WO2008096919A1 - Antibacterial acid dyes and method of preparing the same and antibacterial fiber dyed thereby - Google Patents

Antibacterial acid dyes and method of preparing the same and antibacterial fiber dyed thereby Download PDF

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Publication number
WO2008096919A1
WO2008096919A1 PCT/KR2007/000707 KR2007000707W WO2008096919A1 WO 2008096919 A1 WO2008096919 A1 WO 2008096919A1 KR 2007000707 W KR2007000707 W KR 2007000707W WO 2008096919 A1 WO2008096919 A1 WO 2008096919A1
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Prior art keywords
antibacterial
amino
general formula
hydroxynaphthalene
sulfonic acid
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PCT/KR2007/000707
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French (fr)
Inventor
Sung-Hui Park
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Kolon Industries, Inc
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Priority to PCT/KR2007/000707 priority Critical patent/WO2008096919A1/en
Publication of WO2008096919A1 publication Critical patent/WO2008096919A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
    • C09B29/28—Amino naphthols
    • C09B29/30—Amino naphtholsulfonic acid
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • D06P1/02—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 azo dyes
    • D06P1/04—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 azo dyes not containing metal
    • D06P1/06—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 azo dyes not containing metal containing acid groups
    • 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
    • D06P1/39—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 acid 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
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes

Definitions

  • the present invention relates to antibacterial acid dyes comprising two identical sulfonaminde based antibacterial compounds bonded to acidic dyes by diazotization-coupling reaction, the antibacterial compounds of which have strong antibacterial properties, a method of preparing the same, and antibacterial fiber dyed by the same, which possess a variety of colors and antibacterial properties.
  • a fabric product used in garment or bedclothes needs to undergo a fiber material dyeing process with desired colors to satisfy different tastes of consumers.
  • Such manufactured fabric product often becomes habitable for microorganisms due to poor care, allowing the microorganisms to inhabit and grow with normal bodily secretions as nutrient when the microorganisms contact directly with a human body so that it threatens health of the human body and/ or results bad odor, contamination, discoloration, brittleness of fiber, etc., thereby being a major cause to deteriorate quality of the fabric product such as durability, color fastness or the like.
  • the fabric product may become a medium or habitat for pathogenic bacteria to invade the human body.
  • the fabric product has anti-bacterial properties, it will become a functional fabric product that inhibits inhabitation or growth of microorganisms and, as a result, protects against infectious disease and bad odor, and prevents staining and brittleness of fiber of the fabric product.
  • the post- treatment processes include: as disclosed in Korean Patent Laid-Open No. 2000-007593, a method for giving anti-bacterial properties to fibers, which includes extraction of dyeing ingredient from a natural material such as Saururus chinensis (Lour.) Baill with anti-bacterial properties; a method which cross-links an anti-bacterial material such as organometallic compound or organic material with fibers and thermally fixes the bonded product to surface of the fibers by using a reactant resin; a method which fixes an antibacterial material to surface of fibers by adsorption and so on.
  • the fiber improving processes include: a method which comprises introducing an inorganic anti-bacterial compound within fibers by blend- spinning the inorganic anti-bacterial compound into polymer in a process of manufacturing synthetic fibers; a method which disperses a copper compound into fibers during coagulating and regenerating in a process of manufacturing regenerated fibers; a method for synthesizing polymer, which comprises organic copolymer ingredients with anti-bacterial properties and so on.
  • the anti-bacterial and deodorization processes have not a purpose of sterilization or treatment of diseases but are to inhibit inhabitation and growth of microbes and/ or fungi on fibers.
  • the processes require that an anti-bacterial effect is continuously- maintained at least a predetermined level rather than only exhibiting high anti-bacterial properties for a short time and must safe to human bodies.
  • organic mercury compound, organic tin compound, organic copper compound and organic zinc compound among the organometallic compounds used in the post-treatment processes have very superior anti-bacterial properties, they also have a problem of safety to a human body such as toxicity.
  • organometallic compounds for garments are prohibited by countries such as Japan, U.S.A., etc. but are partially used in applications that do not involve direct contact with the human body, for example, production of carpet or wallpaper, or other industrial fields.
  • such organometallic compounds that have demonstrated problems of undesired adhesion to fibers and low laundry durability are restricted in their permanent anti-bacterial effect.
  • organic anti-bacterial materials that could be easily processed contrary to inorganic materials and do not affect mechanical properties, transparency, color, etc., as much are widely used at present.
  • use of the organic anti-bacterial materials is limited because their anti-bacterial effect is not continued for a long term as described above and they have inferior heat-resistance.
  • some of the organic anti- bacterial materials often have disadvantages of causing skin irritation, tearing property and so on.
  • Dyes extracted from natural materials have a merit that anti-bacterial properties are early given to fibers in a dyeing process. But, they have a restriction in extracting the dyes due to seasonal limitation and a disadvantage that mordant dyeing accompanied with additional heavy metals is required to improve color fastness as a defect of natural dyes.
  • Inorganic anti-bacterial materials are obtained by substitution of an inorganic carrier such as zeolite, silica, alumina, etc. with metal ions such as copper, zinc, etc. having excellent anti-bacterial properties.
