US20010000085A1 - Formaldehyde scavenging in microbiocidal articles - Google Patents
Formaldehyde scavenging in microbiocidal articles Download PDFInfo
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- US20010000085A1 US20010000085A1 US09/727,819 US72781900A US2001000085A1 US 20010000085 A1 US20010000085 A1 US 20010000085A1 US 72781900 A US72781900 A US 72781900A US 2001000085 A1 US2001000085 A1 US 2001000085A1
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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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/09—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with free halogens or interhalogen compounds
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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
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
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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
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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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
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
- D06M13/358—Triazines
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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
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
- D06M13/358—Triazines
- D06M13/364—Cyanuric acid; Isocyanuric acid; Derivatives thereof
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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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/202—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with halogen atoms, e.g. triclosan, povidone-iodine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
Definitions
- this invention relates to methods for generating biocidal materials and improved methods for producing them.
- this invention provides improved processes for producing biocidal materials in the absence of toxic materials.
- U.S. Pat. No. 5,882,357 which issued to Sun et al., on Mar. 16, 1999, discloses the use of heterocyclic amines such as 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH) and monomethylol-5,5-dimethylhydantoin (MDMH), to impart durable and regenerable antimicrobial functions to inter alia, cellulose materials.
- DDMH 1,3-dimethylol-5,5-dimethylhydantoin
- MDMH monomethylol-5,5-dimethylhydantoin
- Formaldehyde causes eye, upper respiratory tract and skin irritation and is a skin sensitizer. Sensory irritation occurs at concentrations as low as 0.1 ppm and significant irritation of the nose and throat occurs at concentration of about 1 ppm. Moreover, dermal contact causes various skin reactions, thus forcing persons sensitized to find other work. In certain instances, a byproduct of producing antimicrobial articles is the presence of free-formaldehyde.
- the present invention provides a process for preparing a microbiocidal article with a reduction in free-formaldehyde release, the process comprising: (a) immersing the article in an aqueous treating solution which comprises a heterocyclic amine and a polyol; and (b) treating the article with a halogenated solution, thereby rendering the article microbiocidal with a reduction in free-formaldehyde release.
- the aqueous treating solution further comprises a catalyst and a wetting agent.
- formaldehyde is scavenged by a polyol that reduces the formaldehyde to a harmless product.
- the preferred polyols include, but are not limited to, diethylene glycol or ethylene glycol.
- the heterocyclic amine is alkylated or partially alkylated. Suitable heterocyclic amines for use in the present invention include, but are not limited to, DMDMH alkylated DMDMH, or a mixture of DMDMH and its unmethylolated dimethylhydantoin (DMH) derivative. Using the aforementioned heterocyclic amines, it is possible to produce microbiocidal articles with low potential for formaldehyde release.
- the present invention provides a process for preparing a microbiocidal article with a reduction in free-formaldehyde release, the process comprising: (a) immersing the article in an aqueous treating solution which comprises an alkylated heterocyclic amine; and (b) treating the article with a halogenated solution, thereby rendering the article microbiocidal with a reduction in free-formaldehyde release.
- the alkylated or partially alkylated heterocyclic amine is less amenable to releasing formaldehyde than a heterocyclic amine.
- a polyol is used in conjunction with an alkylated heterocyclic amine to reduce formaldehyde.
- a catalyst and a wetting agent can optionally be used in the aqueous treating solution.
- DDMH refers to 1,3-dimethylol-5,5-dimethylhydantoin.
- MDMH monomethylol-5,5-dimethylhydantoin
- DMDHEU dimethyloldihydroxy-ethylene urea
- DMH dimethyloldihydroxy-ethylene urea
- alkylated refers to adding alkyl functional groups containing about 1 to 6 carbon atoms to heterocyclic amines having a free hydroxy group (e.g., hemiacetal functionality). These alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, n-pentyl and the like. Partially alkylated means adding alkyl functional groups, but still leaving at least one free hydroxy group (e.g., hemiacetal functionality). In preferred embodiments, DMDMH and MDMH are alkylated or partially alkylated.
- FIG. 1 illustrates various heterocyclic amines suitable for use in the present invention.
- FIG. 2 illustrates a mechanism of imparting microbiocidal properties using a method of the present invention.
- FIG. 3 illustrates a mechanism for formaldehyde scavenging using a process of the present invention.
- the present invention provides a process for preparing a microbiocidal article with a reduction in free-formaldehyde, the process comprising: (a) immersing the article in an aqueous treating solution which comprises a heterocyclic amine and a polyol; and (b) treating the article with a halogenated solution, thereby rendering the article microbiocidal with a reduction in free-formaldehyde.
- the aqueous treating solution further comprises a catalyst and a wetting agent.
- a wide variety of articles are suitable for use in the present invention. These articles include, but are not limited to, textiles such as cellulosic fabric, cellulosic yarn, and cellulosic fiber, wherein the foregoing can be woven or nonwoven; polymers such as polyester and cellulose; cotton fabric/polyester blends; polyester/rayon blends, wood materials such as wood pulp, paper, cardboard; garments such as shirts, pants, undergarments, coats, hoods, cloaks, hats, gloves, protective garments, surgical gowns, garments, masks, boots, aprons, and hospital and laboratory supplies. Those of skill in the art will know of other articles suitable for use in the processes of the present invention.
- the articles such as textiles, provide microbiocidal protection with a concomitant decrease or elimination of formaldehyde production.
- the article e.g., a fabric
- the aqueous treating solution comprises a heterocyclic amine and a polyol.
- the treating solution also comprises a wetting agent and a catalyst.
- wetting agent refers to a substance that increases the rate at which a liquid spreads across a surface, i.e., it renders a surface nonrepellent to a liquid.
- catalyst refers to a substance that augments the rate of a chemical reaction without itself being consumed.
- Suitable catalysts for use in the present invention include, but are not limited to, magnesium salts, zinc salts and ammonium salts.
- the catalysts include, but are not limited to, Catalyst 531, MgCl 2 , Mg(NO 3 ) 2 , Zn(NO 3 ) 2 and NH 4 NO 3 .
- a halogenated solution such as a halogenated aqueous solution.
- the halogenated solution can be a chlorine solution, a bromine solution, and combinations thereof, etc.
- the halogenated solution is sodium hypochlorite (e.g., a chlorine bleach solution such as CLOROX®).
- the treatment of the article with a halogenated solution renders the article microbiocidal.
- the articles become microbiocidal by grafting a heterocyclic N-halamine structure on the article.
- incorporation of a halamine on a fabric such as cotton, with subsequent halogenation renders the article microbiocidal.
- free-formaldehyde can be produced in the process of producing such microbiocidal articles.
- free-formaldehyde can be generated.
- formaldehyde can cause sever skin reactions and is quite toxic to humans.
- formaldehyde reduction or elimination is advantageous.
- Suitable examples include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycols having the formula HO(CH 2 CH 2 O) n H wherein n is about 1 to about 50, glycerin, and the like, and combinations thereof.
- the preferred polyols are diethylene glycol and ethylene glycol.
- the heterocyclic amine: polyol ratio used in the processes of the present invention is generally between about 0.2-1.0:1.0-6.0.
- the heterocyclic amine: polyol ratio is between about 0.5-1.0:1.0-3.0.
- the ratio is between about 0.5-1.0:1.0-3.0 for DMDMH:polyol and between about 0.5-1.0:1.0-2.0 for MDMH:polyol.
