Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
  • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
  • D06L1/14—De-sizing
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
  • D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
  • D06L4/23—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
• • 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
  • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
  • D06P1/613—Polyethers without nitrogen
  • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
  • D06P1/6133—Addition products of hydroxyl groups-containing compounds with oxiranes from araliphatic or aliphatic alcohols
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
  • D06P1/621—Compounds without nitrogen
  • D06P1/627—Sulfates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
  • C11D1/721—End blocked ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • 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
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/03—Organic sulfoxy compound containing

Definitions

• the present invention relates to a new aqueous, storage-stable, low-foaming wetting agent in use, and to its production and use in textile treatment.
• the object of the present invention is to provide a wetting agent whose cloud point enables storage stability up to 40 ° C. and at the same time shows low-foaming behavior in use.
• the substituent R in formula (1) advantageously represents the hydrocarbon radical of an unsaturated or saturated aliphatic monoalcohol with 8 to 22 carbon atoms.
• the hydrocarbon radical can be straight-chain or branched.
• R is preferably an alkyl or alkenyl radical having 9 to 14 carbon atoms.
• natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C9-C11 oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms in Come into consideration. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). (“Alfol" is a registered trademark).
• Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexanedecenyl alcohol or oleyl alcohol.
• the alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups, which are derived from soy fatty acids, palm kernel fatty acids or tallow oils.
• Alkylene-O p chains are preferably of the ethylene glycol, ethylene propylene glycol or ethylene isopropylene glycol type; p is preferably 4 to 20.
• nonionic surfactants are: - Addition products of preferably 4 to 20 moles of alkylene oxides, in particular ethylene oxide, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as isopropylene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols with 8 to 22 carbon atoms.
• non-ionic surfactants correspond to the formula in which one of Y1 and Y2 is methyl or ethyl and the other is hydrogen, n1 is an integer from 2 to 24 and ml is an integer from 0 to 15, the sum of m1 and n1 is a maximum of 24 and R and R1 have the meaning given in formula (1).
• non-ionic surfactants of the formula wherein R2 C9 to C14 alkyl, R3 is hydrogen, butyl, a cycloaliphatic radical with at least 6 carbon atoms or benzyl, of Y3 and Y4 one residue is hydrogen or methyl and the other hydrogen, m2 is an integer from 4 to 8 and n2 is an integer from 4 to 8.
• R2 has the meaning given in formula (3)
• R4 is hydrogen, C1 to C4-alkyl or phenyl-lower alkyl, of Y5 and Y6 one residue is hydrogen and the other is ethyl
• n3 is an integer from 4 to 8
• m3 is an integer from 1 to 3.
• the nonionic surfactants of the formulas (1) to (4) are prepared in a manner known per se, for example by reaction of the corresponding alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a short-chain, cycloaliphatic, fatty, phenyl-lower alkyl or styryl alcohol.
• Particularly preferred hydrotroping agents of component (b) according to the invention are alkyl sulfates of the formula (5) R8O - SO3X, wherein R8 is an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and X represents hydrogen, alkali metal or ammonium.
• alkyl sulfate is in the form of a salt
• sodium, potassium or ammonium salts can be used, for example.
• the sodium salt is preferred.
• Very particularly preferred hydrotroping agents of component (b) are alkyl sulfates in which the substituent R8 in formula (5) is the hydrocarbon radical of an aliphatic saturated monoalcohol having 4 to 24 carbon atoms.
• the hydrocarbon residue can be straight-chain or branched.
• Suitable aliphatic saturated monoalcohols are natural alcohols, such as lauryl, myristyl, cetyl, stearyl, arachnidyl or behenyl alcohol.
• Preferred are compounds in which the substituent R8 is derived from branched aliphatic synthetic alcohols having 4 to 12, in particular 4 to 8, carbon atoms, for example.
• the alkyl sulfates can already be in the form of their salts and can be used alone or as a (technical) mixture with one another in the wetting agent according to the invention.
• alkyl sulfonates of formula (8) and their alkali metal or amine salts can also be used together with other compounds as hydrotroping agents, e.g. with polymerized acrylic acid, C1 to C10 - alkylphosphonic acid or C1 to C10 - alkylphosphonic acid esters.
• alkyl sulfates are prepared in a manner known per se by reacting the corresponding alcohols with e.g. Sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.
• the wetting agent according to the invention can additionally contain an optional component (c).
• Non-polar organic solvents with a flash point above 65 ° C are suitable.
• cyclic straight-chain or in particular branched alcohols are used, such as e.g. Cyclohexanol, methylcyclohexanol, tetralin, n-hexanol, 2-ethylhexanol-1, isooctyl alcohol, isononyl alcohol and especially trimethylhexanol-3,5,5.
• esters such as tributyl citrate or tributyl phosphate can be used as non-polar organic solvents.