  • the inorganic anti-bacterial materials that have three-dimensional structure formed with micro-fine pores demonstrate a large surface area and excellent heat- resistance. It is believed as of now that copper and zinc belong to a few metals with superior anti-bacterial effect and safety, and are harmless to the human body.
  • the inorganic anti-bacterial materials have higher heat- resistance and stability sufficient not to cause volatilization and decomposition thereof in comparison to conventional organic anti-bacterial materials, thereby being used in a wide variety of applications.
  • the inorganic anti-bacterial materials since they express antibacterial effect via activated oxygen ions, the inorganic anti-bacterial materials have an excellent anti-bacterial effect superior to the organic anti-bacterial materials.
  • such metal ions for example, copper or zinc that are apt to deteriorate resin or cause yellowing have a possibility of significantly lowering value of goods containing the same.
  • the inorganic anti-bacterial materials may cause cutting of thread if the inorganic anti-bacterial materials are added to micro-fine fibers during blend- spinning, since they generally have a larger average particle diameter above micron units and a wider distribution of particle size.
  • the present invention is directed to solve the problems of conventional anti-bacterial materials used as dyes as described above and, an object of the present invention is to provide antibacterial acid dyes comprising strong antibacterial groups and a process of preparing the same.
  • Another object of the present invention is to provide antibacterial fibers that are subjected to antibacterial process in a dyeing step, need not alternative process for the purpose of antibacterial treatment, do not lose color in woven or knitted fabric fabricated of the antibacterial fibers because the dyes are decomposed, and have excellent durability to continuously exhibit antibacterial properties for a long period of time.
  • the present invention provides an antibacterial acid dye having a structure represented by chemical formula 1 of which two identical sulfonamide based antibacterial compounds with antibacterial properties are bonded to acidic dye by diazotization-coupling process, and antibacterial fibers dyed with the same.
  • R 1 is H or OH
  • R2 is H, NH2
  • R3 is H, SO3H or sulfonamide based antibacterial compound A
  • R4 is H or SO3H
  • A is sulfonamide based antibacterial compound.
  • the present invention provides a process of preparing the antibacterial acid dye represented by the above chemical formula 1 comprising: (I) first step of conducting diazotization of sulfadiazine or sulfamethiazine by using hydrochloric acid and sodium nitrite; (II) second step of azo-coupling the reactive product from the step (I) with one selected from a group consisting of 6-amino-4-hydroxynaphthalene- 2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4- amino-5-hydroxynaphthalene-l -sulfonic acid and 4-amino-5- hydroxynaphthalene-2,7-sulfonic acid; and (III) third step of azo- coupling the resulting product from the step (II) with the reactive product further obtained from the step (I) by diazotization of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nit
  • Anti-bacterial materials generally used include, for example, penicillin, sulfonamide, fluoroquinolone, tetracycline, aminoglucoside and the like. Among them, preferred are tetracycline, sulfonamide, quinolone, etc. which are widely and commercially available as intermediates of dyes. Of these materials, the present invention especially uses sulfonamide based anti-bacterial compounds capable of inhibiting metabolism function of enzymes in microorganism such as synthesis of nucleic acid in microorganism to endow anti-bacterial properties to a subject matter.
  • Sulfonamide drug that is, the sulfonamide based anti-bacterial compound is one of anti-bacterial compounds having SO2NH2 group and used as a general term for sulfanilamide derivatives that disrupt folic acid synthesis by the microorganisms.
  • the above anti-bacterial compound is one of anti-bacterial materials that inhibit growth of bacteria including: for example, gram-positive cocci such as streptococci, pneumococci; gram-negative cocci such as meningococci, gonococci; gram-positive bacillus such as Escherichia coli, shigellae; and the like.
  • Sulfonamide commonly has a molecular structure of sulfanilamide and includes varied kinds of compounds.
  • Sulfonamide based anti-bacterial materials include, but are not limited to, sulfapyridine, sulfadiazine, silver sulfadiazine, sulfamerazine, sulfamethoxine, sulfapyrazine, phthalylsulfathiazole, sulfathiazole, mafenide, sulfadimidine, sulfamethazine, sulfamethoxazole, sulfanilamide, sulfamethoxypyridazine, sulfaguanidine, sulfadimethoxine, sulfisoxazole, sulfadoxine, sulfamethizole, sulphasalazine, sulphinpyrazone, etc.
  • the present invention is preferably applied to synthesis of anti-bacterial dyes by using sulfadiazine (monosilver-4-amino-N- pyrimidylbenzene sulfonamide) represented by general formula 1 [hereinafter, referred to as "sulfadiazine”] or sulfamethiazine (4-amino- N-5-diadiazolbenzene sulfonamide) represented by general formula 2 [hereinafter, referred to as "sulfamethiazine”] among sulfonamide based anti-bacterial compounds that are mostly available as antibacterial compound, as mostly easily synthesized and exhibit excellent anti-bacterial effect:
  • Sulfadiazine and sulfamethiazine exhibit anti-bacterial ability against yeast as well as numerous gram-positive and gram-negative microorganisms, and are used as a locally and externally applied anti- infectious disease agent effective to protect and treat sepsis of second and /or third degree burns.
