EP1147254B1 - Verfahren und waschmittel zur behandlung von textilen flächengebilden - Google Patents

Verfahren und waschmittel zur behandlung von textilen flächengebilden Download PDF

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Publication number
EP1147254B1
EP1147254B1 EP00972835A EP00972835A EP1147254B1 EP 1147254 B1 EP1147254 B1 EP 1147254B1 EP 00972835 A EP00972835 A EP 00972835A EP 00972835 A EP00972835 A EP 00972835A EP 1147254 B1 EP1147254 B1 EP 1147254B1
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EP
European Patent Office
Prior art keywords
optionally
aqueous liquor
bleach
acid
fabrics
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00972835A
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English (en)
French (fr)
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EP1147254A1 (de
Inventor
Machiel Unilever Research Vlaardingen GOEDHART
Jean-Paul Unilever Rch. Port Sunlight JANSSENS
Karin Unilever Research Vlaardingen VRIESWIJK
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP1147254A1 publication Critical patent/EP1147254A1/de
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Publication of EP1147254B1 publication Critical patent/EP1147254B1/de
Anticipated expiration legal-status Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044Solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3956Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/265Carboxylic acids or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/70Multi-step processes

Definitions

  • the present invention is concerned with a process suitable for removing stains from textile fabrics.
  • the process is for use when washing fabrics by hand.
  • JP 58 008 180A discloses a process for removing coloured disinfectant stains from hospital clothing, in which the clothing is first machine-washed in an acid solution at pH 2.5-4.0, for example at 60°C, then machine-washed with a solution containing sodium hypochlorite bleach, for example at 40°C.
  • the preferred acid for the first step is phosphoric acid, but citric acid may also be used.
  • the acid solution used for the first step may contain a neutral detergent.
  • GB 2 095 254A discloses a composition for reducing discolouration of textiles during washing or dry cleaning, the composition comprising tertiary amine salts of citric acid or tricarballylic acid.
  • JP 61 062 600A discloses a detergent composition for preventing the yellowing of fabrics due to ferrous ions, comprising citric acid, isocitric acid or their salts plus optionally polyethylene glycol, surfactants, builders, bleaches and other conventional ingredients.
  • EP 534 525A discloses a granular detergent composition containing particulate citric acid, plus anionic and/or nonionic surfactants, sodium carbonate, other builder, and preferably also foam depressing agent and bleach components.
  • JP 58 008 180 discloses a two stage stain removal process for washing clothing used in hospitals.
  • the first step is to wash the clothing in acid, preferred pH 2.5 to 4.
  • washing with sodium hypochlorite solution The acid solution may contain a neutral detergent.
  • the present invention provides a process for removal of stains from textile fabrics, which process comprises the steps of:
  • a preferred hand washing stain removal process comprises the steps of:
  • the invention is a wet treatment process.
  • the fabrics are soaked successively in two different aqueous liquors and then rinsed.
  • the fabrics may be rinsed between the two soaking steps.
  • the process of the invention is especially useful, as a supplement to the normal laundry process, for removal of particularly stubborn stains.
  • the process of the invention is carried out by hand, using simple utensils such as buckets or bowls as are usually used in laundering fabrics by hand.
  • the first aqueous liquor has a relatively low pH, in the range of from 2 to 5, and advantageously in the range of from 3.5 to 4.5, most preferably about 4.0.
  • lower pll values for example, 2 to 3.5, are also within the scope of the invention.
  • the first aqueous liquor contains as an essential ingredient a water-soluble solid acid.
  • the water-soluble acid is an organic carboxylic acid, for example, citric acid, oxalic acid, tartaric acid, malonic acid, succinic acid, or ascorbic acid. Acids containing two or more carboxyl groups are especially preferred.
  • the acid is used in admixture with a corresponding water-soluble salt, preferably a sodium salt.
  • a corresponding water-soluble salt preferably a sodium salt.
  • the pH may then be controlled by choice of the ratio of free acid to salt.
  • a preferred acid (i)(a) in accordance with the invention is a solid organic carboxylic acid, preferably containing two or more carboxyl groups, optionally in admixtures with a water-soluble salt thereof.
  • the preferred acid for use in the present invention is citric acid, optionally and more preferably used in admixture with sodium citrate.
  • the concentration of the acid, plus salt if present, in the first aqueous liquor is preferably at least 1 g/litre, and more preferably at least 3 g/litre.
  • the first aqueous liquor also contains an effective amount of an oxidising agent capable of masking and/or neutralising sulphurous odours.
  • an oxidising agent capable of masking and/or neutralising sulphurous odours.
  • odours may be generated when the blueing agent widely used in the Indian subcontinent is converted to a colourless form.
  • Suitable materials are especially oxidative bleaches, preferably selected from alkali metal and alkaline earth metal iodates, peroxomonosulphates, benzenecarboperoxoates and monoperoxyphthalates, and hydrogen peroxide.
  • alkali metal iodates more especially potassium iodate.
  • the amount required to neutralise sulphurous odours may be determined by means of a lead acetate titration test, which is carried out as follows.
  • a monitor is prepared by impregnating a 1 cm x 10 cm strip of Whatman IPS phase-separating filter paper (silicone treated) with lead acetate solution (1 g of lead acetate trihydrate in 100 ml demineralised water).
  • a fabric monitor is placed in 100 ml sample of the treatment liquor (first aqueous liquor) in a 400 ml beaker, the lead acetate strip is moistened with demineralised water and placed above the treatment liquor, and the beaker is closed with a transparent lid. If hydrogen sulphide is formed during the treatment, the lead acetate strip becomes black/brown due to the formation of lead sulphide, and this indicates that the liquor contains an insufficient amount of the oxidising agent.
