this decrease is caused by the loss of some of the dye.
  • the fixed dyes may be divided into water-accessible and water-inaccessible fractions when the temperature is below the Tg of the fabrics.
  • the water-accessible dyes mainly locate on the surface of the fabrics.
  • During washing it is also these water-accessible dyes that are washed away, since they can come into contact with the detergent solutions. After washing, the antimicrobial activity of the treated fabrics dropped significantly, due to the loss of water-accessible dyes.
  • the surface resistivity indicates the amount of dye bound to the surface of the fabrics. Without being bound to any particular theory, it is believed that most of these surface dyes are water-accessible and are lost during washing. Therefore, the surface resistivity of the fabrics was very different before washing compared to after washing. However, K/S measures the shade depth of the fabrics (Yang et al., AATCC Review, 3:29 (2003)). As both water-accessible dyes and water-inaccessible dyes inside the fabrics contribute to the shade depth, the total visual effect is not significantly affected by the loss of the water-accessible dyes.
  • This example illustrates the thermal and hydrolytic stability of compounds of the present invention.
  • Thermal stability analysis Thermal analyses of the QAS-dyes shown in FIG. 2B were performed using a differential scanning calorimeter (DSC) (Shimadzu DSC-50) and a thermal gravimetric analyzer (TGA) (Shimadzu TGA-50). The dye samples were heated at 10° C./min. and nitrogen gas was chosen as the atmosphere.
  • DSC differential scanning calorimeter
  • TGA thermal gravimetric analyzer
  • Hydrolytic stability analysis The dyes were dissolved in aqueous solutions at a concentration of 0.4-1 mMol/L, and the solutions were adjusted to various pH values by using sulfuric acid, acetic acid, sodium acetate, sodium bicarbonate, and/or sodium carbonate. The solutions were heated to the required temperatures. At different time intervals, solution samples were taken and measured by a HITACHI U-2000 spectrophotometer to obtain the UV-vis adsorption spectra. The results were compared with the spectra of original dye solutions to determine the stability of the dyes.
  • anthraquinone structures are thermally stable (Gordon et al., Organic chemistry in colour , Berlin: Springer-Verlag (1983)).
  • the decomposition of the dyes may be caused by the attached quaternary ammonium salt group.
  • the thermal stabilities of quaternary ammonium salts have been investigated elsewhere, and the first stage of the thermal decomposition of a QAS is a dealkylation reaction, caused by a nucleophilic substitution reaction of the halide ion (X ⁇ ) at the a carbon center (Fenton et al., J. Chem. Soc., 989 (1933)).
  • the exothermic peak of the second step of the weight loss in the TGA curves is most likely attributed to the decomposition of the anthraquinone dye structures. Again, because of the same decomposition mechanisms, the DSC and TGA curves of the samples have very similar patterns in this range.
  • FIG. 18 shows the absorption spectra of an m-4 dye solution at 100° C. and at pH 5 at different times.
  • the m-4 dye solution (0.4 mMol/L) was stable for about six hours, evidenced by the almost unchanged visible spectra. After 8 hours, however, the absorbance of the dye solution decreased dramatically. Accompanying the decrease in absorbance, a red precipitate was also observed in the solution. 1 H NMR analysis of the precipitate indicated that 1-aminoanthraquinone was produced as one of the hydrolytic products of m-4 ( FIG. 19 ).
  • aromatic amines absorb from 3.0 to 5.0 ppm (Silverstein et al., Spectrometric identification of organic compounds , New York: John Wiley & Sons (1998)).
  • the peak of the amine protons may be shifted and overlap with other peaks. Therefore, in FIG. 19 , proton H h cannot be detected.
  • the amine protons appear at 7.98 ppm, overlapping with protons H e and H f (Sadtler spectra, 300 MHz proton nuclear magnetic resonance standards, 1793 HB).
  • FIG. 23 shows the period of stability for three different mono-QAS substituted dye solutions at different pH values. All of the dyes tested exhibited the highest stability at pH 3. As such, rather than being stable at the neutral conditions, mono-QAS substituted dyes surprisingly showed the highest stability at an acidic pH. Without being bound to any particular theory, this result is associated with the unique structures of the QAS-dyes of the present invention, as these dyes possess both hydrophobic and hydrophilic features, similar to surfactants.
  • the hydrophobicity of the dye is improved.
  • the surfactant feature of these dyes indicates that the dyes may have properties similar to surfactants in aqueous solutions.
  • the dyes can aggregate in water to form micelles by placing the hydrophilic segment at the outer layer and pushing the hydrophobic alkyl chain into the inner layer. Since the hydrophilic moiety contains a positively charged nitrogen atom, the hydrophilic sections of the aggregates and the outer layer of the micelles possess positive charges. Thus, the aggregates and micelles tend to attract negatively charged species but repel positive ones in the solution. In other words, hydroxide ions (OH ⁇ ) can be favorably attracted to the aggregates or micelles but protons (H + ) are repelled from them.
  • alkylbetaines in water was highly dependent on the number of carbon atoms. Typicaly, the higher the alkyl chain length in betaines, the lower the solubility. For example, ethanesulfobetaine with a hexyl alkyl chain has a solubility of 655.0 g/L at 30° C., while the solubility of the decyl homologue drops to 2.2 g/L, and that of the docosyl homologue was less than 0.1 g/L (Barnhurst, J. Org. Chem., 26:4520 (1961)).
  • bi-QAS substituted dyes exhibited a similar stability trend with respect to pH as mono-QAS substituted dyes, although the bi-QAS substituted dyes had a lower overall stability. Without being bound to any particular theory, it is believed that this may be due to the fact that the bi-QAS substituted dyes have two amide linkages in each compound, making them more susceptible to acid or base attack.
  • the QAS-dyes of the present invention are stable within a pH range of from about 1 to about 4 at 100° C., with pH 3 providing the most optimal stability results.
  • the dyes may be exposed to both acidic conditions at high temperatures.
  • the dyes of the present invention are suitable for use in these applications, as they can withstand the conditions encountered therein.