  • the acid dyes described above comprise 6-amino-4- hydroxynaphthalene-2-sulfonic acid represented by general formula 3, 7-amino-4-hydroxynaphthalene-2-sulfonic acid represented by general formula 4, 4-amino-5-hydroxynaphthalene- 1 -sulfonic acid represented by general formula 5 or 4-amino-5-hydroxynaphthalene-2,7-sulfonic acid represented by general formula 6, etc.
  • the present invention provides the antibacterial acid dye represented by the above chemical formula 1 synthesized by steps of: (I) conducting diazotization of sulfadiazine or sulfamethiazine by using hydrochloric acid and sodium nitrite; (II) azo- coupling the reactive product from the step (I) with one selected from a group consisting of 6-amino-4-hydroxynaphthalene-2-sulfonic acid, 7- amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5- hydroxynaphthalene- 1 -sulfonic acid and 4-amino-5- hydroxynaphthalene-2,7-sulfonic acid; and (III) azo-coupling the resulting product from the step (II) with the reactive product from the step (I), that is, further obtained by diazotization of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite.
  • the antibacterial acid dye represented by the following chemical formula 2 is synthesized by steps of: (I) conducting diazotization of sulfadiazine represented by the following general formula 1 among sulfonamide based anti-bacterial compounds by using hydrochloric acid and sodium nitrite; (II) azo-coupling the reactive product from the step (I) with 6- amino-4-hydroxynaphthalene-2-sulfonic acid represented by the following general formula 3; and (III) again azo-coupling the resulting product from the step (II) with the reactive product from the step (I), that is, further obtained by diazotization of sulfadiazine with hydrochloric acid and sodium nitrite.
  • the antibacterial acid dye represented by the following chemical formula 3 is synthesized by steps of: (I) conducting diazotization of sulfamethiazine represented by the following general formula 2 among sulfonamide based anti-bacterial compounds by using hydrochloric acid and sodium nitrite; (II) azo-coupling the reactive product from the step (I) with 6-amino-4-hydroxynaphthalene-2- sulfonic acid represented by the following general formula 3; and (III) again azo-coupling the above product from the step (II) with the reactive product further obtained from the step (I) by diazotization of sulfamethiazine with hydrochloric acid and sodium nitrite.
  • the antibacterial acid dyes according to the present invention have red and yellow colors to express a variety of colors by blending the dyes together, exhibit strong antibacterial properties when the dyes are employed in dyeing fibers and manufacturing functional fabric products that inhibit growth or inhabitation of microorganisms and, as a result, protect against infectious disease and bad odor, and prevent staining and brittleness of fiber of the fabric product.
  • 0.01 moles of sulfadiazine represented by the general formula 1 is dispersed in distilled water at 3 °C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution. Next, to the treated solution, 0.01 moles of sodium nitrite NaNO2 is slowly introduced to proceed diazotization represented by the following reaction scheme 1 :
  • reaction scheme 3 0.01 moles of sulfadiazine represented by the general formula 1 is dispersed in distilled water at 3°C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution.
  • 0.02 moles of sodium nitrite NaNO2 is slowly introduced to proceed diazotization represented by the above reaction scheme 1.
  • the solution obtained by diazotization is added to the red colored reactive solution represented by the above reaction scheme 2 to proceed azo-coupling reaction represented by the following formula 3 while maintaining the solution at 4°C and pH7: (Reaction scheme 3)
  • the prepared solution is titrated to become pH7, salted out, passed through filter paper and dried to produce an antibacterial acid dye with blue color represented by the above chemical formula 2.
  • reaction scheme 1 0.01 moles of sulfamethiazine represented by the general formula 2 is dispersed in distilled water at 3 ° C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution. Next, to the treated solution, 0.01 moles of sodium nitrite NaNU2 is slowly introduced to proceed diazotization represented by the following reaction scheme 1: (Reaction scheme 1)
  • reaction scheme 3 0.01 moles of sulfamethiazine represented by the general formula 2 is dispersed in distilled water at 3°C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution.
  • 0.02 moles of sodium nitrite NaN ⁇ 2 is slowly introduced to proceed diazotization represented by the above reaction scheme 1.
  • the solution obtained by diazotization is added to the red colored reactive solution represented by the above reaction scheme 2 to proceed azo-coupling reaction represented by the following formula 3 while maintaining the solution at 3 °C and pH7: (Reaction scheme 3)
  • the prepared solution is titrated to become pH7, salted out, passed through filter paper and dried to produce an antibacterial acid dye with blue color represented by the above chemical formula 3.
  • Plain woven nylon fabrics which were dyed with a concentration of 1% o.w.f. (on the weight of fiber) using each of yellow and red color dyes previously synthesized, were tested for anti-bacterial properties by KS K-0693-2001 as a test method for anti-bacterial properties of fabric after washing the fabrics 0 time, 10 times and 20 times.
  • Table 1 that represents anti-bacterial effect of the dyed antibacterial fibers according to the present invention by the following test for anti-bacterial properties.
