EP1147254B1 - Process and product for the treatment of textile fabrics - Google Patents

Process and product for the treatment of textile fabrics 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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German (de)
French (fr)
Other versions
EP1147254A1 (en
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/en
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Publication of EP1147254B1 publication Critical patent/EP1147254B1/en
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • D06L4/70—Multi-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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A process for the removal of stains from textile fabrics comprises soaking the fabrics first in a low-pH aqueous liquor containing, for example, citric acid and sodium citrate, then subsequently in a bleaching liquor, for example, containing a dichlorocyanurate bleach, then rinsing and drying the fabrics. The first aqueous liquor preferably contains an oxidising agent, for example, potassium iodate, to mask and/or neutralise sulphurous odours. The process may suitably be carried out by hand. The product comprises two separately packaged particulate compositions for generating the two liquors; these are preferably packed in visually distinct sachets within common outer packaging.

Description

    Technical field
  • 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.
    • Background
  • In the handwash, for example, as practised on the Indian subcontinent, successful removal of stains from textile fabrics is a persistent problem and acceptable results are difficult to obtain using conventional laundry detergent products and traditional handwashing methods. Removal of strongly coloured stains, for example, tea, coffee, red mud and rust, is especially problematic.
    • Prior art
  • JP 58 008 180A (Kao) 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 (Kreussler) 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 (Kao) 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 (Unilever) 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 (Kao) 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. Then washing with sodium hypochlorite solution. The acid solution may contain a neutral detergent.
    • Definition of the invention
  • The present invention provides a process for removal of stains from textile fabrics, which process comprises the steps of:
    • (i) allowing the fabrics to soak for at least 1 minute in a first aqueous liquor having a pH within the range of from 2 to 5, preferably from 3.5 to 4.5, and comprising
      • (i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
      • (i)(b) a surfactant,
    • (ii) allowing the fabrics to soak for at least 1 minute in a second aqueous liquor comprising
      • (ii)(a) a bleach,
      • (ii) (b) optionally a surfactant, and
      • (ii)(c) optionally an alkaline buffering agent, and
    • (iii) rinsing the fabrics in water.
    wherein the process is carried out by hand and is used for the removal from the fabric of stains selected from the group consisting of coffee, tea, banana, mud/soil, rust, shoe polish, dirty motor oil, lipstick, ink, gravy and mustard. Preferred embodiments of the invention
  • A preferred hand washing stain removal process according to the invention comprises the steps of:
    • (i) allowing the stained fabrics to soak for at least 1 minute in a first aqueous liquor having a pH within the range of from 2 to 5, preferably from 3.5 to 4.5, and comprising
      • (i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
      • (i) (b) a surfactant,
      • (i)(c) optionally an oxidising agent capable of masking and/or neutralising sulphurous odours,
      • (i)(d) optionally a bleach stable and effective at a pH of from 2 to 5, which is not the oxidising agent (i)(c), and
    • (ii) allowing the fabrics to soak for at least 1 minute in a second aqueous liquor comprising
      • (ii) (a) a bleach
      • (ii) (b) optionally a surfactant,
      • (ii) (c) optionally an alkaline buffering agent,
      • (ii)(d) optionally one or more builder and/or filler salts,
      • (ii) (e) optionally a sequestrant bleach stabiliser,
      • (ii) (f) optionally a fluorescer,
      • (ii)(g) optionally one or more detergent enzymes, and
    • (iii) rinsing the fabrics in water.
    Detailed description of the invention
  • The invention is a wet treatment process. In this process the fabrics are soaked successively in two different aqueous liquors and then rinsed. Optionally 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