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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Cited By (11)

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US20050220375A1 (en) * 2002-02-27 2005-10-06 Thomas Toby R Pakages with active agents
US20050220374A1 (en) * 2002-02-27 2005-10-06 Thomas Toby R Packages with active agents
US20060286356A1 (en) * 2002-02-27 2006-12-21 Thomas Toby R Web materials with active agent
US20070055653A1 (en) * 2005-09-02 2007-03-08 Guerra Currie Anne-Marie P System and method of generating automated document analysis tools
KR100821896B1 (ko) 2005-02-23 2008-04-16 주식회사 코오롱 은 함유 항균 산성 염료와 그의 제조 방법 및 그를 이용한항균 섬유
US20080201871A1 (en) * 2003-03-19 2008-08-28 The Regents Of The University Of California Antimicrobial colorants
WO2008030925A3 (fr) * 2006-09-06 2008-11-13 Univ California Colorants antimicrobiens
US8892495B2 (en) 1991-12-23 2014-11-18 Blanding Hovenweep, Llc Adaptive pattern recognition based controller apparatus and method and human-interface therefore
US9535563B2 (en) 1999-02-01 2017-01-03 Blanding Hovenweep, Llc Internet appliance system and method
US9889080B2 (en) 2015-05-07 2018-02-13 Celeb LLC Color depositing shampoo
US10245221B2 (en) 2015-05-07 2019-04-02 Celeb LLC Stabilized color depositing shampoo

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CN108914544A (zh) * 2018-07-20 2018-11-30 启东市新利来制衣有限公司 一种水洗含有罗布麻与棉纤维的面料防水处理工艺

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8892495B2 (en) 1991-12-23 2014-11-18 Blanding Hovenweep, Llc Adaptive pattern recognition based controller apparatus and method and human-interface therefore
US9535563B2 (en) 1999-02-01 2017-01-03 Blanding Hovenweep, Llc Internet appliance system and method
US20050220375A1 (en) * 2002-02-27 2005-10-06 Thomas Toby R Pakages with active agents
US20050220374A1 (en) * 2002-02-27 2005-10-06 Thomas Toby R Packages with active agents
US20060286356A1 (en) * 2002-02-27 2006-12-21 Thomas Toby R Web materials with active agent
US7497623B2 (en) 2002-02-27 2009-03-03 Pactiv Corporation Packages with active agents
US20080201871A1 (en) * 2003-03-19 2008-08-28 The Regents Of The University Of California Antimicrobial colorants
KR100821896B1 (ko) 2005-02-23 2008-04-16 주식회사 코오롱 은 함유 항균 산성 염료와 그의 제조 방법 및 그를 이용한항균 섬유
US20070055653A1 (en) * 2005-09-02 2007-03-08 Guerra Currie Anne-Marie P System and method of generating automated document analysis tools
WO2008030925A3 (fr) * 2006-09-06 2008-11-13 Univ California Colorants antimicrobiens
US9889080B2 (en) 2015-05-07 2018-02-13 Celeb LLC Color depositing shampoo
US10245221B2 (en) 2015-05-07 2019-04-02 Celeb LLC Stabilized color depositing shampoo

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WO2004083336A2 (fr) 2004-09-30

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