  • Table 1 proves antibacterial properties and washing durability of the antibacterial acid dyes according to the present invention.
  • Strain 1 Staphylococcus aureus ATCC 6538
  • Strain 2 Klebsiella pneumoniae ATCC 4352
  • control sample nylon (KS K 0905-1996)
  • non-ionic surfactant Tween 80 (0.05%)
  • the present invention can produce antibacterial fiber product that is subjected to antibacterial process in the dyeing step, needs no alternative process for the purpose of antibacterial treatment, does not lose color in woven or knitted fabric fabricated of the antibacterial fibers because the dyes are decomposed, and has excellent durability to continuously exhibit antibacterial properties for a long period of time.

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Abstract

Disclosed are antibacterial acid dyes comprising two identical sulfonamide based antibacterial compounds bonded to acidic dyes by diazotization-coupling reaction, the antibacterial compounds of which have strong antibacterial properties, and a method of preparing the same. The antibacterial acid dye compound according to the present invention which has strong anti-bacterial properties and dark colors, can be employed in dyeing fibers and fabricating a functional fiber product with anti-bacterial properties that protects against infectious disease and bad odor, and prevents staining and brittleness of fiber of the fabric product.

Description

ANTIBACTERIAL ACID DYES AND METHOD OF PREPARING THE SAME AND ANTIBACTERIAL FIBER DYED THEREBY
TECHNICAL FIELD The present invention relates to antibacterial acid dyes comprising two identical sulfonaminde based antibacterial compounds bonded to acidic dyes by diazotization-coupling reaction, the antibacterial compounds of which have strong antibacterial properties, a method of preparing the same, and antibacterial fiber dyed by the same, which possess a variety of colors and antibacterial properties.
Generally, a fabric product used in garment or bedclothes needs to undergo a fiber material dyeing process with desired colors to satisfy different tastes of consumers.
Such manufactured fabric product often becomes habitable for microorganisms due to poor care, allowing the microorganisms to inhabit and grow with normal bodily secretions as nutrient when the microorganisms contact directly with a human body so that it threatens health of the human body and/ or results bad odor, contamination, discoloration, brittleness of fiber, etc., thereby being a major cause to deteriorate quality of the fabric product such as durability, color fastness or the like.
Accordingly, the fabric product may become a medium or habitat for pathogenic bacteria to invade the human body. However, if the fabric product has anti-bacterial properties, it will become a functional fabric product that inhibits inhabitation or growth of microorganisms and, as a result, protects against infectious disease and bad odor, and prevents staining and brittleness of fiber of the fabric product.
BACKGROUND ART
It is well known that anti-bacterial and deodorization processes are generally classified into post-treatment processes and fiber improving processes. The post- treatment processes include: as disclosed in Korean Patent Laid-Open No. 2000-007593, a method for giving anti-bacterial properties to fibers, which includes extraction of dyeing ingredient from a natural material such as Saururus chinensis (Lour.) Baill with anti-bacterial properties; a method which cross-links an anti-bacterial material such as organometallic compound or organic material with fibers and thermally fixes the bonded product to surface of the fibers by using a reactant resin; a method which fixes an antibacterial material to surface of fibers by adsorption and so on. On the other hand, the fiber improving processes include: a method which comprises introducing an inorganic anti-bacterial compound within fibers by blend- spinning the inorganic anti-bacterial compound into polymer in a process of manufacturing synthetic fibers; a method which disperses a copper compound into fibers during coagulating and regenerating in a process of manufacturing regenerated fibers; a method for synthesizing polymer, which comprises organic copolymer ingredients with anti-bacterial properties and so on. The anti-bacterial and deodorization processes have not a purpose of sterilization or treatment of diseases but are to inhibit inhabitation and growth of microbes and/ or fungi on fibers. Therefore, the processes require that an anti-bacterial effect is continuously- maintained at least a predetermined level rather than only exhibiting high anti-bacterial properties for a short time and must safe to human bodies. Under these circumstances, although organic mercury compound, organic tin compound, organic copper compound and organic zinc compound among the organometallic compounds used in the post-treatment processes have very superior anti-bacterial properties, they also have a problem of safety to a human body such as toxicity. As a result, most of the organometallic compounds for garments are prohibited by countries such as Japan, U.S.A., etc. but are partially used in applications that do not involve direct contact with the human body, for example, production of carpet or wallpaper, or other industrial fields. Furthermore, such organometallic compounds that have demonstrated problems of undesired adhesion to fibers and low laundry durability are restricted in their permanent anti-bacterial effect.
Also, general organic anti-bacterial materials that could be easily processed contrary to inorganic materials and do not affect mechanical properties, transparency, color, etc., as much are widely used at present. However, use of the organic anti-bacterial materials is limited because their anti-bacterial effect is not continued for a long term as described above and they have inferior heat-resistance. Alternatively, some of the organic anti- bacterial materials often have disadvantages of causing skin irritation, tearing property and so on. Dyes extracted from natural materials have a merit that anti-bacterial properties are early given to fibers in a dyeing process. But, they have a restriction in extracting the dyes due to seasonal limitation and a disadvantage that mordant dyeing accompanied with additional heavy metals is required to improve color fastness as a defect of natural dyes.