- the foregoing ratios are based on a mole/mole ratio. Microbiocidal fabrics treated using polyols in the aqueous treating solution achieved significant formaldehyde reduction on cotton and on polyester/cotton blends.
- the method further comprises removing excess aqueous treating solution from the article before treating the article with a halogenated aqueous solution.
- the excess aqueous treating solution is removed by ordinary mechanical methods, such as by passing the article (e.g., textile) between squeeze rolls, by centrifugation, by draining or by padding.
- the excess aqueous treating solution is removed by padding.
- the process optionally further comprises drying the article after removing excess aqueous treating solution to produce a dried article.
- the article is 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 and, more preferably, for about 5 minutes.
- the dried article can optionally be cured to produce a cured article.
- the curing process is conducted at a temperature ranging from about 120° C. to about 200° C. and, more preferably, at a temperature ranging from about 140° C. to about 160° C. for a period of time ranging from about 3 to about 8 minutes and, more preferably, for about 5 minutes.
- the heating can be carried out in an oven, preferably one having a forced draft of air directed at the surface of the article and exhausting through a vent to remove fumes.
- the cured article is then optionally washed to remove excess reagents. Washing of the treated article can be done with water.
- the covalent bonds formed are stable, insoluble, and durable to the mechanical agitation, spraying and rubbing that occurs in washing machines or in large scale continuous or batchwise textile washing equipment.
- the process further comprises drying the washed article to remove water.
- the article can optionally be dried before treating the article with a halogenated aqueous solution, to render the article microbiocidal. Drying of the article, such as a fabric, can be carried out by any ordinary means such as oven drying, line drying or, tumble drying in a mechanical clothes dryer. A drying temperature of about 80° C. to about 120° C. is particularly preferred. Suitable drying times are generally less than 15 minutes in duration.
- the present invention provides a process for preparing a mnicrobiocidal article with a reduction in free-formaldehyde release, comprising: (a) immersing the article in an aqueous treating solution which comprises a catalyst, a wetting agent, a heterocyclic amine and a polyol; (b) removing the excess treating solution from the article; (c) drying the article; (d) curing the article; (e) washing the cured article to remove excess reagents; (f) drying the washed article to remove water; and (g) treating the article with a halogenated aqueous solution, thereby rendering the article microbiocidal.
- an aqueous treating solution which comprises a catalyst, a wetting agent, a heterocyclic amine and a polyol
- removing the excess treating solution from the article comprising: (a) immersing the article in an aqueous treating solution which comprises a catalyst, a wetting agent, a heterocyclic amine and a
- heterocyclic amine refers to a 4- to 7-membered ring, having at least 3 members of the ring being carbon, and from 1 to 3 members of the ring being nitrogen, and from 0 to 1 member of the ring being an oxygen, wherein from 0 to 2 carbon members comprise a carbonyl group, and wherein at least 1 to 3 nitrogen atoms are substituted with a hydrogen or hydroxyalkyl group, such as —CH 2 OH, or a alkoxyalkyl group, such as —CH 2 OCH 3 . After halogenation, at least one ring nitrogen has bonded thereto a halogen atom.
- the preferred heterocyclic amines suitable for use in the present invention include, but are not limited to, monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidinfone, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin; and monoalkylated and dialkylated derivatives of monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetra
- the heterocyclic amine is alkylated.
- the alkylation process involves reacting a hydantoin derivative (e.g., DMDMH or MDMH) and an alcohol in an alcoholic solution.
- Suitable alcohols include, but are not limited to, alkanols such as methanol, ethanol, propanol, butanol, and combinations thereof, etc.
- the reaction can be carried-out within the temperature range of between about 10° C. to about 100° C., and preferably within the range between of about 40° C. to 80° C.
- the duration of the reaction is about 1 to about 24 hours, and preferably for about 2 to about 6 hours.
- the pH of the reaction mixture can range between about 1.0 to about 6.0 and preferably within the range of between about 2.0 to about 4.0.
- the pH of the reaction solution can be adjusted with any suitable mineral acids including, but not limited to, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid; as well as any organic acid including, but not limited to, acetic acid, glycolic acid, maleic acid, lactic acid, tartaric acid, oxalic acid, citric acid or combinations thereof.
- the aqueous treating solution comprises an alkylated heterocyclic amine or partially alkylated heterocyclic amine and a polyol.
- the alkylated or partially alkylated heterocyclic amine: polyol ratio is generally as set forth above.
- Using both an alkylated or partially alkylated heterocyclic amine and a polyol has an additive effect on the reduction on formaldehyde. For example, by admixing alkylated DMDMH with diethylene glycol the formaldehyde release reduction reached about 50-85% on cotton and about 55%-80% on polyester/cotton blends.
- the aqueous treating solution of the present invention comprises a heterocyclic amine (e.g. DMDMH or MDMH, an alkylated heterocyclic amine (e.g., alkylated or partially alkylated DMDMH or MDMH and a polyol such as diethylene glycol.
- a heterocyclic amine e.g. DMDMH or MDMH
- an alkylated heterocyclic amine e.g., alkylated or partially alkylated DMDMH or MDMH
- a polyol such as diethylene glycol.
- the heterocyclic amine i.e., the combination of heterocyclic amine and alkylated heterocyclic amine or partially alkylated
- polyol ratio used in the processes of the present invention is generally between about 0.2-1.0:1.0-6.0 mole/mole.
- the heterocyclic amine i.e., the combination of heterocyclic amine and alkylated heterocyclic amine or partially alkylated
- polyol ratio is between about 0.5-1.0:1.0-3.0 mole/mole.
- the aqueous treating solution for imparting low formaldehyde and formaldehyde free antimicrobial finishing comprises a heterocyclic amine (e.g., DMDMH, alkylated DMDMH, or a mixture thereof) with DMDHEU.
- the foregoing aqueous treating solution optionally comprises a polyol.
- the heterocyclic amine:DMDHEU ratio is generally between about 0.2-1.0:1.0-6.0 and preferably between about 0.5-1.0:1.0-0.5 mole/mole.
- the heterocyclic amine: polyol ratio is between about 0.2-1.0:1.0-6.0, and preferably, between about 0.5-1.0:1.0-3.0 mole/mole. Admixing DMDMH or MDMH with DMDHEU results in formaldehyde reduction in a range of about 70% on cotton and about 80% on polyester/cotton blends.
- the aqueous treating solution for imparting low formaldehyde and formaldehyde free antimicrobial finishing comprises a heterocyclic amine (e.g., DMDMH, alkylated DMDMH, or a mixture thereof) with DMH.
- a heterocyclic amine e.g., DMDMH, alkylated DMDMH, or a mixture thereof
- the foregoing aqueous treating solution optionally comprises a polyol. Admixing DMDMH or MDMH with DMH results in formaldehyde reduction in a range of about 60% on cotton and about 60% on polyester/cotton blends.
- additives can optionally be incorporated into the aqueous treating solution to impart favorable characteristics to microbiocidal articles.
- Such additives can include softeners and waterproofing agents that are known to and used by those of skill in the art.
- 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.).
- waterproofing agents which can be added to the aqueous treating solution include, but are not limited to, SEQUAPEL® (Sequa Chemical Inc., Chester, S.C.), SCOTCHGARD® (3M, St. Paul, Minn.) and other water repellent finishing solutions used by those of skill in the art.
- the microbiocidal articles produced using the present processes possess regenerable and durable properties. For instance, after effective microbiocidal activity is obtained, and subsequently exhausted, the article can be rendered capable of possessing microbiocidal properties again. By retreating the article with a halogenated solution the microbiocidal activity can be regenerated. As such, using the processes of the present invention, microbiocidal properties are imparted onto articles, such as textiles, and these properties are regenerable.
