Classifications

• • 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
  • D06M13/244—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 sulfur or phosphorus
  • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
  • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
• • 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
  • D06M13/244—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 sulfur or phosphorus
  • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
  • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
• • 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
  • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/02—Water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/40—Fatty vegetable or animal oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/40—Fatty vegetable or animal oils
  • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/10—Amides of carbonic or haloformic acids
  • C10M2215/102—Ureas; Semicarbazides; Allophanates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/042—Metal salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/46—Textile oils
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S260/00—Chemistry of carbon compounds
  • Y10S260/15—Antistatic agents not otherwise provided for
  • Y10S260/16—Antistatic agents containing a metal, silicon, boron or phosphorus
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2904—Staple length fiber
  • Y10T428/2907—Staple length fiber with coating or impregnation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
  • Y10T428/2969—Polyamide, polyimide or polyester
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality
  • Y10T442/2451—Phosphorus containing

Definitions

• This invention relates to antistatic preparations and to a process of treating textile materials, and more particularly synthetic textile materials or mixtures of synthetic and natural fibers, with such preparations so as to pre vent generation and accumulation of static electricity in said textile materials.
• Another object of the present invention is to provide preparations for the treatment of synthetic fiber materials, which preparations prevent generation and accu- .mulation of static electricity in said fibers on subsequent spinning and further processing.
• a further object of the present invention is to provide an impregnating preparation for the treatment of finished woven or 'knitted fabrics made of synthetic fiber material, said impregnating preparation safeguarding such fabrics against accumulation of static charges.
• Still another object of the present invention is to provide synthetic. fiber material which is substantially free of static electricity and does not develop static charges on processing it and on wearing garments or using products made therefrom.
• the present invention consists in treating the textile material during its manufacture, during processing and finishing, or during its use with neutral alkylene oxide addition compounds of acid phosphoric acid esters of higher molecular hydroxyl compounds.
• generation and accumulation of static electricity in said textile materials are prevented or at least reduced to such an extent that it has no more disturbing effect on processing and using said materials.
• the antistatic preparations used for the treatment of textile materials and more particularly of synthetic textile materials are preferably aqueous solutions or dispersions of such alkylene oxide addition compounds of acid phosphoric acid esters of higher molecular hydroxyl compounds. contain at least about 1 g. of said addition compounds per liter. Amounts between about 1 g. and about 50 g. per liter are ordinarily suflicient to produce the desired effect. Higher concentrations may, of course, also be employed but usually will serve no useful purpose.
• concentration of the addition compound in the aqueous solution or dispersion depends upon the type of textile material to be treated and the method of treatment to be employed. It is readily possible to determine by simple preliminary tests the optimum concentration of the addition compound which should be used for each preparation, for each textile material and for each method of treatment.
• One of the methods advantageously used in this treatment comprises spraying or sprinkling the fiber material, for instance, in the form of staple fiber on conveyor belts, with antistatic solutions or dispersions according to the present invention, or the textile material may be sprayed therewith in suitable chambers from which unabsorbed,
• treatment material may be recovered, or it may be dipped or immersed into said solutions or dispersions.
• the antistatic treatment can also be effected during winding, spooling, doubling, twisting, and the like operations, by using spooling and spinning oils containing such antistatic addition compounds.
• emulsifier and dispersing agents may be added to the antistatic preparations according to the present invention; also hygroscopic agents, lubricants, brightening agents andother agents facilitating further processing and imparting to the treated textile materials additional improving effects may be used.
• Mineral, animal or vegetable oils, fats or waxes which are held in emulsion by said antistatic alkylene oxide addition compounds may be used as lubricants in the textile processing operations.
• the acid phosphoric acid esters used in the production of the alkylene oxide addition compounds forming the basis of the new antistatic preparations described herein may be produced according to methods known per se, for instance, by esterifying higher molecular alcohols with phosphorus .pentoxide, pyrophosphori-c acid, metaphosphoric acid and other phosphoric acids containing less water in their molecule than pyrophosphoric acid, as well as with mixtures of such acids or With phosphorus oxychloride.