Inorganic anti-bacterial materials are obtained by substitution of an inorganic carrier such as zeolite, silica, alumina, etc. with metal ions such as copper, zinc, etc. having excellent anti-bacterial properties. The inorganic anti-bacterial materials that have three-dimensional structure formed with micro-fine pores demonstrate a large surface area and excellent heat- resistance. It is believed as of now that copper and zinc belong to a few metals with superior anti-bacterial effect and safety, and are harmless to the human body. The inorganic anti-bacterial materials have higher heat- resistance and stability sufficient not to cause volatilization and decomposition thereof in comparison to conventional organic anti-bacterial materials, thereby being used in a wide variety of applications. In addition, since they express antibacterial effect via activated oxygen ions, the inorganic anti-bacterial materials have an excellent anti-bacterial effect superior to the organic anti-bacterial materials. However, such metal ions, for example, copper or zinc that are apt to deteriorate resin or cause yellowing have a possibility of significantly lowering value of goods containing the same. There is another concern with the inorganic anti-bacterial materials in that they may cause cutting of thread if the inorganic anti-bacterial materials are added to micro-fine fibers during blend- spinning, since they generally have a larger average particle diameter above micron units and a wider distribution of particle size.
DISCLOSURE OF THE INVENTION
(TECHNICAL PROBLEM)
Accordingly, the present invention is directed to solve the problems of conventional anti-bacterial materials used as dyes as described above and, an object of the present invention is to provide antibacterial acid dyes comprising strong antibacterial groups and a process of preparing the same.
Another object of the present invention is to provide antibacterial fibers that are subjected to antibacterial process in a dyeing step, need not alternative process for the purpose of antibacterial treatment, do not lose color in woven or knitted fabric fabricated of the antibacterial fibers because the dyes are decomposed, and have excellent durability to continuously exhibit antibacterial properties for a long period of time. (TECHNICAL MEANS TO SOLVE THE PROBLEM) The present invention provides an antibacterial acid dye having a structure represented by chemical formula 1 of which two identical sulfonamide based antibacterial compounds with antibacterial properties are bonded to acidic dye by diazotization-coupling process, and antibacterial fibers dyed with the same. (Chemical formula 1)
Figure imgf000007_0001
wherein R1 is H or OH, R2 is H, NH2, SO3H or sulfonamide based antibacterial compound A, R3 is H, SO3H or sulfonamide based antibacterial compound A, R4 is H or SO3H, and A is sulfonamide based antibacterial compound.
The present invention provides a process of preparing the antibacterial acid dye represented by the above chemical formula 1 comprising: (I) first step of conducting diazotization of sulfadiazine or sulfamethiazine by using hydrochloric acid and sodium nitrite; (II) second step of azo-coupling the reactive product from the step (I) with one selected from a group consisting of 6-amino-4-hydroxynaphthalene- 2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4- amino-5-hydroxynaphthalene-l -sulfonic acid and 4-amino-5- hydroxynaphthalene-2,7-sulfonic acid; and (III) third step of azo- coupling the resulting product from the step (II) with the reactive product further obtained from the step (I) by diazotization of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite.
Hereinafter, the present invention will be described in detail, especially, for construction thereof.
Anti-bacterial materials generally used include, for example, penicillin, sulfonamide, fluoroquinolone, tetracycline, aminoglucoside and the like. Among them, preferred are tetracycline, sulfonamide, quinolone, etc. which are widely and commercially available as intermediates of dyes. Of these materials, the present invention especially uses sulfonamide based anti-bacterial compounds capable of inhibiting metabolism function of enzymes in microorganism such as synthesis of nucleic acid in microorganism to endow anti-bacterial properties to a subject matter. Sulfonamide drug, that is, the sulfonamide based anti-bacterial compound is one of anti-bacterial compounds having SO2NH2 group and used as a general term for sulfanilamide derivatives that disrupt folic acid synthesis by the microorganisms. The above anti-bacterial compound is one of anti-bacterial materials that inhibit growth of bacteria including: for example, gram-positive cocci such as streptococci, pneumococci; gram-negative cocci such as meningococci, gonococci; gram-positive bacillus such as Escherichia coli, shigellae; and the like. Since it had been initially found that Prontosil® rubrum developed by Gerhard Domagk, a German scientist, in 1932 was in vivo metabolized into sulfanilamide to express strong anti-bacterial effect, a number of derivatives have been synthesized. Sulfonamide commonly has a molecular structure of sulfanilamide and includes varied kinds of compounds. Sulfonamide based anti-bacterial materials include, but are not limited to, sulfapyridine, sulfadiazine, silver sulfadiazine, sulfamerazine, sulfamethoxine, sulfapyrazine, phthalylsulfathiazole, sulfathiazole, mafenide, sulfadimidine, sulfamethazine, sulfamethoxazole, sulfanilamide, sulfamethoxypyridazine, sulfaguanidine, sulfadimethoxine, sulfisoxazole, sulfadoxine, sulfamethizole, sulphasalazine, sulphinpyrazone, etc. The present invention is preferably applied to synthesis of anti-bacterial dyes by using sulfadiazine (monosilver-4-amino-N- pyrimidylbenzene sulfonamide) represented by general formula 1 [hereinafter, referred to as "sulfadiazine"] or sulfamethiazine (4-amino- N-5-diadiazolbenzene sulfonamide) represented by general formula 2 [hereinafter, referred to as "sulfamethiazine"] among sulfonamide based anti-bacterial compounds that are mostly available as antibacterial compound, as mostly easily synthesized and exhibit excellent anti-bacterial effect:
(General formula 1) Sulfadiazine
Figure imgf000009_0001
(General formula 2) Sulfamethiazine
Figure imgf000009_0002
Sulfadiazine and sulfamethiazine exhibit anti-bacterial ability against yeast as well as numerous gram-positive and gram-negative microorganisms, and are used as a locally and externally applied anti- infectious disease agent effective to protect and treat sepsis of second and /or third degree burns.