- microbiocidal properties imparted onto articles are durable.
- the durability of the process and its potential to antimicrobial was demonstrated after laundering.
- the functional finishing on the article e.g., cotton/polyester fabric
- these finished fabrics can therefore provide optimum protection as well as comfort to the wearers.
- This Example illustrates the use of an alkylated heterocyclic amine to reduce free-formaldehyde.
- a solution of 18.8 parts of DMDMH and 64 parts of methanol were acidified with hydrochloric acid to a pH value of 2.5-3.5 and then heated for 2 hours at 50° C.
- the resulting product was a clear liquid with a very slight odor of formaldehyde and this product was used to treat a 100% cotton fabric as follows.
- a 100 mL aqueous solution containing 17 parts of the product, 2 parts of Catalyst 531 (Sequa Chemical Inc., Chester, S.C.) and 0.1 part of TRITON-X 100 was applied to the fabric by padding at a wet pick-up of 90% based on the weight of the fabric.
- the treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C.
- the fabric was tested for formaldehyde content on fabric without washing. The results indicated a 58% reduction of formaldehyde on pure cotton and a 70% reduction on polyester/cotton blends.
- This Example illustrates the use of a heterocyclic amine and a polyol to reduce free-formaldehyde.
- the product was then used to treat a 100% cotton fabric as follows. A 100 mL aqueous solution containing 15.88 parts of the product, 2 parts of Catalyst 531 and 0.1 part of TRITON-X 100 was applied to the fabric by padding at a wet pick-up of 90% based on the weight of the fabric. The treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric without washing. The results indicated a 48% reduction of formaldehyde on cotton and a 46% reduction on polyester/cotton blends.
- a 100 mL of an aqueous finishing solution containing 17 parts of the product of Example 1 and two parts of Catalyst 531, 0.1 parts of TRITON-X and 4.34 parts of diethylene glycol were applied to a fabric under the same conditions as set forth in Example 1.
- the treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C.
- the fabric was tested for free-formaldehyde on fabric without washing. The results indicted a 68-82% reduction of formaldehyde on cotton and a 63-73% reduction on polyester/cotton blends.
- This Example illustrates the use of a heterocyclic amine and a polyol to reduce free-formaldehyde.
- a 600 mL aqueous solution containing 69 parts of a 34.78% DMDMH solution (0.1277 moles) and 30 parts of diethylene glycol (0.2830 moles), 12 parts of Sequa Catalyst 531, and 0.6 parts of TRITON X-100 were applied to a fabric.
- the treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C.
- the fabric was tested for free-formaldehyde on fabric. The results indicated a 58-70% reduction of formaldehyde on cotton and a 67-70% reduction on polyester/cotton blends.
- This Example illustrates the use of a heterocyclic amine, a polyol and softener to reduce free-formaldehyde.
- the treated fabric was dried for 5 minutes at 80° C. and cured one sample for 1.5 minutes at 200° C.
- the fabric was tested for free-formaldehyde on fabric, with a 78-80% reduction on cotton and a 67-79% reduction on polyester/cotton.
- This Example illustrates the use of a heterocyclic amine and polyol to reduce free-formaldehyde.
- a 100 mL aqueous finishing solution containing 16.12 parts of the product of Example 2 and 4.35 parts of diethylene glycol, 2 parts of catalyst 531, 0.1 parts of TRITON-X was applied to a fabric.
- the treated fabric was dried for 5 minutes at 80° C. and cured for 1.5 minutes at 200° C.
- the fabric was tested for free-formaldehyde on fabric. The results indicated a 80% reduction of formaldehyde on cotton and a 79% reduction on polyester/cotton blends.
- This Example illustrates the use of a combination of heterocyclic amines, a polyol and softener to reduce free-formaldehyde.
- a 100 mL aqueous finishing solution containing 2 parts of DMDMH (0.0106 mole) and 1.89 parts of DMDHEU (0.0106 mole), 2 parts of Catalyst 531, 0.1 parts of TRITON-X with or without 3 parts of a fabric softener was applied to a fabric.
- the treated fabric was dried for 5 minutes at 80° C. and cured for 1.5 minutes at 200° C.
- the fabric was tested for free-formaldehyde on fabric. The results indicated a 77% reduction of formaldehyde on cotton and an 82% reduction on polyester/cotton blends.
- the fabric after bleaching in a chlorine solution exhibited durable biocidal effects.
- This Example illustrates the use of a combination of heterocyclic amines and softener to reduce free-formaldehyde.
- a 100 mL aqueous finishing solution containing 3.85 parts of DMDMH (0.02 moles) and 3.2 parts of 5,5-dimethylhydantoin (0.025 moles), 2 parts of Catalyst 531, 0.1 parts of TRITON-X with or without 3% fabric softener (MYKON) was applied to a fabric.
- the treated fabric was dried for 5 minutes at 80° C. and cured one sample for 1.5 minutes at 200° C.
- the fabric was tested for free-formaldehyde on fabric. The results indicated a 59% reduction of formaldehyde on cotton and a 63% reduction on polyester/cotton blends.
- This Example illustrates a control process using a heterocyclic amine only.
- the fabric was treated with DMDMH instead of the product of this invention under the same conditions.
- the fabric was tested for free-formaldehyde on fabric without washing, with 1191-1333 ppm on cotton and 950-1141 ppm on polyester/cotton.
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Abstract
Improved methods for durable and regenerable antimicrobial finishing of fabrics are disclosed. In certain embodiments, the methods reduce the amount of free-formaldehyde released during processing by using a formaldehyde scavenger such as a polyol. The improved process imparts regenerable antimicrobial functions to cellulose articles including textiles, papers, wood pulp, and any cellulose-containing materials. The treated product acquire antimicrobial properties after being treated with a halogenated solution.
Description
- 1. This application is a continuation-in-part of U.S. patent application Ser. No. 09/102,525, filed Jun. 22, 1998, which is a divisional of U.S. patent application Ser. No. 08/713,406, filed Sep. 13, 1996, now U.S. Pat. No. 5,882,357, both disclosures of which are hereby incorporated by reference in their entirety for all purposes.
- 2. In general, this invention relates to methods for generating biocidal materials and improved methods for producing them. In particular, this invention provides improved processes for producing biocidal materials in the absence of toxic materials.
- 3. Studies indicate that formaldehyde is a potential human carcinogen. Airborne concentrations above 0.1 ppm can cause irritation of the eyes, nose and throat. The severity of irritation increases as concentrations increase; at 100 ppm it is immediately dangerous to life and health. Facilities that manufacture, consume or produce formaldehyde must control workers exposure in accordance with strict regulations. Dermal contact causes various skin reactions including sensitization, which could force persons thus sensitized to find other work.
- 4. The permissible exposure limit (PEL) for formaldehyde in all workplaces (including general industry, construction, and maritime, but not in agriculture) covered by the Occupational Safety and Health Act is 0.75 ppm measured as an 8-hour time weighted average (TWA). This standard includes a 2 ppm short-term exposure limit (STEL) (i.e., maximum exposure allowed during a 15-minute period). The “action level” is 0.5 ppm measured over 8 hours.
- 5. U.S. Pat. No. 5,882,357, which issued to Sun et al., on Mar. 16, 1999, discloses the use of heterocyclic amines such as 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH) and monomethylol-5,5-dimethylhydantoin (MDMH), to impart durable and regenerable antimicrobial functions to inter alia, cellulose materials. In certain instances, during the process of imparting antimicrobial properties to cellulosic materials, free-formaldehyde can be generated. Moreover, when these microbiocidal textiles are stored under humid conditions, free-formaldehyde can be released.