• Said acid esters are converted into their alkylene oxide addition compounds, i. e. the corresponding neutral mixed 7 esters, by the addition of alkylene oxides, especially of ethylene oxide, at a temperature between about 50C. and about C. in the absence of catalysts. Thereby l to 4 or even more mols of ethylene oxide are added to each available acid group of the ester used as one of the reaction components.
• Such aqueous solutions or dispersions must As hygroscopic agents there ass-aces phosphoric acid esters there are employed aliphatic, cycloaliphatic, cycloaliphatic-aromatic, and aliphatic-aromatic hydroxyl compounds with at least 6 carbon atoms in their molecule, such as hexanol, octanol, dodecanol, oleyl alcohol, octadecanol, cyclohexancl, alkyl cyclohexyl alcohols, naphthene alcohols, benzyl alcohol, tetrahydronaphthol, decahydronaphthol, alkyl phenols and the like hydroxyl compounds.
• the hydroxyl compounds may also contain substituents or their hydrocarbon chain may be interrupted by hetero atoms, such as oxygen, sulfur, or nitrogen, or by hetero atom groups derived from said hetero atoms.
• alkylene oxide there is primarily used ethyl ne oxide, but propylene oxide, glycide, and the like alkylene com pounds may also be employed.
• Alkylene oxide addition compounds of acid phosphoric acid esters as they are contained in antistatic preparations produced according to the present invention may be, for instance, the following compounds:
• Example I Cut staple fibers of polyvinyl chloride, polyamides, polyacrylonitrile, or polyesters are treated with an aqueous dispersion containing 5 g. per liter of a condensation product of 2 mols of a mixture of fatty alcohols having 16 and 18 carbon atoms in their molecules, 1 mol of phosphorus pentoxide, and 4 to 6 mols of ethylene oxide by sprinkling the fibers on a conveyor sit with said aqueous dispersion. Thereafter the treated fibers are centrifuged and dried in a conventional manner.
• the resulting fibers do not generate and accumulate static electricity and can be processed with great ease by spinning.
• Example II Example II 'mixture (3 ,43 1 mol of phosphorus pentoxide, and 4 to 8 mols of ethylene oxide. in this manner, antistatic finished yarns of excellent closeness of the twist and good elastic properties are obtained.
• Example III For-spinning synthetic fibers as set forth in Example I in mixture with natural fibers such as wool or cotton, wool oils and spinning oils prepared, for instance, on the basis of fatty acids, fatty acid glycerides, and/ or mineral oils, are conventionally used. According to the present invention 2% to 5% of the condensation product of 2 mols of decanol, 1 mol of phosphorus pentoxide, and 4 to 8 mols of ethylene oxide are added to such wool oils and spinning oils and are finely and uniformly dispersed therethrough. The resulting preparations not only impart satisfactory antistatic properties to yarns spun therewith but also excellent resistance against distortion and draft and warping, and yield yarns of uniform quality.
• An antistatic synthetic textile material impregnated with a neutral condensation product formed by esterifying 1 mol prosphorus pentoxide with 2 mols of fatty alcohol with from 6 to 18 carbon atoms, and subjecting the resulting acid phosphoric acid ester to a condensation reaction with from 1 to .10 mols ethylene oxide at a temperature between 50 and'l00 C., in an amount sulficient to impart antistatic properties to said synthetic textile material.
• An antistatic synthetic textile material impregnated with a neutral condensation product formed by esterifying 1 mol phosphorus pentoxide with 2 mols of a mixture of fatty alcohols having from 16 to 18 carbon atoms, and subjecting the resulting acid phosphoric acid ester to a condensation reaction with 4 to 6 mols ethylene oxide at a temperature between 50 and C., in an amount sufficient to impart antistatic properties to said synthetic textile material.
• An antistatic synthetic textile material impregnated with a neutral condensation product formed by esterifying 1 mol phosphorus pentoxide with 2 mols of a mixture of fatty alcohols having from 12 to l8 carbon atoms, and subjecting the resulting acid phosphoric acid ester to a condensation reaction with 4 to 8 mols ethylene oxide at a temperature between 50 and 100 C., in a suflicient amount to impart antistatic properties to the textile material.
• An antistatic synthetic textile material impregnated with a neutral condensation product formed by esterifying 1 mol phosphorus pentoxide with 2 mols decanol, and subjecting the resulting acid phosphoric acid ester to a condensation reaction with 4 to 8 mols ethylene oxide at a temperature between 50 and 100 C., in an amount sufiicient to impart antistatic properties to the textile material.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Publications (1)

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Family Applications (1)

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Cited By (21)

Families Citing this family (4)

Citations (4)

• 1954
  • 1954-12-16 US US475812A patent/US2842462A/en not_active Expired - Lifetime
  • 1954-12-16 FR FR1115874D patent/FR1115874A/fr not_active Expired
  • 1954-12-17 GB GB36547/54A patent/GB769039A/en not_active Expired

Patent Citations (4)

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