  • the first aqueous liquor may contain a bleach stable and effective at a pH of from 2 to 5.
  • stable and effective is meant that the bleach must be stable in a product on storage at a pH of from 2 to 5, soluble when the product is dissolved in water, and function effectively as a bleach at the pH of the product.
  • odour-masking or odour-neutralising agents are also stable and effective bleaches at a pH of from 2 to 5.
  • the chosen oxidising agent is, for example, potassium iodate, it may be preferred for an additional bleach stable at low pH also to be present.
  • Preferred bleaches are alkali metal dichlorocyanurates.
  • Materials that may function both as odour-masking or neutralising agents and as stable and effective bleaching agents at a pH below 5.0 include magnesium monoperoxyphthalate and potassium benzenecarboperoxoate.
  • the first aqueous liquor also contains one or more surfactants.
  • Anionic and/or nonionic surfactants are preferred, especially anionic surfactants used alone and combinations of anionic and nonionic surfactants in which the anionic surfactant predominates.
  • a preferred surfactant system comprises an anionic surfactant selected from linear alkylbenzene sulphonate and alpha-olefin sulphonate, optionally together with at least one ethoxylated C 8 -C 20 alcohol nonionic surfactant having an average degree of ethoxylation of from 2 to 10.
  • perfumes may be present, generally in minor amounts.
  • the fabrics are allowed to soak in the first aqueous liquor for at least 1 minute, preferably from 1 to 60 minutes, more preferably from 10 to 45 minutes, and most preferably from 15 to 30 minutes.
  • the fabrics are then allowed to soak in the second aqueous liquor.
  • the second aqueous liquor contains as an essential ingredient a bleach.
  • Other ingredients including surfactants and alkaline buffering agents may if desired be present, but that is not essential.
  • Suitable bleaches include chlorine bleaches such as alkali metal hypochlorite, organic chloramides (eg alkali metal dichlorocyanurate (DCCA) or trichlorocyanurate); peracids, for example, N,N'-phthaloylaminoperoxycaproic acid (PAP), diperdodecanoic acid (DPDA); inorganic persalts, for example, alkali metal perborate or percarbonate, together with a bleach activator (peracid precursor) such as alkylsulphophenyl carbonate (ASPC), cholylsulphophenylcarbonate (CSPC), or SNOBS and similar materials. If desired, two or more bleaches may be used in combination.
  • a bleach activator peracid precursor
  • APC alkylsulphophenyl carbonate
  • CSPC cholylsulphophenylcarbonate
  • SNOBS SNOBS
  • the second aqueous liquor may also contain a bleach stabiliser (heavy metal sequestrant), for example, an aminopolycarboxylate or aminopolyphosphonate.
  • a bleach stabiliser for example, an aminopolycarboxylate or aminopolyphosphonate.
  • Preferred materials include EDTA, NTA, EDDS, and EDTMP and DETPMP (Dequests (Trade Mark)).
  • a sequestrant is desirable or preferred when the bleach system includes PAP, but may be omitted if the bleach is NaDCCA.
  • the concentration of bleach in the second aqueous liquor is preferably at least 0.05 g/litre, more preferably at least 0.1 g/litre and most preferably at least 0.2 g/litre.
  • Surfactants may also be present. Especially preferred are anionic and/or nonionic surfactants. As in the first aqueous liquor, anionic surfactants alone and anionic/nonionic combinations in which the anionic surfactant predominates are preferred.
  • the second aqueous liquor may also contain an alkaline buffering agent, which may suitably be selected from sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate and combinations of these.
  • an alkaline buffering agent which may suitably be selected from sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate and combinations of these.
  • builder and/or filler salts suitably selected from sodium tripolyphosphate, other sodium phosphates, sodium sulphate, and combinations of these.
  • the second aqueous liquor may also comprise one or more detergent enzymes, preferably selected from proteases, cellulases and combinations thereof.
  • the second aqueous liquor may be purely a bleach solution; or may to a greater or lesser extent contain other detergent or cleaning ingredients. At one extreme the second aqueous liquor may be generated purely by dissolving bleach in water; at the other extreme, the second aqueous liquor may be generated by dissolving or dispersing a fully formulated bleaching detergent composition, or a fully formulated non-bleaching detergent composition plus separate bleach, in water.
  • the fabrics are allowed to soak in the second aqueous liquor for a period of at least 1 minute, preferably from 1 to 60 minutes, more preferably from 10 to 30 minutes.
  • the fabrics are rinsed in water.
  • a first particulate composition 1(i) having a 1 wt% solution pH of 4.0 had the following formulation: wt% Citric acid 41.40 Trisodium citrate 2aq 35.60 Linear alkylbenzene sulphonate 98% 19.40 Na DCCA 2.00 Potassium iodate 1.00 Perfume 0.60
  • a second particulate composition 1(ii) had the following formulation: wt% N,N'-phthaloylaminoperoxycaproic acid (PAP)(34%) 11.10 Sodium carbonate (anhydr) 17.68 Sodium bicarbonate 6.60 Sodium tripolyphosphate (anhydr) 16.31 Sodium silicate 9.90 Sodium sulphate 7.0.07 Linear alkylbenzene sulphonate 98% 23.24 Ca FDTMP (Dequest* 2047) 0.50 Fluorescers Tinopal* DhSS-X and CBS-X 0.42 Protease (Savinase*) 1.99 Cellulase (Celluzyme*) 1.99 Perfume 0.20
  • compositions 1(i) and 1(ii) were packaged in sachets of nonwoven fabric.
  • Example 1 The stain removal performance of the product of Example 1 was compared with that of a commercially available laundry detergent powder sold on the Indian market.
  • Stained cotton monitors were each soaked for 30 minutes in a 5.0 g/l solution of composition 1(a), then soaked for 30 minutes in a 5.0 g/l solution of composition 1(b), then rinsed twice in large volumes of water and allowed to dry.
  • monitors carrying the same stains were each soaked for 30 minutes in a 5.0 g/l solution of a commercially available Indian laundry detergent powder, rinsed twice in large volumes of water, and allowed to dry.
  • the commercial product contained LAS, nonionic surfactant, sodium tripolyphosphate, sodium carbonate, sodium carboxymethylcellulose, photobleach, protease, cellulase, lipase and conventional minor ingredients.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (10)