- 6. Thus, despite the advances made by U.S. Pat. No. 5,882,357, there remains a need to reduce the amount of formaldehyde released during preparation of microbiocidal products. The present invention remedies such need by providing processes that reduce the amount of formaldehyde during the preparation of microbiocidal articles.
- 7. Formaldehyde causes eye, upper respiratory tract and skin irritation and is a skin sensitizer. Sensory irritation occurs at concentrations as low as 0.1 ppm and significant irritation of the nose and throat occurs at concentration of about 1 ppm. Moreover, dermal contact causes various skin reactions, thus forcing persons sensitized to find other work. In certain instances, a byproduct of producing antimicrobial articles is the presence of free-formaldehyde. To remedy this drawback, the present invention provides a process for preparing a microbiocidal article with a reduction in free-formaldehyde release, the process comprising: (a) immersing the article in an aqueous treating solution which comprises a heterocyclic amine and a polyol; and (b) treating the article with a halogenated solution, thereby rendering the article microbiocidal with a reduction in free-formaldehyde release. Preferably, the aqueous treating solution further comprises a catalyst and a wetting agent.
- 8. In certain preferred aspects, formaldehyde is scavenged by a polyol that reduces the formaldehyde to a harmless product. The preferred polyols include, but are not limited to, diethylene glycol or ethylene glycol. In certain preferred embodiments, the heterocyclic amine is alkylated or partially alkylated. Suitable heterocyclic amines for use in the present invention include, but are not limited to, DMDMH alkylated DMDMH, or a mixture of DMDMH and its unmethylolated dimethylhydantoin (DMH) derivative. Using the aforementioned heterocyclic amines, it is possible to produce microbiocidal articles with low potential for formaldehyde release.
- 9. In another aspect, the present invention provides a process for preparing a microbiocidal article with a reduction in free-formaldehyde release, the process comprising: (a) immersing the article in an aqueous treating solution which comprises an alkylated heterocyclic amine; and (b) treating the article with a halogenated solution, thereby rendering the article microbiocidal with a reduction in free-formaldehyde release. In this aspect, the alkylated or partially alkylated heterocyclic amine is less amenable to releasing formaldehyde than a heterocyclic amine. Optionally, a polyol is used in conjunction with an alkylated heterocyclic amine to reduce formaldehyde. Moreover, a catalyst and a wetting agent can optionally be used in the aqueous treating solution.
- 10. These and other aspects of the present invention will be readily apparent when read with the detailed description and figures that follow.
- 11. As used herein, the acronym “DMDMH” refers to 1,3-dimethylol-5,5-dimethylhydantoin.
- 12. As used herein, the acronym “MDMH” refers to monomethylol-5,5-dimethylhydantoin.
- 13. As used herein, the acronym “DMDHEU” refers to dimethyloldihydroxy-ethylene urea.
- 14. As used herein, the acronym “DMH” refers to dimethyloldihydroxy-ethylene urea.
- 15. The term “alkylated” or “partially alkylated” refers to adding alkyl functional groups containing about 1 to 6 carbon atoms to heterocyclic amines having a free hydroxy group (e.g., hemiacetal functionality). These alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, n-pentyl and the like. Partially alkylated means adding alkyl functional groups, but still leaving at least one free hydroxy group (e.g., hemiacetal functionality). In preferred embodiments, DMDMH and MDMH are alkylated or partially alkylated.
- 16.FIG. 1 illustrates various heterocyclic amines suitable for use in the present invention.
- 17.FIG. 2 illustrates a mechanism of imparting microbiocidal properties using a method of the present invention.
- 18.FIG. 3 illustrates a mechanism for formaldehyde scavenging using a process of the present invention.
- 19. Heterocyclic amines have been used as agents to impart durable and regenerable antimicrobial functions to cellulose materials. In certain instances, a byproduct of producing antimicrobial articles is the presence of free-formaldehyde. As explained above, the presence of free-formaldehyde is undesirable for health and safety reasons.
- 20. As such, the present invention provides a process for preparing a microbiocidal article with a reduction in free-formaldehyde, the process comprising: (a) immersing the article in an aqueous treating solution which comprises a heterocyclic amine and a polyol; and (b) treating the article with a halogenated solution, thereby rendering the article microbiocidal with a reduction in free-formaldehyde. Preferably, the aqueous treating solution further comprises a catalyst and a wetting agent.
- 21. A wide variety of articles are suitable for use in the present invention. These articles include, but are not limited to, textiles such as cellulosic fabric, cellulosic yarn, and cellulosic fiber, wherein the foregoing can be woven or nonwoven; polymers such as polyester and cellulose; cotton fabric/polyester blends; polyester/rayon blends, wood materials such as wood pulp, paper, cardboard; garments such as shirts, pants, undergarments, coats, hoods, cloaks, hats, gloves, protective garments, surgical gowns, garments, masks, boots, aprons, and hospital and laboratory supplies. Those of skill in the art will know of other articles suitable for use in the processes of the present invention.
- 22. Using the methods of the present invention, the articles, such as textiles, provide microbiocidal protection with a concomitant decrease or elimination of formaldehyde production. The article (e.g., a fabric) is immersed in an aqueous treating solution. In certain embodiments, the aqueous treating solution comprises a heterocyclic amine and a polyol. Preferably, the treating solution also comprises a wetting agent and a catalyst. As used herein, “wetting agent” refers to a substance that increases the rate at which a liquid spreads across a surface, i.e., it renders a surface nonrepellent to a liquid. Examples of suitable wetting agents include, but are not limited to, TRITON®X-100 which is generically a polyoxyethylene (10) isooctylphenyl ether commercially available from Sigma Chemical Co., St. Louis, Mo; SEQUAWET® which is generically, a wetting agent containing nonionic surfactants commercially available from Sequa Chemical Inc., Chester, S.C.; and AMWET® which is generically, a wetting agent containing nonionic surfactants commercially available from 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. As used herein, “catalyst” refers to a substance that augments the rate of a chemical reaction without itself being consumed. Suitable catalysts for use in the present invention include, but are not limited to, magnesium salts, zinc salts and ammonium salts. In presently preferred embodiments, the catalysts include, but are not limited to, Catalyst 531, MgCl2, Mg(NO3)2, Zn(NO3)2 and NH4NO3.
- 23. After the article, such as a fabric, is immersed in the above-described aqueous treating solution, the article is then treated with a halogenated solution, such as a halogenated aqueous solution. The halogenated solution can be a chlorine solution, a bromine solution, and combinations thereof, etc. In a presently preferred embodiment, the halogenated solution is sodium hypochlorite (e.g., a chlorine bleach solution such as CLOROX®). The treatment of the article with a halogenated solution renders the article microbiocidal.
- 24. As disclosed in U.S. Pat. No. 5,882,357, the articles become microbiocidal by grafting a heterocyclic N-halamine structure on the article. With reference to FIG. 2, incorporation of a halamine on a fabric such as cotton, with subsequent halogenation renders the article microbiocidal. However, in certain embodiments, in the process of producing such microbiocidal articles, free-formaldehyde can be produced. Moreover, when microbiocidal articles are stored under humid conditions, free-formaldehyde can be generated. As discussed above, formaldehyde can cause sever skin reactions and is quite toxic to humans. Thus, from an industrial hygiene point of view, formaldehyde reduction or elimination is advantageous.