  • 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. However, 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.
  • According to a preferred embodiment of the invention, 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.
  • Examples of some suitable solid acids include the following:
    Acid Formula
    DL-Lactic acid H3C-CHO-COOH
    Glycolic acid H2-C-OH-COOH
    Fumaric acid HOOC-CH=HC-COOH
    Malonic acid HOOC-CH2-COOH
    Malic acid HOOC-CH2-CHOH-COOH
    Salicylic acid OH- (C6H4) -COOH
    Oxalic acid 2aq HOOC-COOH
    Succinic acid HOOC-CH2-CH2-COOH
    Benzoic acid (C6H4) -COOH
    Tartaric acid HOOC-HCOH-HCOH-COOH
    Adipic acid HOOC-CH2-CH2-CH2-CH2-COOH
    Glutaric acid HOOC-CHOH-CHOH-CHOH-COOH
    Glycine H2-N-CH2-COOH
    Sokalan DCS Mixed adipic glutaric succinic acids
    Citric acid 1aq HO-(-C-COOH)3
    Ascorbic acid HO-CH2-CHOH-CH-CH=CH-C=O..O (3-6)
    Boric acid HBO3
    Asparagine 1aq HOOC-CH2-NH2-CH2-COOH
    Sodium dihydrogen phosphate 2aq NaH2PO4
    Arginine H2N-C(=NH-(CH2)3-CH(NH2)-COOH
    Salicyl salicylic acid OH- (C6H4) -COO- (C6H4) -COOH
    Cysteine HS-CH2-CH(NH2)-COOH
  • According to a preferred embodiment of the invention, the acid is used in admixture with 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.
  • Thus 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.
  • Desirably the first aqueous liquor also contains an effective amount of an oxidising agent capable of masking and/or neutralising sulphurous odours. Such 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. Especially preferred are 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.
  • According to an especially preferred embodiment of the invention, the first aqueous liquor may contain a bleach stable and effective at a pH of from 2 to 5. By "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.
  • Some but not all of the materials disclosed above as odour-masking or odour-neutralising agents are also stable and effective bleaches at a pH of from 2 to 5. However, if 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 C8-C20 alcohol nonionic surfactant having an average degree of ethoxylation of from 2 to 10.
  • Other ingredients, for example perfumes, may be present, generally in minor amounts.
  • In the first step of the process of the invention, 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.
  • With or without an intermediate rinse, the fabrics are then allowed to soak in the second aqueous liquor.
    • 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.
  • Preferred bleaches are alkali metal hypochlorite, alkali metal dichlorocyanurate (DCCA), alkali metal perborate, and N,N'-phthaloylaminoperoxycaproic acid (PAP), and combinations thereof. Especially preferred bleaches are sodium DCCA, PAP, and combinations thereof.
  • Advantageously the second aqueous liquor may also contain a bleach stabiliser (heavy metal sequestrant), 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.
  • It may also contain one or more 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.
  • Thus 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.
  • In the second step of the process of the invention, 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.
  • In a final step, the fabrics are rinsed in water.
    • EXAMPLES
  • The invention will now be described in more detail in the following non-limiting Examples, in which all parts and percentages are by weight unless otherwise stated.
  • Trade marks are indicated by an asterisk.
    • EXAMPLE 1: product used in the process
  • 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
  • 7.5 g doses of Compositions 1(i) and 1(ii) were packaged in sachets of nonwoven fabric.
    • EXAMPLE 5: stain removal
  • 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.
  • All wash liquors were prepared, and rinses carried out, using 24° (French) hard water.
  • 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.
  • In a control experiment, 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.
  • Reflectance increases (ΔR) at 460 nm and at 600 nm were measured before and after treatment. The results are shown in the following Table.
    Stain ΔR460 ΔR600
    Control Example 1 product Control Example 1 product
    Coffee 18.21 25.79 8.73 18.5
    Tea 3.2 15.99 2.55 21.02
    Banana -7.53 4.54 -10.36 5.11
    Mud/Soil 6.18 22.53 5.46 26.16
    Rust 11.42 20.69 6.81 22.14
    Shoe polish 15.15 21.12 11.2 15.8
    Dirty motor oil 6.14 10.23 5.84 8.67
    Lipstick 7.51 9.56 12.59 23.07
    Food grease 9.55 6.79 12.06 16.99
    Ink 10.5 11.57 10.56 14.01
    Gravy 26.9 35.56 20.01 23.3
    Mustard 9.93 11.97 -1.27 2.11

Claims (10)