• the new wetting agents can be prepared by simply stirring the components (a), (b) and, if appropriate, (c).
• the preparation is preferably carried out by mixing components (a), (b) and optionally (c) with stirring and adding deionized water until a homogeneous solution is obtained.
• Preferred wetting agents according to the invention particularly advantageously contain, based on the mixture as a whole, 15 to 60% by weight of component (a), 2 to 10% by weight of component (b), 0 to 4% by weight of component (c) and ad 100% water.
• the new wetting agents are aqueous formulations with low foaming in use, which are characterized by a cloud point which is above 40 ° C. and which are stable up to 40 ° C.
• wetting agents are used in textile treatment, especially in pretreatment, such as in long liquor bleaching or in chlorine and peroxide hot bleaching.
• the amounts in which the wetting agent according to the invention is added to the treatment liquors are between 0.1 and 10, preferably 0.5 and 5 g per liter of treatment liquor.
• the fleet can also contain other additives, e.g. Desizing agents, dyes, optical brighteners, synthetic resins and alkalis such as sodium hydroxide.
• Fiber materials Cellulose, in particular untreated natural cellulose such as hemp, linen, jute, cellulose, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber blends, e.g. those made of polyacrylonitrile / cotton or polyester / cotton.
• the fiber material to be treated can be in various processing stages, e.g. the cellulose-containing material as loose material, yarn, woven or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers.
• the fiber material can be treated continuously or discontinuously in an aqueous liquor.
• the aqueous treatment liquors can be applied to the fiber materials in a known manner, advantageously by impregnation on the padder, the liquor absorption being about 50 to 120% by weight.
• the padding process is used in particular in the pad-steam process, the pad-thermofix process and the pad-batch process.
• the impregnation can be carried out at 10 to 60 ° C, but preferably at room temperature.
• the cellulose material is optionally after intermediate drying, heat treatment, e.g. Subject to temperatures from 95 to 210 ° C.
• the heat treatment can be carried out after intermediate drying of the goods at 80 to 120 ° C, by heat setting at a temperature of 120 to 210 ° C, preferably 140 to 180 ° C.
• the heat treatment is direct, i.e. without intermediate drying, by steaming at 95 to 120 ° C, preferably 100 to 106 ° C.
• the heat treatment can take 30 seconds to 30 minutes.
• the impregnated goods are rolled up without drying and then optionally packed with a plastic film and stored at room temperature for 1 to 24 hours.
• the treatment of the fiber materials can also in so-called long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:25 and at 10 to 100, preferably 80 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger, jet or reel runner. If necessary, however, the treatment can also be carried out up to 150 ° C., preferably 105 to 140 ° C., under pressure in so-called high-temperature apparatus (HT apparatus).
• HT apparatus high-temperature apparatus
• the fiber materials are washed with hot water at around 90 to 98 ° C and then with warm and finally with cold water rinsed thoroughly, neutralized if necessary and then dried preferably at elevated temperatures.
• the main advantages of the wetting agents according to the invention are their good storage stability and their low-foaming behavior in use.
• Formulations A, B, C and D are prepared by mixing the components listed in Table I according to their weight proportions with stirring until a homogeneous solution is obtained.
• Table I A B C. D
• Nonionic surfactant of formula (1) for example 15 moles of the ethylene / propylene oxide adduct with 1 mole of a C9 - C11 fatty alcohol 25th 25th 25th 25th 2-ethylhexanol sulfate sodium salt (40% solution) 9 9 3,5,5-trimethylhexanol 3rd 2nd Sodium cumene sulfonate 100% 10th 10th Isopropanol 5 water 66 63 63 60 Cloud point [° C] * 40.5 41.5 45.3 55.5 Foam height [ml] of 2 g / l of the formulation ** 70 50 50 80 * Cloud point of the formulation tel quel; ** Foam test based on DIN 53902
• a raw cotton jersey is bleached in a ®AHIBA dyeing machine in a bath, which is per liter 2g of formulation B 0.2g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US-PS 4254063, Na-gluconate and magnesium chloride (ratio 2: 1: 1) 1g NaOH solid and Contains 5 ml H2O2 (35%).
• the bleach bath is heated to 90 ° C. within 20 minutes and then held at this temperature for a further 30 minutes.
• the substrate is then washed out hot and cold and neutralized. No disruptive foaming occurs during bleaching.
• the result is a uniform degree of whiteness, which is increased from ⁇ 72 to 50 CIBA-GEIGY whiteness units.
• a raw cotton jersey with a running weight of 80 g is passed through a chlorine bleaching bath per liter in a Galaxy system (Benninger, Switzerland) at a speed of 54 m / min 4g active chlorine 1.5g NaOH (100%) and Contains 2 g of formulation B.
• the residence time is 15 minutes at 16 ° C.
• the goods are evenly wetted and the chlorine bleach bath is foam-free.
• the goods are squeezed and passed through an H2O2 bleaching bath, which is per liter 2 g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US Pat. No. 4,254,063, Na gluconate and magnesium chloride (ratio 2: 1: 1) 3g NaOH (100%) 3 ml water glass 38 ° Be 0.5 g of formulation B and Contains 15 ml H2O2 (35%).
• the residence time is 35 minutes at 85 ° C. No annoying foam formation occurs in the peroxide bleaching bath either.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Detergent Compositions (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Applications Claiming Priority (2)