- 25. Surprisingly, the inventor has discovered that if a polyol is used in the process of making the article microbiocidal, free-formaldehyde can be reduced or eliminated entirely. Without being bound by any particular theory, it is believed that the formaldehyde reacts with a polyol and is reduce to a harmless product. With reference to FIG. 3, one possible mechanism of action of scavenging formaldehyde is shown. The term “polyol” refers to a compound containing a plurality of hydroxyl groups. Suitable examples include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycols having the formula HO(CH2CH2O)nH wherein n is about 1 to about 50, glycerin, and the like, and combinations thereof. The preferred polyols are diethylene glycol and ethylene glycol.
- 26. In certain embodiments, the heterocyclic amine: polyol ratio used in the processes of the present invention is generally between about 0.2-1.0:1.0-6.0. Preferably, the heterocyclic amine: polyol ratio is between about 0.5-1.0:1.0-3.0. In certain preferred embodiments, the ratio is between about 0.5-1.0:1.0-3.0 for DMDMH:polyol and between about 0.5-1.0:1.0-2.0 for MDMH:polyol. The foregoing ratios are based on a mole/mole ratio. Microbiocidal fabrics treated using polyols in the aqueous treating solution achieved significant formaldehyde reduction on cotton and on polyester/cotton blends.
- 27. In certain aspects of the present invention, several steps can optionally be inserted between steps (a) and (b) above. For instance, in certain preferred aspects, the method further comprises removing excess aqueous treating solution from the article before treating the article with a halogenated aqueous solution. In this aspect, the excess aqueous treating solution is removed by ordinary mechanical methods, such as by passing the article (e.g., textile) between squeeze rolls, by centrifugation, by draining or by padding. In a preferred embodiment, the excess aqueous treating solution is removed by padding.
- 28. In addition, the process optionally further comprises drying the article after removing excess aqueous treating solution to produce a dried article. In this aspect, the article is 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 and, more preferably, for about 5 minutes.
- 29. Moreover, the dried article can optionally be cured to produce a cured article. The curing process is conducted at a temperature ranging from about 120° C. to about 200° C. and, more preferably, at a temperature ranging from about 140° C. to about 160° C. for a period of time ranging from about 3 to about 8 minutes and, more preferably, for about 5 minutes. The heating can be carried out in an oven, preferably one having a forced draft of air directed at the surface of the article and exhausting through a vent to remove fumes.
- 30. The cured article is then optionally washed to remove excess reagents. Washing of the treated article can be done with water. The covalent bonds formed are stable, insoluble, and durable to the mechanical agitation, spraying and rubbing that occurs in washing machines or in large scale continuous or batchwise textile washing equipment. In certain preferred embodiments, the process further comprises drying the washed article to remove water.
- 31. The article can optionally be dried before treating the article with a halogenated aqueous solution, to render the article microbiocidal. Drying of the article, such as a fabric, can be carried out by any ordinary means such as oven drying, line drying or, tumble drying in a mechanical clothes dryer. A drying temperature of about 80° C. to about 120° C. is particularly preferred. Suitable drying times are generally less than 15 minutes in duration.
- 32. In certain preferred aspects, the present invention provides a process for preparing a mnicrobiocidal article with a reduction in free-formaldehyde release, comprising: (a) immersing the article in an aqueous treating solution which comprises a catalyst, a wetting agent, a heterocyclic amine and a polyol; (b) removing the excess treating solution from the article; (c) drying the article; (d) curing the article; (e) washing the cured article to remove excess reagents; (f) drying the washed article to remove water; and (g) treating the article with a halogenated aqueous solution, thereby rendering the article microbiocidal.
- 33. As used herein, “heterocyclic amine,” refers to a 4- to 7-membered ring, having at least 3 members of the ring being carbon, and from 1 to 3 members of the ring being nitrogen, and from 0 to 1 member of the ring being an oxygen, wherein from 0 to 2 carbon members comprise a carbonyl group, and wherein at least 1 to 3 nitrogen atoms are substituted with a hydrogen or hydroxyalkyl group, such as —CH2OH, or a alkoxyalkyl group, such as —CH2OCH3. After halogenation, at least one ring nitrogen has bonded thereto a halogen atom. In addition, the ring members can be further substituted with alkyl groups, such as methyl, ethyl, etc., or hydroxy groups. Heterocyclic N-halamines are generally disclosed in U.S. Pat. No. 5,490,983 issued to Worley, et al. on Feb. 13, 1996, the teachings of which are incorporated herein by reference for all purposes.
- 34. The preferred heterocyclic amines suitable for use in the present invention include, but are not limited to, monomethylol-5,5-dimethylhydantoin (MDMH), 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH); monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidinfone, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin; and monoalkylated and dialkylated derivatives of monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid, 5,5-dimethylhydantoin, 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one and mixtures thereof Preferably the heterocyclic amine is monomethylol-5,5-dimethylhydantoin (MDM), and 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH) (see, FIG. 1). In certain preferred embodiments, the heterocyclic amine is DMDMH, an alkylated DMDMH, or a mixture of DMDMH and its unmethylolated dimethylhydantoin (DMH) or DMDHEU.
- 35. In certain other embodiments, the heterocyclic amine is alkylated. In general, the alkylation process involves reacting a hydantoin derivative (e.g., DMDMH or MDMH) and an alcohol in an alcoholic solution. Suitable alcohols include, but are not limited to, alkanols such as methanol, ethanol, propanol, butanol, and combinations thereof, etc. The reaction can be carried-out within the temperature range of between about 10° C. to about 100° C., and preferably within the range between of about 40° C. to 80° C. The duration of the reaction is about 1 to about 24 hours, and preferably for about 2 to about 6 hours. The pH of the reaction mixture can range between about 1.0 to about 6.0 and preferably within the range of between about 2.0 to about 4.0. The pH of the reaction solution can be adjusted with any suitable mineral acids including, but not limited to, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid; as well as any organic acid including, but not limited to, acetic acid, glycolic acid, maleic acid, lactic acid, tartaric acid, oxalic acid, citric acid or combinations thereof.
- 36. In another embodiment, the aqueous treating solution comprises an alkylated heterocyclic amine or partially alkylated heterocyclic amine and a polyol. Preferably, the alkylated or partially alkylated heterocyclic amine: polyol ratio is generally as set forth above. Using both an alkylated or partially alkylated heterocyclic amine and a polyol has an additive effect on the reduction on formaldehyde. For example, by admixing alkylated DMDMH with diethylene glycol the formaldehyde release reduction reached about 50-85% on cotton and about 55%-80% on polyester/cotton blends.
- 37. In yet another embodiment, the aqueous treating solution of the present invention comprises a heterocyclic amine (e.g. DMDMH or MDMH, an alkylated heterocyclic amine (e.g., alkylated or partially alkylated DMDMH or MDMH and a polyol such as diethylene glycol. In certain embodiments, the heterocyclic amine (i.e., the combination of heterocyclic amine and alkylated heterocyclic amine or partially alkylated): polyol ratio used in the processes of the present invention is generally between about 0.2-1.0:1.0-6.0 mole/mole. Preferably, the heterocyclic amine (i.e., the combination of heterocyclic amine and alkylated heterocyclic amine or partially alkylated): polyol ratio is between about 0.5-1.0:1.0-3.0 mole/mole. By admixing a heterocyclic amine, an alkylated heterocyclic amine (or partially alkylated heterocyclic amine) and a polyol, formaldehyde release was reduced in a range of about 70% on cotton and about 80% on polyester/cotton blends.