  1. A textile fabric treatment process comprising the steps of:
    (i) allowing the fabrics to soak for at least 1 minute in a first aqueous liquor having a pH within the range of from 2 to 5, preferably from 3.5 to 4.5, and comprising
    (i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
    (i) (b) a surfactant,
    (ii) allowing the fabrics to soak for at least 1 minute in a second aqueous liquor comprising
    (ii) (a) a bleach
    (ii) (b) optionally a surfactant,
    (ii) (c) optionally an alkaline buffering agent, and
    (iii) rinsing the fabrics in water
    characterised in that the process is carried out by hand and is used for the removal from the fabric of stains selected from the group consisting of coffee, tea, banana, mud/soil, rust, shoe polish, dirty motor oil, lipstick, ink, gravy and mustard.
  2. A process as claimed in claim 1, in which the first aqueous liquor comprises:
    (i) (a) a water-soluble solid acid, optionally in admixture with a water-soluble salt thereof,
    (i) (b) a surfactant,
    (i) (c) an oxidising agent capable of masking and/or neutralising sulphurous odours,
    (i) (d) a bleach stable and effective at a pH of from 2 to 5, which is not the oxidising agent (i)(c),
    and the second aqueous liquor comprises:
    (ii) (a) a bleach
    (ii) (b) optionally a surfactant,
    (ii) (c) optionally an alkaline buffering agent,
    (ii) (d) optionally one or more builder and/or filler salts,
    (ii) (e) optionally a sequestrant bleach stabiliser,
    (ii) (f) optionally a fluorescer,
    (ii) (g) optionally one or more detergent enzymes.
  3. A process as claimed in claim 2, characterised in that the first aqueous liquor comprises as oxidising agent (i)(c) an alkali metal iodate.
  4. A process as claimed in claim 2 or claim 3, characterised in that the first aqueous liquor comprises as bleach (i)(d) an alkali metal dichlorocyanurate.
  5. A process as claimed in any preceding claim, characterised in that the water-soluble solid acid is an organic carboxylic acid having at least two carboxyl groups, preferably citric acid optionally in admixture with sodium citrate.
  6. A process as claimed in any preceding claim, characterised in that the concentration of the water-soluble acid and, if present, salt thereof in the first aqueous liquor is at least 1 g/l, preferably at least 3 g/l.
  7. A process as claimed in any preceding claim, characterised in that the second aqueous liquor comprises a bleach (ii) (a) selected from alkali metal dichlorocyanurate and N,N'-phthaloylaminoperoxycaproic acid.
  8. A process as claimed in any preceding claim, characterised in that the concentration of the bleach (ii)(a) in the second aqueous liquor is at least 0.05 g/l, preferably at least 0.2 g/l.
  9. A process as claimed in any preceding claim, characterised in that in step (i) the fabrics are allowed to soak for a period of from 1 to 60 minutes, preferably from 10 to 45 minutes.
  10. A process as claimed in any preceding claim, characterised in that in step (ii) the fabrics are allowed to soak for a period of from 1 to 60 minutes, preferably from 10 to 30 minutes.
EP00972835A 1999-11-26 2000-10-19 Process and product for the treatment of textile fabrics Expired - Lifetime EP1147254B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9928079.4A GB9928079D0 (en) 1999-11-26 1999-11-26 Process and product for the treatment of textile fabrics
GB9928079 1999-11-26
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 (en) 2001-10-24
EP1147254B1 true EP1147254B1 (en) 2006-06-21

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EP00972835A Expired - Lifetime EP1147254B1 (en) 1999-11-26 2000-10-19 Process and product for the treatment of textile fabrics

Country Status (8)

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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1593733A1 (en) * 2004-04-05 2005-11-09 The Procter & Gamble Company Liquid bleaching compositions
WO2005100529A1 (en) * 2004-04-05 2005-10-27 The Procter & Gamble Company Liquid bleaching compositions
EP2904085B1 (en) * 2012-10-04 2018-11-07 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 (en) * 1981-07-09 1985-06-14 花王株式会社 How to wash hospital clothing
DE3466013D1 (en) * 1983-10-03 1987-10-15 Akzo Nv Dosing unit comprising a detergent and/or bleaching agent
JPS6119866A (en) * 1984-06-29 1986-01-28 四国化成工業株式会社 Removal of yellowness of towel
DE4208106B4 (en) * 1991-03-20 2006-10-05 Clariant Finance (Bvi) Ltd. Pretreatment of textile fiber material
BR9910766A (en) * 1998-05-29 2001-10-02 Unilever Nv Process and product for the treatment of textile fabrics to improve, restore or maintain whiteness

Also Published As

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

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