Meanwhile, the acid dyes described above comprise 6-amino-4- hydroxynaphthalene-2-sulfonic acid represented by general formula 3, 7-amino-4-hydroxynaphthalene-2-sulfonic acid represented by general formula 4, 4-amino-5-hydroxynaphthalene- 1 -sulfonic acid represented by general formula 5 or 4-amino-5-hydroxynaphthalene-2,7-sulfonic acid represented by general formula 6, etc.
(General formula 3)
6-amino-4-hydroxynaphthalene-2-sulfonic acid
Figure imgf000010_0001
(General formula 4)
7-amino-4-hydroxynaphthalene-2-sulfonic acid
Figure imgf000010_0002
(General formula 5) 4-amino-5-hydroxynaphthalene- 1 -sulfonic acid
Figure imgf000011_0001
(General formula 6) 4-amino-5-hydroxynaphthalene-2,7-sulfonic acid
Figure imgf000011_0002
In the following, detailed description is given of a process for preparing the antibacterial acid dye represented by the following chemical formula 1 according to the present invention.
More particularly, the present invention provides the antibacterial acid dye represented by the above chemical formula 1 synthesized by steps of: (I) conducting diazotization of sulfadiazine or sulfamethiazine by using hydrochloric acid and sodium nitrite; (II) azo- coupling the reactive product from the step (I) with one selected from a group consisting of 6-amino-4-hydroxynaphthalene-2-sulfonic acid, 7- amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5- hydroxynaphthalene- 1 -sulfonic acid and 4-amino-5- hydroxynaphthalene-2,7-sulfonic acid; and (III) azo-coupling the resulting product from the step (II) with the reactive product from the step (I), that is, further obtained by diazotization of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite.
According to a preferred embodiment of the present invention, the antibacterial acid dye represented by the following chemical formula 2 is synthesized by steps of: (I) conducting diazotization of sulfadiazine represented by the following general formula 1 among sulfonamide based anti-bacterial compounds by using hydrochloric acid and sodium nitrite; (II) azo-coupling the reactive product from the step (I) with 6- amino-4-hydroxynaphthalene-2-sulfonic acid represented by the following general formula 3; and (III) again azo-coupling the resulting product from the step (II) with the reactive product from the step (I), that is, further obtained by diazotization of sulfadiazine with hydrochloric acid and sodium nitrite.
(General formula 1)
Silversulfadizine
Figure imgf000012_0001
(General formula 3) 6-amino-4-hydroxynaphthalene-2-sulfonic acid
Figure imgf000012_0002
(Chemical formula 2)
Figure imgf000013_0001
wherein SO3H is replaceable by SOaNa.
According to another preferred embodiment of the present invention, the antibacterial acid dye represented by the following chemical formula 3 is synthesized by steps of: (I) conducting diazotization of sulfamethiazine represented by the following general formula 2 among sulfonamide based anti-bacterial compounds by using hydrochloric acid and sodium nitrite; (II) azo-coupling the reactive product from the step (I) with 6-amino-4-hydroxynaphthalene-2- sulfonic acid represented by the following general formula 3; and (III) again azo-coupling the above product from the step (II) with the reactive product further obtained from the step (I) by diazotization of sulfamethiazine with hydrochloric acid and sodium nitrite.
(General formula 2) Sulfamethiazine
Figure imgf000013_0002
(General formula 3) 6-amino-4-hydroxynaphthalene-2-sulfonic acid
Figure imgf000014_0001
(Chemical formula 3)
Figure imgf000014_0002
wherein SO3H is replaceable by SOβNa. Features of the present invention described above and other advantages will be more clearly understood by the following non-limited examples, which are not intended to restrict the scope of the invention but are instead illustrative embodiments of the present invention. Accordingly, it will be obvious to those skilled in the art that the present invention is not restricted to the specific matters stated above and the examples below. (ADVANTAGEOUS EFFECTS)
As described in detail above, the antibacterial acid dyes according to the present invention have red and yellow colors to express a variety of colors by blending the dyes together, exhibit strong antibacterial properties when the dyes are employed in dyeing fibers and manufacturing functional fabric products that inhibit growth or inhabitation of microorganisms and, as a result, protect against infectious disease and bad odor, and prevent staining and brittleness of fiber of the fabric product.