- 38. In another embodiment, the aqueous treating solution for imparting low formaldehyde and formaldehyde free antimicrobial finishing comprises a heterocyclic amine (e.g., DMDMH, alkylated DMDMH, or a mixture thereof) with DMDHEU. In a preferred embodiment, the foregoing aqueous treating solution optionally comprises a polyol. In certain embodiments, the heterocyclic amine:DMDHEU ratio is generally between about 0.2-1.0:1.0-6.0 and preferably between about 0.5-1.0:1.0-0.5 mole/mole. In certain embodiments, the heterocyclic amine: polyol ratio is between about 0.2-1.0:1.0-6.0, and preferably, between about 0.5-1.0:1.0-3.0 mole/mole. Admixing DMDMH or MDMH with DMDHEU results in formaldehyde reduction in a range of about 70% on cotton and about 80% on polyester/cotton blends.
- 39. In still yet another embodiment, the aqueous treating solution for imparting low formaldehyde and formaldehyde free antimicrobial finishing comprises a heterocyclic amine (e.g., DMDMH, alkylated DMDMH, or a mixture thereof) with DMH. In a preferred embodiment, the foregoing aqueous treating solution optionally comprises a polyol. Admixing DMDMH or MDMH with DMH results in formaldehyde reduction in a range of about 60% on cotton and about 60% on polyester/cotton blends.
- 40. Those of skill in the art will readily appreciate that other additives can optionally be incorporated into the aqueous treating solution to impart favorable characteristics to microbiocidal articles. Such additives can include softeners and waterproofing agents that are known to and used by those of skill in the art. Examples of 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.). Examples of waterproofing agents which can be added to the aqueous treating solution include, but are not limited to, SEQUAPEL® (Sequa Chemical Inc., Chester, S.C.), SCOTCHGARD® (3M, St. Paul, Minn.) and other water repellent finishing solutions used by those of skill in the art.
- 41. In certain aspects, the microbiocidal articles produced using the present processes possess regenerable and durable properties. For instance, after effective microbiocidal activity is obtained, and subsequently exhausted, the article can be rendered capable of possessing microbiocidal properties again. By retreating the article with a halogenated solution the microbiocidal activity can be regenerated. As such, using the processes of the present invention, microbiocidal properties are imparted onto articles, such as textiles, and these properties are regenerable.
- 42. Furthermore, the microbiocidal properties imparted onto articles are durable. The durability of the process and its potential to antimicrobial was demonstrated after laundering. Thus, the functional finishing on the article (e.g., cotton/polyester fabric) is durable, surviving many machine washes without compromising its microbiocidal potential. These finished fabrics can therefore provide optimum protection as well as comfort to the wearers.
- 43. The following examples are offered to illustrate, but not to limit the claimed invention.
- 44. This Example illustrates the use of an alkylated heterocyclic amine to reduce free-formaldehyde.
- 45. A solution of 18.8 parts of DMDMH and 64 parts of methanol were acidified with hydrochloric acid to a pH value of 2.5-3.5 and then heated for 2 hours at 50° C. The resulting product was a clear liquid with a very slight odor of formaldehyde and this product was used to treat a 100% cotton fabric as follows. A 100 mL aqueous solution containing 17 parts of the product, 2 parts of Catalyst 531 (Sequa Chemical Inc., Chester, S.C.) and 0.1 part of TRITON-X 100 was applied to the fabric by padding at a wet pick-up of 90% based on the weight of the fabric. The treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C. The fabric was tested for formaldehyde content on fabric without washing. The results indicated a 58% reduction of formaldehyde on pure cotton and a 70% reduction on polyester/cotton blends.
- 46. This Example illustrates the use of a heterocyclic amine and a polyol to reduce free-formaldehyde.
- 47. 48 grams of DMDMH (0.2553 mole) and 60 grams of diethylene glycol (0.5660 mole) were reacted in 93 grams of water and were subsequently acidified with sulfuric acid to a pH value of 3.0 and heated for 6 hours at 75° C. The resulting product was a clear liquid with a very slight odor of formaldehyde.
- 48. The product was then used to treat a 100% cotton fabric as follows. A 100 mL aqueous solution containing 15.88 parts of the product, 2 parts of Catalyst 531 and 0.1 part of TRITON-X 100 was applied to the fabric by padding at a wet pick-up of 90% based on the weight of the fabric. The treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric without washing. The results indicated a 48% reduction of formaldehyde on cotton and a 46% reduction on polyester/cotton blends.
- 49. This Example illustrates the use of an alkylated heterocyclic amine and a polyol to reduce free-formaldehyde.
- 50. A 100 mL of an aqueous finishing solution containing 17 parts of the product of Example 1 and two parts of Catalyst 531, 0.1 parts of TRITON-X and 4.34 parts of diethylene glycol were applied to a fabric under the same conditions as set forth in Example 1. The treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric without washing. The results indicted a 68-82% reduction of formaldehyde on cotton and a 63-73% reduction on polyester/cotton blends.
- 51. This Example illustrates the use of a heterocyclic amine and a polyol to reduce free-formaldehyde.
- 52. A 600 mL aqueous solution containing 69 parts of a 34.78% DMDMH solution (0.1277 moles) and 30 parts of diethylene glycol (0.2830 moles), 12 parts of Sequa Catalyst 531, and 0.6 parts of TRITON X-100 were applied to a fabric. The treated fabric was dried for 5 minutes at 80° C. and cured for 6 minutes at 160° C. or 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric. The results indicated a 58-70% reduction of formaldehyde on cotton and a 67-70% reduction on polyester/cotton blends.
- 53. This Example illustrates the use of a heterocyclic amine, a polyol and softener to reduce free-formaldehyde.
- 54. A 100 mL aqueous solution containing 3.85 Parts of DMDMH (0.02 moles) and 6.51 parts of diethylene glycol (0.06 moles), 2 parts of catalyst 531, 0.1 parts of TRITON-X, with or without 3% fabric softener (MYKON available from Sequa Chemical Inc. Chester, S.C.) was applied to a fabric. The treated fabric was dried for 5 minutes at 80° C. and cured one sample for 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric, with a 78-80% reduction on cotton and a 67-79% reduction on polyester/cotton.
- 55. This Example illustrates the use of a heterocyclic amine and polyol to reduce free-formaldehyde.
- 56. A 100 mL aqueous finishing solution containing 16.12 parts of the product of Example 2 and 4.35 parts of diethylene glycol, 2 parts of catalyst 531, 0.1 parts of TRITON-X was applied to a fabric. The treated fabric was dried for 5 minutes at 80° C. and cured for 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric. The results indicated a 80% reduction of formaldehyde on cotton and a 79% reduction on polyester/cotton blends.
- 57. This Example illustrates the use of a combination of heterocyclic amines, a polyol and softener to reduce free-formaldehyde.
- 58. A 100 mL aqueous finishing solution containing 2 parts of DMDMH (0.0106 mole) and 1.89 parts of DMDHEU (0.0106 mole), 2 parts of Catalyst 531, 0.1 parts of TRITON-X with or without 3 parts of a fabric softener was applied to a fabric. The treated fabric was dried for 5 minutes at 80° C. and cured for 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric. The results indicated a 77% reduction of formaldehyde on cotton and an 82% reduction on polyester/cotton blends. The fabric after bleaching in a chlorine solution exhibited durable biocidal effects.