  1. Textilbehandlungsverfahren, umfassend die Schritte von:
    (i) Einweichen lassen der Textilien für mindestens eine Minute in einer ersten wässrigen Flüssigkeit mit einem pH-Wert im Bereich von 2 bis 5, vorzugsweise 3,5 bis 4,5, und umfassend
    (i) (a) eine in Wasser lösliche feste Säure, gegebenenfalls in Anmischung mit einem in Wasser löslichen Salz davon,
    (i) (b) ein Tensid;
    (ii) Einweichen lassen der Textilien für mindestens eine Minute in einer zweiten wässrigen Flüssigkeit, umfassend
    (ii) (a) ein Bleichmittel,
    (ii) (b) gegebenenfalls ein Tensid,
    (iii) (c) gegebenenfalls ein alkalisches Puffermittel und
    (iii) Spülen der Textilien in Wasser,
    dadurch gekennzeichnet, dass das Verfahren mit der Hand ausgeführt wird und für die Entfernung von Flecken, ausgewählt aus der Gruppe, bestehend aus Kaffee, Tee, Bananen, Schlamm/Schmutz, Rost, Schuhcreme, schmutzigem Motoröl, Lippenstift, Tinte, Soße und Senf, aus dem Textil eingesetzt wird.
  2. Verfahren nach Anspruch 1, wobei die erste wässrige Flüssigkeit umfasst:
    (i) (a) eine in Wasser lösliche feste Säure, gegebenenfalls in Anmischung mit einem in Wasser löslichen Salz davon,
    (i) (b) ein Tensid,
    (i) (c) ein Oxidationsmittel, das schwefelhaltige Gerüche maskieren und/oder neutralisieren kann,
    (i) (d) ein Bleichmittel, das bei einem pH-Wert von 2 bis 5 stabil und wirksam ist, das nicht das Oxidationsmittel (i)(c) darstellt,
    und die zweite wässrige Flüssigkeit umfasst:
    (ii) (a) ein Bleichmittel,
    (ii) (b) gegebenenfalls ein Tensid,
    (ii) (c) gegebenenfalls ein alkalisches Puffermittel,
    (ii) (d) gegebenenfalls einen oder mehrere Builder und/oder Füllstoffsalze,
    (ii) (e) gegebenenfalls einen maskierenden Bleichmittelstabilisator,
    (ii) (f) gegebenenfalls ein Fluoreszenzmittel,
    (ii) (g) gegebenenfalls ein oder mehrere Waschmittelenzyme.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die erste wässrige Flüssigkeit als Oxidationsmittel (i) (c) ein Alkalimetalljodat umfasst.
  4. Verfahren nach Anspruch 2 oder Anspruch 3, dadurch gekennzeichnet, dass die erste wässrige Flüssigkeit als Bleichmittel (i) (d) ein Alkalimetalldichlorcyanurat umfasst.
  5. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass die in Wasser lösliche feste Säure eine organische Carbonsäure mit mindestens zwei Carboxylgruppen, vorzugsweise Zitronensäure, gegebenenfalls in Anmischung mit Natriumcitrat, darstellt.
  6. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass die Konzentration der in Wasser löslichen Säure und, falls vorliegend, des Salzes davon, in der ersten wässrigen Flüssigkeit mindestens 1 g/l, vorzugsweise mindestens 3 g/l, ist.
  7. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass die zweite wässrige Flüssigkeit ein Bleichmittel (ii)(a), ausgewählt aus Alkalimetalldichlorcyanurat und N,N'-Phthaloylaminoperoxycapronsäure, umfasst.
  8. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass die Konzentration des Bleichmittels (ii) (a) in der zweiten wässrigen Flüssigkeit mindestens 0,05 g/l, vorzugsweise mindestens 0,2 g/l, ist.
  9. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass man in Schritt (i) die Textilien für einen Zeitraum von 1 bis 60 Minuten, vorzugsweise 10 bis 45 Minuten, einweichen lässt.
  10. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass man in Schritt (ii) die Textilien für einen Zeitraum von 1 bis 60 Minuten, vorzugsweise 10 bis 30 Minuten, einweichen lässt.
EP00972835A 1999-11-26 2000-10-19 Verfahren und waschmittel zur behandlung von textilen flächengebilden Expired - Lifetime EP1147254B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9928079 1999-11-26
GBGB9928079.4A GB9928079D0 (en) 1999-11-26 1999-11-26 Process and product for the treatment of textile fabrics
PCT/EP2000/010380 WO2001038626A1 (en) 1999-11-26 2000-10-19 Process and product for the treatment of textile fabrics