BEST MODE FOR CARRYING OUT THE INVENTION [Example 1 : Preparation of antibacterial acid dye with blue color represented by the chemical formula 2]
0.01 moles of sulfadiazine represented by the general formula 1 is dispersed in distilled water at 3 °C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution. Next, to the treated solution, 0.01 moles of sodium nitrite NaNO2 is slowly introduced to proceed diazotization represented by the following reaction scheme 1 :
(Reaction scheme 1)
In alternative reaction vessel, 0.01 moles of 6-amino-4- hydroxynaphthalene-2-sulfonic acid represented by the above general formula 3 and 0.01 moles of Na2CO3 are dissolved together in distilled water and maintained at 3 °C .
To this solution, slowly introduced is the solution obtained by diazotization to proceed azo-coupling reaction represented by the following reaction scheme 2, thereby resulting in a reactive solution with red color:
(Reaction scheme 2)
Figure imgf000016_0001
After then, in another reaction vessel, 0.01 moles of sulfadiazine represented by the general formula 1 is dispersed in distilled water at 3°C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution. Next, to the treated solution, 0.02 moles of sodium nitrite NaNO2 is slowly introduced to proceed diazotization represented by the above reaction scheme 1. Herein, the solution obtained by diazotization is added to the red colored reactive solution represented by the above reaction scheme 2 to proceed azo-coupling reaction represented by the following formula 3 while maintaining the solution at 4°C and pH7: (Reaction scheme 3)
Figure imgf000017_0001
Finally, after completing the reaction, the prepared solution is titrated to become pH7, salted out, passed through filter paper and dried to produce an antibacterial acid dye with blue color represented by the above chemical formula 2.
[Example 2: Preparation of antibacterial acid dye with blue color represented by the chemical formula 3]
0.01 moles of sulfamethiazine represented by the general formula 2 is dispersed in distilled water at 3°C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution. Next, to the treated solution, 0.01 moles of sodium nitrite NaNU2 is slowly introduced to proceed diazotization represented by the following reaction scheme 1: (Reaction scheme 1)
Figure imgf000018_0001
In alternative reaction vessel, 0.01 moles of 6-amino-4- hydroxynaphthalene-2-sulfonic acid represented by the above general formula 3 and 0.01 moles of Na2CO3 are dissolved together in distilled water and maintained at 3 °C .
To this solution, slowly introduced is the solution obtained by diazotization to proceed azo-coupling reaction represented by the following reaction scheme 2, thereby resulting in a reactive solution with red color:
(Reaction scheme 2)
Figure imgf000018_0002
After then, in another reaction vessel, 0.01 moles of sulfamethiazine represented by the general formula 2 is dispersed in distilled water at 3°C , mixed with 6ml of hydrochloric acid, and dissolved under agitation to become a solution. Next, to the treated solution, 0.02 moles of sodium nitrite NaNθ2 is slowly introduced to proceed diazotization represented by the above reaction scheme 1. Herein, the solution obtained by diazotization is added to the red colored reactive solution represented by the above reaction scheme 2 to proceed azo-coupling reaction represented by the following formula 3 while maintaining the solution at 3 °C and pH7: (Reaction scheme 3)
Figure imgf000019_0001
Finally, after completing the reaction, the prepared solution is titrated to become pH7, salted out, passed through filter paper and dried to produce an antibacterial acid dye with blue color represented by the above chemical formula 3.
After preparing 1.0% aqueous solution for each of the obtained dyes represented by the chemical formulae 2 and 3, and adding glacial acetic acid and dispersant thereto to form a dye solution, the resulting solution is employed in dyeing fibers at 98 °C for 60 minutes. The treated fibers are soaped and dried to form anti-bacterial fibers with color. [Evaluation of anti-bacterial properties]
Plain woven nylon fabrics which were dyed with a concentration of 1% o.w.f. (on the weight of fiber) using each of yellow and red color dyes previously synthesized, were tested for anti-bacterial properties by KS K-0693-2001 as a test method for anti-bacterial properties of fabric after washing the fabrics 0 time, 10 times and 20 times.
The result is shown in Table 1 that represents anti-bacterial effect of the dyed antibacterial fibers according to the present invention by the following test for anti-bacterial properties. Table 1 proves antibacterial properties and washing durability of the antibacterial acid dyes according to the present invention.
TABLE 1 Test result for anti-bacterial properties
Figure imgf000020_0001
[Test of anti-bacterial properties]
Conditions of the test for determining anti-bacterial properties of the antibacterial fiber containing silver according to the present invention are as follows:
1. Test types of strain
1) Strain 1 : Staphylococcus aureus ATCC 6538 2) Strain 2 : Klebsiella pneumoniae ATCC 4352
2. Concentration of challenged strain of bacteria
1) Strain 1 : 1.3 x 105 numbers/ ml
2) Strain 2 : 1.5 x 105 numbers/ ml
3. Increasing rate: 1) strain 1 : 40 fold increase
2) strain 2 : 46 fold increase
4. control sample: nylon (KS K 0905-1996)
5. non-ionic surfactant: Tween 80 (0.05%)
INDUSTRIAL APPLICABILITY
As described in detail above, the present invention can produce antibacterial fiber product that is subjected to antibacterial process in the dyeing step, needs no alternative process for the purpose of antibacterial treatment, does not lose color in woven or knitted fabric fabricated of the antibacterial fibers because the dyes are decomposed, and has excellent durability to continuously exhibit antibacterial properties for a long period of time.