- 59. This Example illustrates the use of a combination of heterocyclic amines and softener to reduce free-formaldehyde.
- 60. A 100 mL aqueous finishing solution containing 3.85 parts of DMDMH (0.02 moles) and 3.2 parts of 5,5-dimethylhydantoin (0.025 moles), 2 parts of Catalyst 531, 0.1 parts of TRITON-X with or without 3% fabric softener (MYKON) was applied to a fabric. The treated fabric was dried for 5 minutes at 80° C. and cured one sample for 1.5 minutes at 200° C. The fabric was tested for free-formaldehyde on fabric. The results indicated a 59% reduction of formaldehyde on cotton and a 63% reduction on polyester/cotton blends.
- 61. This Example illustrates a control process using a heterocyclic amine only.
- 62. The fabric was treated with DMDMH instead of the product of this invention under the same conditions. The fabric was tested for free-formaldehyde on fabric without washing, with 1191-1333 ppm on cotton and 950-1141 ppm on polyester/cotton.
- 63. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.
Claims (33)
1. A process for preparing a microbiocidal article with a reduction in free-formaldehyde release, said process comprising:
(a) immersing said article in an aqueous treating solution which comprises a heterocyclic amine and a polyol; and
(b) treating said article with a halogenated solution, thereby rendering said article microbiocidal with a reduction in free-formaldehyde release.
2. The process according to , wherein said aqueous treating solution further comprises a catalyst and a wetting agent.
claim 1
3. The process according to , wherein said heterocyclic amine is alkylated or partially alkylated.
claim 1
4. The process according to , wherein said polyol is a member selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycols having the formula HO(CH2CH2O)nH wherein n is about 1 to about 50, glycerin and combinations thereof.
claim 1
5. The process according to , wherein said polyol is ethylene glycol.
claim 4
6. The process according to , wherein said polyol is diethylene glycol.
claim 4
7. The process according to , wherein said heterocyclic amine and said polyol are present in said treating solution in a heterocyclic amine:polyol ratio between about 0.2:1.0 to about 1.0:6.0 mole/mole.
claim 1
8. The process according to , wherein said heterocyclic amine:polyol ratio is about 0.5:1.0 to about 1.0:3.0 mole/mole.
claim 7
9. The process according to , wherein said heterocyclic amine is a member selected from the group consisting of monomethylol-5,5-dimethylhydantoin (MDS), 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH), 5,5-dimethylhydantoin (DMH); monoalkylolated and dialklylolated derivatives of 2,2,5,5-tetramethytl-1,3-imidazolidin-4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid and 5,5-dimethylhydantoin (DMH); and monoalkylated and dialkylated derivatives of monoalkylolated and dialkylolated derivatives of 2,2,5,5-tetramethyl-1,3-imidazolidin4-one, 6,6-dimethyl-1,3,5-triazine-2,4-dione, 4,4,5,5-tetramethyl-1,3-imidazolidin-2-one, cyanuric acid, 5,5-dimethylhydantoin, 2,2,5,5-tetramethyl-1,3-imidazolidin-4-one, an alkylated derivative thereof and mixtures thereof.
claim 1
10. The process according to , wherein said heterocyclic amine is 1,3-dimethylol-5,5-dimethylhydantoin (MDMH) or an alkylated derivative thereof.
claim 9
11. The process according to , wherein said heterocyclic amine is monomethylol-5,5-dimethylhydantoin (MDMH) or an alkylated derivative thereof.
claim 9
12. The process according to further comprising dimethyloldihydroxyethylene urea (DMDHEU) or an alkylated derivative thereof.
claim 11
13. The process according to , further comprising dimethyloldihydroxyethylene urea (DMDHEU) or an alkylated derivative thereof.
claim 10
14. The process according to , further comprising dimethyloldihydroxyethylene urea (DMDHEU) or an alkylated derivative thereof.
claim 11
15. The process according to , further comprising 5,5-dimethylhydantoin (DMH).
claim 10
16. The process according to , further comprising 5,5-dimethylhydantoin (DMH).
claim 11
17. The process of , further comprising removing excess aqueous treating solution from said article before treating said article with a halogenated aqueous solution.
claim 1
18. The process of , further comprising drying said article after removing excess aqueous treating solution to produce a dried article.
claim 17
19. The process of , further comprising curing said dried article to produce a cured article.
claim 18
20. The process of , further comprising washing said cured article to remove excess reagents.
claim 19
21. The process of , further comprising drying said washed article to remove water.
claim 20
22. The process of , wherein said article is a textile.
claim 1
23. The process of , wherein said textile is a member selected from the group consisting of cellulosic fabric, cellulosic yarn, and cellulosic fiber.
claim 22
24. The process of , wherein said textile is cotton fabric.
claim 22
25. The process of , wherein said textile is cotton fabric/polyester blend.
claim 22
26. The process of , wherein said article is a polymer.
claim 1
27. The process of , wherein said polymer is a member selected from the group consisting of cellulose and a synthetic polymer.
claim 26
28. The process of , wherein said halogenated aqueous solution comprises sodium hypochlorite.
claim 1
29. The process of , wherein said catalyst is a member selected from the group consisting of Catalyst 531, MgCl2, Mg(NO3)2, Zn(NO3)2 and NH4NO3.
claim 1
30. A process for preparing a microbiocidal article with a reduction in free-formaldehyde release, said process comprising:
(a) immersing said article in an aqueous treating solution which comprises an alkylated heterocyclic amine; and
(b) treating said article with a halogenated solution, thereby rendering said article microbiocidal with a reduction in free-formaldehyde release.
31. The process according to , wherein said alkylated heterocyclic amine is alkylated or partially alkylated 1,3-dimethylol-5,5-dimethylhydantoin (DMDMH).
claim 30
32. The process according to , wherein said alkylated heterocyclic amine is alkylated or partially alkylated monomethylol-5,5-dimethylhydantoin (MDMH).