Publications (3)

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Family Applications (1)

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Cited By (10)

Families Citing this family (9)

Family Cites Families (42)

• 1990
  • 1990-09-17 DE DE59009494T patent/DE59009494D1/de not_active Expired - Fee Related
  • 1990-09-17 DK DK90810704.8T patent/DK0420802T3/da not_active Application Discontinuation
  • 1990-09-17 AT AT90810704T patent/ATE126289T1/de not_active IP Right Cessation
  • 1990-09-17 ES ES90810704T patent/ES2075891T3/es not_active Expired - Lifetime
  • 1990-09-17 EP EP90810704A patent/EP0420802B1/fr not_active Expired - Lifetime
  • 1990-09-19 PT PT95351A patent/PT95351B/pt not_active IP Right Cessation
  • 1990-09-24 DD DD90344147A patent/DD298062A5/de not_active IP Right Cessation
  • 1990-09-24 CA CA002026039A patent/CA2026039C/fr not_active Expired - Fee Related
  • 1990-09-24 MX MX022527A patent/MX173539B/es unknown
  • 1990-09-24 AR AR90317940A patent/AR247433A1/es active
  • 1990-09-25 BR BR909004788A patent/BR9004788A/pt not_active IP Right Cessation
  • 1990-09-25 ZA ZA907642A patent/ZA907642B/xx unknown
  • 1990-09-26 JP JP2254361A patent/JP2763190B2/ja not_active Expired - Lifetime
• 1993
  • 1993-12-08 US US08/163,612 patent/US5484553A/en not_active Expired - Fee Related

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