While the present invention has been described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various modifications and variations may be made therein without departing from the scope of the present invention as defined by the appended claims.

Claims

WHAT IS CLAIMED IS:
1. An antibacterial acid dye having a structure represented by chemical formula 1, comprising two identical sulfonamide based antibacterial compounds bonded to acidic dye by diazotization-coupling reaction:
(Chemical formula 1)
Figure imgf000023_0001
wherein R1 is H or OH, R2 is H, NH2, SO3H or sulfonamide based antibacterial compound A, R3 is H, SO3H or sulfonamide based antibacterial compound A, R4 is H or SO3H, and A is sulfonamide based antibacterial compound.
2. The antibacterial acid dye according to Claim 1, wherein the sulfonamide based antibacterial compound is sulfadiazine represented by general formula 1 , or sulfamethazine represented by general formula 2:
(General formula 1) Sulfadiazine
Figure imgf000023_0002
(General formula 2) Sulfamethiazine
Figure imgf000024_0001
3. The antibacterial acid dye according to Claim 1, wherein the acidic dye is one selected from a group consisting of 6-amino-4- hydroxynaphthalene-2-sulfonic acid represented by general formula 3, 7-amino-4-hydroxynaphthalene-2-sulfonic acid represented by general formula 4, 4-amino-5-hydroxynaphthalene- 1 -sulfonic acid represented by general formula 5, and 4-amino-5-hydroxynaphthalene-2,7-sulfonic acid represented by general formula 6:
(General formula 3)
6-amino-4-hydroxynaphthalene-2-sulfonic acid
Figure imgf000024_0002
(General formula 4)
7 - amino - 4 - hy droxynaphthalene - 2 - sulfonic acid
Figure imgf000024_0003
(General formula 5) 4-amino-5-hydroxynaphthalene- 1 -sulfonic acid
Figure imgf000025_0001
(General formula 6)
4 - amino- 5 -hydroxy naphthalene -2,7- sulfonic acid
Figure imgf000025_0002
4. A process for preparing antibacterial acid represented by the following chemical formula 1 , comprising: (I) first step of conducting diazotization of sulfadiazine or sulfamethiazine by using hydrochloric acid and sodium nitrite; (II) second step of azo-coupling the reactive product from the step (I) with one selected from a group consisting of 6- amino-4-hydroxynaphthalene-2-sulfonic acid, 7-amino-4- hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene- 1- sulfonic acid and 4-amino-5-hydroxynaphthalene-2,7-sulfonic acid; and (III) third step of azo-coupling the above resulting product from the step (II) with the reactive product further obtained from the step (I) by diazotization of sulfadiazine or sulfamethiazine with hydrochloric acid and sodium nitrite:
(Chemical formula 1)
Figure imgf000026_0001
wherein R1 is H or OH, R2 is H, NH2, SO3H or sulfonamide based antibacterial compound A, R3 is H, SO3H or sulfonamide based antibacterial compound A, R4 is H or SO3H, and A is sulfonamide based antibacterial compound.
5. An antibacterial fiber dyed by the antibacterial acid dye as defined in Claim 1.
PCT/KR2007/000707 2007-02-09 2007-02-09 Antibacterial acid dyes and method of preparing the same and antibacterial fiber dyed thereby WO2008096919A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05214256A (en) * 1991-05-15 1993-08-24 Ciba Geigy Ag Azo dye
WO1998044051A1 (en) * 1997-03-31 1998-10-08 Nippon Kayaku Kabushiki Kaisha Water-soluble disazo compounds, water-base ink composition, and colored object
KR20060002366A (en) * 2004-07-02 2006-01-09 주식회사 코오롱 Antibacterial acidic dyes having the sulphonamides as diazo component and antibacterial fiber thereby
KR20060094194A (en) * 2005-02-23 2006-08-29 주식회사 코오롱 Antibacterail acid dyes containing silver and a method of preparing the same and antibacterial fiber thereby

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05214256A (en) * 1991-05-15 1993-08-24 Ciba Geigy Ag Azo dye
WO1998044051A1 (en) * 1997-03-31 1998-10-08 Nippon Kayaku Kabushiki Kaisha Water-soluble disazo compounds, water-base ink composition, and colored object
KR20060002366A (en) * 2004-07-02 2006-01-09 주식회사 코오롱 Antibacterial acidic dyes having the sulphonamides as diazo component and antibacterial fiber thereby
KR20060094194A (en) * 2005-02-23 2006-08-29 주식회사 코오롱 Antibacterail acid dyes containing silver and a method of preparing the same and antibacterial fiber thereby

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