claim 30
33. The process according to , wherein said aqueous treating solution further comprises a catalyst and a wetting agent.
claim 30
Priority Applications (1)
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US09/727,819 US20010000085A1 (en) | 1996-09-13 | 2000-11-30 | Formaldehyde scavenging in microbiocidal articles |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/713,406 US5882357A (en) | 1996-09-13 | 1996-09-13 | Durable and regenerable microbiocidal textiles |
US09/102,525 US6077319A (en) | 1996-09-13 | 1998-06-22 | Processes for preparing microbiocidal textiles |
US09/416,203 US6241783B1 (en) | 1996-09-13 | 1999-10-08 | Formaldehyde scavenging in microbiocidal articles |
US09/727,819 US20010000085A1 (en) | 1996-09-13 | 2000-11-30 | Formaldehyde scavenging in microbiocidal articles |
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US09/416,203 Continuation US6241783B1 (en) | 1996-09-13 | 1999-10-08 | Formaldehyde scavenging in microbiocidal articles |
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US09/416,203 Expired - Fee Related US6241783B1 (en) | 1996-09-13 | 1999-10-08 | Formaldehyde scavenging in microbiocidal articles |
US09/727,819 Abandoned US20010000085A1 (en) | 1996-09-13 | 2000-11-30 | Formaldehyde scavenging in microbiocidal articles |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040191315A1 (en) * | 2003-03-24 | 2004-09-30 | Mike Slattery | Office products containing antimicrobial agent |
CN113842764A (en) * | 2021-09-28 | 2021-12-28 | 布鲁舍(北京)环境技术有限公司 | Formaldehyde and peculiar smell scavenging agent and preparation method thereof |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6770287B1 (en) * | 2000-06-19 | 2004-08-03 | The Regents Of The University Of California | Biocidal cellulosic material |
WO2002079563A1 (en) * | 2001-03-30 | 2002-10-10 | The Regents Of The University Of California | Multifunctional textiles |
US6962608B1 (en) | 2002-10-01 | 2005-11-08 | The Regents Of The University Of California | Regenerable antimicrobial polymers and fibers with oxygen bleaches |
US20050011012A1 (en) * | 2003-03-19 | 2005-01-20 | Regents Of The University Of California | Multifunctional antimicrobial dyes |
US20080201871A1 (en) * | 2003-03-19 | 2008-08-28 | The Regents Of The University Of California | Antimicrobial colorants |
KR100622714B1 (en) | 2004-12-14 | 2006-09-19 | 현대자동차주식회사 | Antibacterial polymer adaptable of an automobile |
US7541398B2 (en) * | 2005-01-03 | 2009-06-02 | Board Of Regents, The University Of Texas System | Method for transformation of conventional and commercially important polymers into durable and rechargeable antimicrobial polymeric materials |
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US7998886B2 (en) * | 2005-10-24 | 2011-08-16 | Milliken & Company | Hindered amine treated textiles |
US20070218562A1 (en) * | 2006-03-20 | 2007-09-20 | Shulong Li | Color indicator for halamine treated fabric |
US8486428B2 (en) * | 2006-03-27 | 2013-07-16 | Board Of Regents, The University Of Texas System | Compositions and methods for making and using acyclic N-halamine-based biocidal polymeric materials and articles |
US8211361B2 (en) * | 2007-03-26 | 2012-07-03 | Board Of Regents, The University Of Texas System | N-halamine-based rechargeable biofilm-controlling tubular devices, method of making and using |
US7858539B2 (en) * | 2007-04-09 | 2010-12-28 | Milliken & Company | Processes for generating halamine compounds on textile substrates to produce antimicrobial finish |
WO2009039180A2 (en) * | 2007-09-19 | 2009-03-26 | Board Of Regents, The University Of Texas System | Colorants based n-halamines compositions and method of making and using |
CN112586502A (en) * | 2020-12-18 | 2021-04-02 | 湖南幻影三陆零科技有限公司 | Disinfectant suitable for high-temperature and high-pressure spray disinfection pipeline and disinfection composition containing disinfectant |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2950553A (en) | 1957-01-16 | 1960-08-30 | Rohm & Haas | Method of producing wrinkle resistant garments and other manufactured articles of cotton-containing fabrics |
US3061469A (en) | 1959-11-05 | 1962-10-30 | Givaudan Corp | Antibacterial textile fabrics |
US3260565A (en) | 1961-02-03 | 1966-07-12 | American Cyanamid Co | Novel imidazolidinones and their use as textile finishing agents |
US3445279A (en) | 1964-07-09 | 1969-05-20 | Dexter Chem Corp | Process of making uron resins and products thereof including modified textile fabrics |
US3401005A (en) | 1965-10-22 | 1968-09-10 | Gaf Corp | Germicidal material produced by modifying textile fibers with a methylolated lactam and treating same with iodine |
US3441367A (en) | 1965-12-22 | 1969-04-29 | Us Agriculture | Method for setting finishes on cellulosic textiles with catalyst composition of magnesium halide and organic acid |
CH1258167D (en) | 1966-09-08 | |||
US3576591A (en) | 1968-04-23 | 1971-04-27 | Proctor Chemical Co Inc | Methylolated cyclic urea compositions containing sodium formate or sodium tetraborate |
CH498858A (en) | 1968-11-01 | 1970-12-31 | Ciba Geigy | Process for the preparation of heterocyclic compounds containing eight ring members |
US3650667A (en) | 1969-02-26 | 1972-03-21 | Steiner American Corp | Laundry process for producing fabrics that are substantially free from bacteria and bacterial spores |
US3594113A (en) | 1969-12-03 | 1971-07-20 | Kendall & Co | Bacteriostatic finish for cellulosic fabrics |
US3812201A (en) | 1972-02-25 | 1974-05-21 | Corning Corp | Textile finishing composition and process |
AU7691474A (en) | 1974-01-14 | 1976-07-01 | American Cyanamid Co | Treatment of cellulosic textiles |
US4199322A (en) | 1978-08-17 | 1980-04-22 | The United States Of America As Represented By The Secretary Of Agriculture | Antibacterial textile finishes utilizing zinc acetate and hydrogen peroxide |
US4284758A (en) | 1979-11-08 | 1981-08-18 | Sun Chemical Corp. | Glyoxal/cyclic urea condensates |
US4300898A (en) | 1979-11-08 | 1981-11-17 | Sun Chemical Corporation | Compositions for treating textile fabrics |
US4306872A (en) | 1980-01-17 | 1981-12-22 | American Cyanamid Company | Imidazolidinones in a durable press process |
US4396391B2 (en) | 1982-06-30 | 1993-03-16 | Treating cellulose textile fabrics with dimenthylol dihydroyethyleneuree-polyol | |
US4585650A (en) | 1982-10-04 | 1986-04-29 | White Laboratories, Inc. | Skin lubricating cosmetic composition |
GB2161399B (en) | 1984-07-06 | 1987-12-16 | Turabi Mohammed El Hassan El | Pulverization of cellulosic material |
US4844891A (en) | 1988-02-03 | 1989-07-04 | Lonza, Inc. | Admixtures of iodopropargyl compounds and a formaldehyde donor |
JP2661241B2 (en) | 1988-03-03 | 1997-10-08 | 住友化学工業株式会社 | Disinfectant and disinfectant resin composition containing ethylene copolymer as active ingredient |
US5104649A (en) | 1988-05-11 | 1992-04-14 | Monsanto Company | Surface-functionalized biocidal polymers |
US5221574A (en) | 1991-04-02 | 1993-06-22 | Olin Corporation | Biocidal clothes dryer additive for laundered fabrics |
DE4125431A1 (en) | 1991-08-01 | 1992-07-30 | Pfersee Chem Fab | Heavyweight cellulosic fabric treatment to inhibit rotting - using imidazolidinone cpd. which does not release formaldehyde, used e.g. for tarpaulin or canvas |
DE69321461D1 (en) | 1992-03-03 | 1998-11-12 | Reginald Keith Whiteley | DISINFECTING COMPOSITION |
ZA933464B (en) | 1992-05-21 | 1993-12-20 | Lonza Ag | A method for preparing low free formaldehyde methylolhydantoins and compositions thereof |
US5352693A (en) | 1992-09-25 | 1994-10-04 | Lonza Inc. | Preservative mixtures |
ATE212851T1 (en) | 1993-03-12 | 2002-02-15 | Univ Auburn | BIOCIDAL POLYMERS CYCLIC N-HALAMINS |
US5707404A (en) | 1994-01-14 | 1998-01-13 | Westpoint Stevens, Inc. | Formaldehyde free method for imparting permanent press properties to cotton and cotton blends |
-
1999
- 1999-10-08 US US09/416,203 patent/US6241783B1/en not_active Expired - Fee Related
-
2000
- 2000-11-30 US US09/727,819 patent/US20010000085A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040191315A1 (en) * | 2003-03-24 | 2004-09-30 | Mike Slattery | Office products containing antimicrobial agent |
CN113842764A (en) * | 2021-09-28 | 2021-12-28 | 布鲁舍(北京)环境技术有限公司 | Formaldehyde and peculiar smell scavenging agent and preparation method thereof |
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