Publications (2)

Publication Number Publication Date
EP1147254A1 EP1147254A1 (de) 2001-10-24
EP1147254B1 true EP1147254B1 (de) 2006-06-21

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Application Number Title Priority Date Filing Date
EP00972835A Expired - Lifetime EP1147254B1 (de) 1999-11-26 2000-10-19 Verfahren und waschmittel zur behandlung von textilen flächengebilden

Country Status (8)

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EP (1) EP1147254B1 (de)
AT (1) ATE331065T1 (de)
AU (1) AU1142801A (de)
BR (1) BR0007725A (de)
DE (1) DE60028930D1 (de)
GB (1) GB9928079D0 (de)
WO (1) WO2001038626A1 (de)
ZA (1) ZA200105008B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1593733A1 (de) * 2004-04-05 2005-11-09 The Procter & Gamble Company Flüssige Bleichmittelzusammensetzungen
WO2005100529A1 (en) * 2004-04-05 2005-10-27 The Procter & Gamble Company Liquid bleaching compositions
US8753453B2 (en) * 2012-10-04 2014-06-17 Ecolab Usa Inc. Pre-soak technology for laundry and other hard surface cleaning
WO2023175537A1 (en) * 2022-03-17 2023-09-21 Diversey, Inc. Synergistic rust stain removal compositions and methods of removing rust stain from fabric

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6024859B2 (ja) * 1981-07-09 1985-06-14 花王株式会社 病院衣料の洗浄方法
ATE29523T1 (de) * 1983-10-03 1987-09-15 Akzo Nv Ein reinigungsmittel und/oder ein bleichmittel enthaltende dosiereinheit.
JPS6119866A (ja) * 1984-06-29 1986-01-28 四国化成工業株式会社 おしぼりの黄ばみ除去方法
DE4208106B4 (de) * 1991-03-20 2006-10-05 Clariant Finance (Bvi) Ltd. Vorbehandlung von Textilfasermaterial
WO1999061572A1 (en) * 1998-05-29 1999-12-02 Unilever Plc Process and product for the treatment of textile fabrics

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Publication number Publication date
DE60028930D1 (de) 2006-08-03
WO2001038626A1 (en) 2001-05-31
BR0007725A (pt) 2001-10-30
ATE331065T1 (de) 2006-07-15
AU1142801A (en) 2001-06-04
GB9928079D0 (en) 2000-01-26
EP1147254A1 (de) 2001-10-24
ZA200105008B (en) 2002-06-19

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